C
CHA Zeolite Membrane
Tsuneji Sano
Department of Applied Chemistry, Hiroshima
University, Graduate School of Engineering,
Higashi-Hiroshima, Japan
Zeolites are a class of crystalline aluminosilicates
with highly regular and open microporous struc-
tures. More than 200 types of zeolite frameworks
have been identified by the Structure Commis-
sion of the International Zeolite Association.
Zeolite membranes combine the great advantages
of inorganic membranes, such as temperature
stability and resistance against solvents, with the
molecular sieving effect.
Zeolite chabazite (CHA, where the three char-
acters indicate the framework type) with Si/Al
ratios of 2 ~ 3 is known to possess a three-
dimensional pore system with large ellipsoidal
cages (6.7
10 Å) that are accessible via eight-
membered ring windows (3.8
3.8 Å). Figure 1
shows the framework structure of CHA zeolite
(IZA web. 2013). High-silica CHA (Si/Al ratio
> 5) has attracted great interest owing to its ther-
mal and acid stabilities, and hence, application of
this material to membrane has been widely inves-
tigated. The high-silica CHA zeolite membrane
can separate light-gas mixtures of CO/N2, CO2/
CH4, H2/CH4, and H2/n-C4H10 with notably
higher selectivity than that allowed by the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1-1
Knudsen mechanism (Kalipcilar et al. 2002).
The high-silica CHA zeolite membrane also
exhibits excellent dehydration performance for
water/alcohol mixtures (Hasegawa et al. 2010).
As the high-silica CHA zeolite has only been
synthesized using expensive N,N,N-trimethyl-1-
adamantammonium cation (TMAda+) as a
structure-directing agent (SDA). Very recently,
success was achieved in synthesizing high-silica
CHA zeolites with Si/Al ratios of 5–21 from FAU
zeolite using the benzyltrimethylammonium cat-
ion (BTMA+) instead of the expensive TMAda+.
The high-silica CHA zeolite synthesized by the
interzeolite conversion of FAU zeolite has supe-
rior acid stability (structural and compositional
stabilities) as compared to the CHA zeolite syn-
thesized using TMAda+ (Yamanaka et al. 2012).
Polycrystalline high-silica CHA zeolite mem-
branes can be formed by the secondary growth of
seed crystals on the outer surface of porous sup-
ports such as a porous a-alumina tube. Seed crys-
tals are applied to the outer surface of the support
tube by rubbing in order to implant the seed
crystals for nucleation. The secondary growth
solution with a chemical composition of
SiO2:0.03Al2O3:0.2BTMA:0.1NaCl:10H2O is
prepared from the dealuminated FAU,
BTMAOH, NaCl, and distilled water. Thereafter,
a hydrothermal reaction is carried out at 130  C
for 7 days using a Teflon ®-lined autoclave. After
cooling the autoclave, the support tube is recov-
ered, washed with distilled water, and dried
2 CHA Zeolite Membrane
overnight in air at room temperature. Finally, the
support tube is calcined at 550  C for 20 h.
Figure 2 shows scanning electron micrographs
(SEM) of the surface and cross section of the
CHA membrane on the a-alumina support
(Yamanaka et al. 2012). The high-silica
CHA-type zeolite membrane prepared on the
a-alumina tube is connected with the stainless
steel tube using heat shrink tubing, and the tube
is subsequently set in the conventional batch-type
pervaporation apparatus. An acetic acid aqueous
CHA Zeolite Membrane, Fig. 1 Framework structure
of CHA zeolite (IZA web. 2013)
CHA Zeolite Membrane, a b
Fig. 2 SEM images of (a)
outer surface and (b) cross
section of CHA zeolite
membrane (Reproduced
from Yamanaka
et al. (2012) with the
permission of Elsevier)
solution (50/50 wt%) is used as the feed at
75  C. The compositions of the feed and
the permeate are determined by FID-gas chroma-
tography (5MS capillary column). The perme-
ation flux and separation factor, a(H2O/
CH3COOH), are calculated from the following
equations:
Flux ðkg=m2 hÞ ¼
ðweight of permeate, kgÞ
ðmembrane area, m2 Þ
ðpermeation time, hÞ
(1)
Separation factor aðH2 O=CH3 COOHÞ
½CH2 O =CCH3 COOH Permeate
¼ (2)
½CH2 O =CCH3 COOH Feed
where the CCH3 COOH and CH2 O are the weight
fractions of acetic acid and water, respectively.
The permeate flux and separation factor,
a(H2O/CH3COOH), are 7.9 kg/m2 h and ca.
2500, respectively, and the membrane perfor-
mance is identical to that of commercially
available NaLTA zeolite membranes used for
the dehydration of alcohol solution (Sato
et al. 2008). The long-range time courses of
both the separation factor and the flux are listed
CHA
Al2O3 support
5 µm 5 µm
CHA Zeolite Membrane 3

CHA Zeolite Membrane, Table 1 Time course of References

CHA-type zeolite membrane performance for dehydration
of 50 wt% acetic acid aqueous solution at 75  C Hasegawa Y, Abe C, Nishioka M, Sato K, Nagase T,
(Reproduced from Yamanaka et al. (2012) with the per- Hanaoka T (2010) Formation of high flux CHA-type
mission of Elsevier) zeolite membranes and their application to the dehy-
Permeation dration of alcohol solutions. J Membr Sci 363:318–324
time/h a(H2O/CH3COOH) Flux/kg/m2 h International Zeolite Association Web site (2013) http://
1 2500 7.96 www.iza-online.org/
Kalipcilar H, Bowen TC, Noble RD, Falconer JL
22 2480 7.88 (2002) Synthesis and separation performance of
77 2500 7.91 SSZ-13 zeolite membranes on tubular supports.
125 2380 7.80 Chem Mater 14:3458–3464
170 2480 7.80 Sato K, Sugimoto K, Nakane T (2008) Preparation of
higher flux NaA zeolite membrane on asymmetric
porous support and permeation behavior at higher
temperatures up to 145  C in vapor permeation.
J Membr Sci 307:181–195
in Table 1 (Yamanaka et al. 2012). The CHA Yamanaka N, Itakura M, Kiyozumi Y, Ide Y, Sadakane M,
membrane prepared by the interzeolite conver- Sano T (2012) Acid stability evaluation of CHA-type
zeolites synthesized by interzeolite conversion of
sion of FAU zeolites has high potential for use in FAU-type zeolite and their membrane application for
the separation of water from acidic organic sol- dehydration of acetic acid aqueous solution. Micropo-
vents and is not limited to acetic acid. rous Mesoporous Mater 158:141–147
A
Aerobic Membrane Bioreactor
A. Achilli1 and R. W. Holloway2
1
Environmental Resources Engineering
Department, Humboldt State University, Arcata,
CA, USA
2
Department of Civil and Environmental
Engineering, Colorado School of Mines, Golden,
CO, USA
Synonyms
Cross-flow membrane bioreactor; Membrane
bioreactor; Microfiltration membrane bioreactor;
Submerged membrane bioreactor; Ultrafiltration
membrane bioreactor
Introduction
Aerobic membrane bioreactors (MBRs) are one
of the leading technologies to achieve sustain-
ability in wastewater treatment through reuse,
decentralization, and low energy consumption
(Fane and Fane 2005; Fawehinmi et al. 2005).
In aerobic MBRs, aerated activated sludge is
coupled with membrane process to remove
dissolved contaminants (carbon and ammonia)
and separate solids from the treated municipal
or industrial wastewater. Carbon is removed by
microorganisms that metabolize the carbon in the
presence of dissolved oxygen for microbial
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_7-1
growth and respiration (organic carbon reduced
to carbon dioxide). Ammonia is removed through
ammonia oxidation (nitrification). Nitrification is
a microbially mitigated reduction process that
occurs in an aquatic environment that contains
moderate to high concentrations of ammonia and
dissolved oxygen and low concentrations of
organic carbon.
In submerged MBRs (Fig. 1), microporous
(microfiltration (MF) or ultrafiltration
(UF) (▶ Ultrafiltration)) membranes are
immersed in a bioreactor, and water is filtered
(▶ Permeate) through the membranes using vac-
uum; suspended solids are retained in the system;
and high levels of treatment (including nutrient
removal) can be achieved (Judd 2006). The MBR
replaces the two-stage conventional activated
sludge process (biotreatment and clarification)
with a single, integrated process (▶ Wastewater
Treatment in Membrane Bioreactors). The
advantages of MBRs over conventional treatment
have been thoroughly reviewed (Stephenson
et al. 2000), and they include product consis-
tency, reduced footprint, reduced sludge produc-
tion, and nearly complete suspended solid
separation from the effluent. Additionally, MBR
effluent may be suitable for use as irrigation
water, as process water, or as a pretreatment for
potable reuse applications (▶ Membrane Biore-
actors for Reuse; ▶ Potable Water Production)
(Lawrence et al. 2002).
However, the establishment of membrane bio-
reactor technology (▶ Anaerobic Membrane
2 Aerobic Membrane Bioreactor
Aerobic Membrane
Bioreactor,
Fig. 1 Schematic Membrane
representation of a Channels
submerged aerobic MBR
system
Bioreactor; ▶ Attached Growth Membrane Bio-
reactor; ▶ Membrane Bioreactors (MBR) for
Plants; ▶ Submerged Membrane Bioreactor) has
been slower than expected because decision-
makers view MBRs as high risk and costly com-
pared to conventional technology (Judd 2006).
To date, MBRs have been used to treat municipal
and industrial wastewater where water reuse is
desired, a small footprint is required, or stringent
discharge standards exist (Kang et al. 2007; Yang
et al. 2006).
Current Limitations
One of the major limitations to widespread appli-
cation of MBR technologies is to control mem-
brane fouling with modest energy and chemical
input (▶ Irreversible Fouling; ▶ Reversible Foul-
ing) (Le-Clech et al. 2006). Membrane fouling
(▶ Biological Fouling; ▶ Cake Layer; ▶ Inor-
ganic Scaling) has been investigated from various
perspectives, including the causes, characteris-
tics, and mechanisms of fouling and methods, to
prevent or reduce membrane fouling (Achilli
et al. 2011; Judd 2005; Le-Clech et al. 2006;
Meng et al. 2009; Wang and Wu 2009). Fouling
markedly affects membrane cleaning (Membrane
cleaning, 369690) and replacement intervals, sys-
tem productivity, and membrane integrity; all of
which are factors that affect energy requirements
and costs (Judd 2006; Le-Clech et al. 2006).
Membrane
Cassette
Activated
Sludge
Product
Water
Membranes
Operation
In order to operate conventional MBRs at con-
stant flux, physical membrane-cleaning tech-
niques are utilized; they include air scouring,
backwashing, relaxation, or a combination of
the three, depending on the membrane configura-
tion (hollow fibers, flat sheet, or tubular). Air
scouring is required for submerged MBR config-
urations to gas lift fresh sludge through the mem-
brane bundle or cassette and to scour solids from
the membrane surface. During backwashing, per-
meate is pumped in the opposite direction
through the membrane, effectively removing
most of the reversible fouling (▶ Backwashing).
The efficiency of backwashing has been studied
in detail, and the key parameters have been found
to be frequency, duration, and intensity
(▶ Backwashing Frequency) (Bouhabila
et al. 2001; Psoch and Schiewer 2005, 2006).
During membrane relaxation, permeate suction
is stopped, and the back transport of foulants is
naturally enhanced as reversibly attached
foulants diffuse away from the membrane
surface.
Membrane backwashing and relaxation are
regularly used for tubular and hollow fiber mem-
branes to control fouling (Bouhabila et al. 2001;
Hong et al. 2002; Psoch and Schiewer 2005,
2006; Smith et al. 2005). This is not the case for
flat-sheet membranes that cannot be backwashed
due to their inability to withstand pressure in the
opposite direction of the operating flow; for this
Aerobic Membrane Bioreactor 3

reason, relaxation is used to control the fouling of microbial products (SMP) and bio-fouling in anaero-
these membranes (Le-Clech et al. 2006). Regard- bic membrane bioreactors. In: IWA specialized con-
ference on water environment
less of the membrane configuration, chemicals Hong SP, Bae TH, Tak TM, Hong S, Randall A (2002)
must be used at regular intervals to enhance phys- Fouling control in activated sludge submerged hollow
ical cleaning (Le-Clech et al. 2005). fiber membrane bioreactors. Desalination
143:219–228
Judd S (2005) Fouling control in submerged membrane
bioreactors. Water Sci Technol 51(6–7):27–34
Cross-References Judd S (2006) The MBR book: principles and applications
of membrane bioreactors in water and wastewater
▶ Anaerobic Membrane Bioreactor treatment. Elsevier Science, Oxford
Kang Y-T, Cho Y-H, Chung E-H (2007) Development of
▶ Attached Growth Membrane Bioreactor the wastewater reclamation and reusing system with a
▶ Backwashing submerged membrane bioreactor combined
▶ Backwashing Frequency bio-filtration. Desalination 202:68–76
▶ Biological Fouling Lawrence P, Adham S, Barro L (2002) Ensuring water
re-use projects succeed – institutional and technical
▶ Cake Layer issues for treated wastewater re-use. Desalination
▶ Inorganic Scaling 152:291–298
▶ Irreversible Fouling Le-Clech P, Fane A, Leslie G, Childress A (2005) MBR
▶ Membrane Bioreactor for Reuse focus: the operators’ perspective. Filtr Sep
42(5):20–23
▶ Membrane Bioreactor (MBR) Plants Le-Clech P, Chen V, Fane TAG (2006) Fouling in mem-
▶ Membrane Cleaning brane bioreactors used in wastewater treatment.
▶ Permeate J Membr Sci 284:17–53
▶ Potable Water Production Meng FG, Chae SR, Drews A, Kraume M, Shin HS, Yang
FL (2009) Recent advances in membrane bioreactors
▶ Reversible Fouling (MBRs): membrane fouling and membrane material.
▶ Submerged Membrane Bioreactor Water Res 43(6):1489–1512
▶ Ultrafiltration Psoch C, Schiewer S (2005) Critical flux aspect of air
▶ Wastewater Treatment in Membrane sparging and backflushing on membrane bioreactors.
Desalination 175:61–71
Bioreactors Psoch C, Schiewer S (2006) Resistance analysis for
enhanced wastewater membrane filtration. J Membr
Sci 280:284–297
References Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen H
(2005) Design of a generic control system for
optimising back flush durations in a submerged
Achilli A, Marchand EA, Childress AE membrane hybrid reactor. J Membr Sci 255:99–106
(2011) A performance evaluation of three membrane Stephenson T, Judd S, Jefferson B, Brindle K (2000)
bioreactor systems: aerobic, anaerobic, and attached- Membrane bioreactors for wastewater treatment.
growth. Water Sci Technol 63:2999–3005 IWA Publishing, London
Bouhabila EH, Ben-Aim R, Buisson H (2001) Fouling Wang ZW, Wu ZC (2009) A review of membrane fouling
characterisation in membrane bioreactors. Sep Purif in MBRs: characteristics and role of sludge cake
Technol 22–23:123–132 formed on membrane surfaces. Sep Sci Technol
Fane AG, Fane SA (2005) The role of membrane technol- 44(15):3571–3596
ogy in sustainable decentralized wastewater systems. Yang W, Cicek N, Ilg J (2006) State of the art of mem-
Water Sci Technol 51(10):317–325 brane bioreactors: worldwide research and commer-
Fawehinmi F, Lens P, Stephenson T, Rogalla F, Jefferson cial applications in north America. J Membr Sci
B (2005) The influence of operating conditions on 270:201–211
extracellular polymeric substances (EPS), soluble
A
Affinity Membranes
Francesca Militano and Lidietta Giorno
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, National
Research Council of Italy, Rende (CS), Calabria,
Italy
Introduction
Affinity separation methods rely on a “molecular
recognition” phenomenon between species.
A molecule, known as the ligand, is permanently
bounded onto an inert matrix and specifically
recognizes the molecule of interest, known as
the ligate, that can be separated. The ligand can
be a naturally occurring molecule, an engineered
macromolecule, or a synthetic molecule linked to
the matrix by covalent coupling. The ligand-
ligate interaction is selective and reversible,
enabling the separation and fine purification of
biological substances such as proteins, peptides,
and nucleic acids on the basis of its individual
chemical structure or biological function (Wilson
and Poole 2009).
Among the separation techniques based on the
affinity method, affinity chromatography is the
most widely used. Due to the limitation associ-
ated to the traditional affinity chromatography
with porous bead-packed columns (i.e., limited
flow rate by pore diffusion), the membrane-based
separation technique is gaining an increasing
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_8-1
importance. Indeed, affinity membranes combine
the specificity of affinity adsorption (of the com-
mon affinity resins) with the high productivity
associated with filtration membranes. They pro-
vide low pressure separation systems without
diffusional limitation, as the mass transfer is
mainly governed by convection (Klein 2000).
Microporous membranes, both in flat sheet and
hollow fiber configuration, coupled with biologi-
cal or biomimetic ligands have been used as
affinity membrane chromatography supports
(Zou et al. 2001).
Affinity Membrane Preparation
The realization of affinity membranes usually
involves three steps: (1) preparation of the basic
membrane, (2) activation (functionalization) of
the basic membrane, and (3) coupling of affinity
ligands to the activated membrane.
Membrane Material
The membrane materials should possess some
characteristics: (i) hydrophilicity to minimize
the nonspecific adsorption of bioactive species,
(ii) chemical and physical stability under harsh
conditions used during ligand coupling and
ligand-ligate complex formation, (iii) large sur-
face area relative to membrane volume,
(iv) biocompatibility when the membrane is
used for blood treatment, and (v) presence of
2 Affinity Membranes

Affinity Membranes, Table 1 Some commonly used activation agents for affinity membrane preparation
Activation agent Structure Functional groups of the basic membrane
Cyanogen bromide –OH
N C Br
Carbonyldiimidazole –OH, –NH2
O

N N
N N

2-Amino-4,6-trichloro-s-triazine –OH
Cl

N N

Cl N NH2
Glutaraldehyde –OH, –SH, –NH2
O O
Divinyl sulfone –OH, –SH
O CH2
S
H2C O
Epichlorohydrin –OH, NH2
O
Cl

functional groups required for the coupling of the
ligands (such as –OH, –NH, –SH, –COOH).
The commercially available materials used for
affinity membrane preparation include organic
(natural or synthetic polymer), inorganic, and
composite materials.
Among the first materials used for affinity
membrane preparation, cellulose and its deriva-
tives (regenerated cellulose, cellulose acetate)
were the most common. These present a hydro-
philic and biocompatible surface, low
nonspecific adsorption, and abundant reactive
hydroxyl groups that can be easily activated by
different strategies for the ligand coupling. To
improve the density of functional groups and
increase the mechanical strength, composite cel-
lulose membranes have been also prepared by
chemical grafting with acrylic polymers.
Another suitable membrane material is poly-
vinyl alcohol, thanks to its hydrophilicity and
biocompatibility. Like cellulose, it contains
hydroxyl groups that can be easily activated.
Polyamide and nylon have been also used for
the preparation of affinity membranes, thanks to
their good mechanical and chemical stability.
Nylon membranes have a low concentration of
amino groups to serve as functional groups for
ligand coupling. Also, due to the hydrophobic
surface, the membrane presents a high
nonspecific adsorption of biomolecules during
affinity separation process. Therefore, the hydro-
lysis of the membrane is generally performed to
increase the density of reactive groups and to
prevent electrostatic interaction with proteins.
To overcome these problems, composite nylon
membranes have been also prepared.
Other materials that have been used for affin-
ity membranes are poly(methyl methacrylate),
polysulfone and its derivative, polycaprolactam,
polyvinylidene difluoride, poly(ether-urethane-
urea), and inorganic materials such as glass.
Affinity Membranes 3

Affinity Membranes, Table 2 Some examples of the use of affinity membranes for isolation and purification of
biomolecules
Membrane Ligand Ligate Application
Cellulose and regenerated Cibacron Blue F3GA Alkaline phosphatase Purification
cellulose Protein A/G IgG Purification
Histidine Endotoxin Removal of
endotoxin
Poly(ethylene-co-vinyl Histidine IgG Purification
alcohol)
Nylon Cibacron Blue Glucose-6-phosphate Purification
dehydrogenase
Protein G IgG Purification
Histidine Endotoxin Removal of
endotoxin
Polyvinylidene difluoride Protein A IgG Purification
(PVDF)
Polysulfone (PS) Trypsin Trypsin inhibitor Purification
Iminodiacetic acid Histidine/tryptophan Purification
(IDA)
Glass IDA-Cu2+ Lysozyme, cytochrome c, Purification
ribonuclease A

Membrane Activation and Ligand Coupling
If the basic membrane does not possess the func-
tional groups for ligand coupling, it can be
activated.
In Table 1 are reported the commonly used
activation agents with respect to the functional
groups present on the basic membrane.
The coupling of the ligand directly on the
activated membranes may result in low binding
specificity due to the low steric availability
(in particular when the ligand is a small mole-
cule). This problem is generally overcome by the
introduction of a spacer molecule to the mem-
brane prior to attaching the ligand, improving the
ligand accessibility for the molecule to be sepa-
rated. Spacer arms are bifunctional molecules
able to react with both the membrane and ligand.
Affinity Ligands
Affinity ligands can be classified into biospecific
and pseudo-biospecific ligands (Klein 1991).
Biospecific ligands are biomolecules such as anti-
bodies, antigens, and proteins A and G that show
specificity for only one complementary
biomolecule.
Because of their selectivity, biomolecules
have been the most widely used affinity ligands
on affinity membrane separation technology. One
of the most common applications is the use of
immobilized monoclonal antibodies for
immunoaffinity separation. Another important
example is membranes with covalently coupled
protein A or protein G for immunoglobulin puri-
fication from plasma, serum, or cell culture
supernatants.
Although the biospecific ligands possess high
specificity for proteins, they have some limitation
for large-scale application due to their poor sta-
bility and high price.
The alternative approach to biospecific
ligands involves the use of pseudo-biospecific
ligands. These are usually molecules with higher
chemical and physical stability than biomole-
cules. Pseudo-biospecific ligands can be distin-
guished by biological (amino acids, specially
histidine, lysine, tryptophan) or non-biological
molecules (dyes, chelated metal ions).
The working principle of pseudo-biospecific
ligands relies on the complementarity of
4 Affinity Membranes
structural features of ligand and ligate rather than
on a biological function. Immobilized dyes have
been found to act as affinity ligands for a wide
variety of biological molecules. For example,
triazine-linked dyes have been used to mimic
coenzymes that bind a number of dehydroge-
nases, hexokinases, and alkaline phosphatases;
the reactive triazine groups can be linked to any
matrix containing hydroxyl groups by mixing the
two together. Cibacron Blue F3GA (a textile dye)
has been employed as ligand in affinity mem-
branes for the purification of over 80 enzymes
and proteins.
Another important example of pseudo-
biospecific affinity ligands is chelated metal
ions used for the purification of histidine-tagged
fusion proteins.
Molecular Imprinted Membranes
A different approach for the preparation of affin-
ity membranes is the use of molecularly
imprinted polymeric materials. These are pro-
duced by entrapping a template molecule (the
molecule to be separated) in a polymer matrix
during polymerization and subsequent extraction.
In this way, binding sites are introduced in the
polymer that are complementary in shape and
functionality to the target molecule.
Applications of Affinity Membranes
Affinity membranes are used for several different
applications such as purification of biomolecules,
removal of unwanted substances from biological
fluids, and also small-scale analytical
separations.
The most common application is the separa-
tion and purification of biomolecules and espe-
cially proteins for large-scale production.
In Table 2 are reported some typical examples
of their use for the separation and purification of
biomolecules.
References
Klein E (ed) (1991) Affinity membranes: their chemistry
and performance in adsorptive separation processes.
Wiley, New York
Klein E (2000) Affinity membranes: a 10-year review.
J Membr Sci 179:1–27
Wilson ID, Poole CF (2009) Handbook of methods and
instrumentation in separation science,
vol 1. Academic, Boston
Zou H, Luo Q, Zhou D (2001) Affinity membrane chro-
matography for the analysis and purification of pro-
teins. J Biochem Biophys Methods 49:199–240
A
Air Dehydration by Membrane
Technology
Wei Liu
Energy and Environmental Technology, Pacific
Northwest National Laboratory, Richland, WA,
USA
Synonym
Membrane air dehydration
Air dehydration refers to removal of moisture
from humid air and is also termed as air dehu-
midification and air drying. Due to the ubiquitous
presence of moisture in air, air dehydration rep-
resents one of the largest membrane applications.
Air dehydration through a membrane is essen-
tially a vapor-phase separation process (Fig. 1),
which can be carried out in two ways. In one way,
moisture in the feed air diffuses across the mem-
brane and is swept out of the membrane unit with
a sweep gas stream (Fig. 1a). In another way, the
permeated moisture is pulled away from the
membrane unit by vacuum (Fig. 1b).
In the sweeping process, degree of air dehu-
midification will be limited by moisture content
in the sweep gas and operation pressures, as
explained by the following equations:
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_11-1
Dp ¼ xF  pF  xS  pP > 0
x P  pP
xF >
pF
Low molar fraction of moisture in sweep gas
(xP), low permeate pressure (pP), and high feed
pressure (pF) favor for deep dehumidification,
i.e., allowing low moisture content in feed air
(xF).
If no sweep gas is used, the permeate pressure
has to be decreased by vacuum to obtain a posi-
tive partial pressure gradient of water vapor
across the membrane:
pP < x F  pF
Membrane dehydration is commonly used in
industries for removal of moisture from pressur-
ized air. In these applications, ambient air at
atmospheric pressure is often used as sweep gas.
Though moisture content (such as molar fraction)
in the sweep air may be the same as in the process
air, a significant partial pressure gradient of water
vapor can be managed due to high pressures in
the process air. For example, hollow fiber mem-
branes are used for drying of the air pressurized to
about 10 bar (Morgan et al. 1996). Air-sweep
dehumidification can also be found in some lab-
oratory membrane devices, such as Nafion mem-
brane tubes for moisture exchange (Ye and
LeVan 2003).
2 Air Dehydration by Membrane Technology

Air Dehydration by Membrane Technology, Fig. 1 Removal of moisture from humid air through a membrane

WATER
VAPOR

LOW
HUMID
HUMIDITY
AIR
DEHUMIDIFICATION AIR
1 UNIT

2 3 CONDENSER 4
“COMPRESSOR”

5 NON-CONDENSABLE
VACUUM
PUMP GAS

LIQUID LIQUID
RESERVOIR PUMP
LIQUID

Air Dehydration by Membrane Technology, Fig. 2 Process flow diagram of a membrane dehumidification system

When humid air is at low or atmospheric pres-
sures, using ambient air as a sweep stream is no
longer practical, and pulling vacuum in the per-
meate side becomes necessary. In this case, sev-
eral other pieces of equipment in addition to the
membrane separator are required to make an
integrated dehumidification system (Fig. 2).
Such a membrane dehumidifier has been recently
proposed and is still under development (Xing
et al. 2013). An array of membrane units can be
assembled together that the permeate sides of all
the membrane units are connected to one com-
mon vacuum line. The vacuum is generated by
the use of a vacuum pump or gas compressor. The
permeated moisture is compressed to a pressure
above water dew point at environmental temper-
ature so that water vapor is condensed into liquid-
phase water by rejecting heat of condensation
into environment. The condensed water is col-
lected in a reservoir. Water in the reservoir may
be discharged using a liquid pump, while residual
air – noncondensable gas – is discharged into
environment using a secondary vacuum pump.
References
Morgan WH, Bleikamp LK, Kalthod DG (1996) Hollow
fiber membrane dryer with internal sweep, US patent
no. 5,525,143
Xing R, Rao Y, TeGrotenhuis W, Canfield N, Zheng F,
Winiarski DW, Liu W (2013) Advanced thin zeolite/
metal flat sheet membrane for energy efficient air
dehumidification and conditioning. Chem Eng Sci
104:596–609
Ye X, LeVan MD (2003) Water transport properties of
Nafion membranes: part I. Single-tube membrane
module for air drying. J Membr Sci 221:147–161
A
Air Enrichment, by Polymeric
Magnetic Membranes
Anna Strzelewicz
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
The idea of using magnetic membranes for
enrichment of air by oxygen is based on the
observation that oxygen and nitrogen have quite
different magnetic properties, i.e., oxygen is
paramagnetic whereas nitrogen
diamagnetic. The oxygen molecule is paramag-
netic with a magnetic moment of
mO2 ¼ 2:73  1023 JT 1 : Magnetic susceptibil-
ity of nitrogen is equal to w ¼ 150:8  106
mol1 ¼ 2:5  1028 molecule1 which corre-
sponds only to m ¼ 2:5  1028 JT 1 in a mag-
netic field of 1 T, a value five orders of magnitude
smaller than the O2 magnetic moment (Morrish
1965; Borys et al. 2011).
Magnetic membranes are polymeric mem-
branes (ethyl cellulose (EC) or poly
(2,6-dimethyl-1,4-phenylene oxide) (PPO)) with
dispersed magnetic powder (ferrite, praseodym-
ium, and neodymium). The membranes are made
by casting of appropriate polymer solution with
dispersed magnetic powder in an external mag-
netic field of a specially designed coil (stable
magnetic field with range of induction
0–40 mT). Removed from Petri dish membranes
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_12-4
are dried in 40  C for at least 2 days and then are
stored in an exsiccator under the vacuum condi-
tions (p = 3 mmHg). Collection of permeation
quantities both for individual gases (O2, N2) and
for their mixture (air 21 %O2/79 % N2) is mea-
sured in experimental setup (Fig. 1).
The measurements are carried out in room
temperature for membranes with dispersed mag-
netic powder before and after magnetization in a
field magnet with magnetic induction about
2.5 T. The setup furnished with a gas chromato-
graph allows to measure the oxygen and the
nitrogen concentration in permeate. The main
part of the experimental setup is diffusive cham-
ber, where the membrane is put in the form of
disk. The setup is used for a low-pressure (from
0.1 to 1.0 MPa) analysis of gas permeation.
Transport coefficients can be calculated using
flow rate data and percentage of air enrichment.
The flow rate of the permeate can be recorded
using a flowmeter. Integration of flux with
respect to time allows to sketch a downstream
permeation curve. Typical plot of Qa(l,t) versus
time is presented in the Fig. 2.
Time-lag method and D1-D8 system allow to
get some insight into the nature of the considered
transport process. In papers (Strzelewicz and
Grzywna 2007, 2008; Rybak et al. 2009a, b,
2012; Grzywna et al. 2010) a concept of magnetic
membranes for air enrichment is explained. The
authors observed an increase in the oxygen flux
with respect to the nitrogen flux and the enrich-
ment in the oxygen content of the permeate up to
2 Air Enrichment, by Polymeric Magnetic Membranes

Air Enrichment, by
Polymeric Magnetic
Membranes,
Fig. 1 Scheme of the
experimental setup

Air Enrichment, by a
Q
Polymeric Magnetic point for checking
Membranes, oxygen content
stationary state
Fig. 2 Downstream
absorption permeation
curve
a
Q (I, t)

La(L) t

– C0 1
6

55.6 % for ethyl cellulose magnetic membranes.
Further permeation measurements done in
polyphenylene oxide (PPO) magnetic mem-
branes provided higher enrichments, up to
61.9 % (Table 1).
The transport of the molecules through the
magnetic membranes can be modeled by a diffu-
sion with a position-dependent diffusion coeffi-
cient. Such a diffusion coefficient reflects the
changes in the membrane composition along the
permeation axis. One can observe on the scan-
ning electron microscope photograph (Borys
et al. 2011) of the magnetic membrane cross
section that the feed side of the membrane is
composed of a pure polymer while the output
side consists of the polymer with dispersed mag-
netic granules. When the magnetic field is too
strong, then magnetic aggregates are created,
which influence the permeation of gases.
Detailed analysis of the available data and
microscopy images allowed to arrive four con-
clusions (Borys et al. 2011):
Air Enrichment, by Polymeric Magnetic Membranes
Air Enrichment, by Polymeric Magnetic Membranes, Table 1 Air enrichment for various membranes (Strzelewicz
and Grzywna 2007)
Membrane B[mT]
EC + 1.38 g Nd 0.79
EC + 1.49 g Nd 1.25
PPO + 1.80 g Nd 1.70
PPO + 1.80 g Nd 2.70
1. There are magnetic channels formed around
the magnetic granules.
2. The channels provide high permeability
“highways” for the diffusion of permeating
molecules.
3. The oxygen molecules, due to their paramag-
netic properties, stick to these “highways” for
a longer time than nitrogen, which is probably
based on the interaction with the Weiss molec-
ular field of the permanent magnet.
4. The magnetic field induces aggregation
between oxygen and nitrogen which enhances
the transport of both nitrogen and oxygen by
prolonging their residence in the channel.
The method of air enrichment by magnetic
membranes seems to be effective and efficient.
References
Borys P, Pawelek K, Grzywna ZJ (2011) On the magnetic
channels in polymer membranes. Phys Chem Chem
Phys 13:17122–17129
3
Oxygen content in permeate [%]
40.7  1.1
43.8  1.1
54.1  1.4
61.9  1.5
Grzywna ZJ, Rybak A, Strzelewicz A (2010) Air enrich-
ment by polymeric magnetic membrane. In:
Yampolskii Y, Freeman B (eds) Membrane gas sepa-
ration. Wiley, Chichester, pp 159–182
Morrish AH (1965) The physical principles of magnetism,
1st edn. Wiley, New York
Rybak A, Krasowska M, Strzelewicz A, Grzywna ZJ
(2009a) “Smoluchowski type” equations for modelling
of air separation by membranes with various structure.
Acta Phys Pol B 40:1447–1454
Rybak A, Grzywna ZJ, Kaszuwara W (2009b) On the air
enrichment by polymer magnetic membranes.
J Membr Sci 336:79–85
Rybak A, Strzelewicz A, Krasowska M, Dudek G,
Grzywna ZJ (2012) On the air separation process by
magnetic membranes influence of various parameters.
Sep Sci Technol 47:1395–1404
Strzelewicz A, Grzywna ZJ (2007) Studies on the air
membrane separation in the presence of magnetic
field. J Membr Sci 294:60–67
Strzelewicz A, Grzywna ZJ (2008) On the permeation
time lag for different transport equations by Frisch
method. J Membr Sci 322:460–465
A
Air Separation
A. F. Ismail1,2 and M. H. D. Othman1,2
1
Advanced Membrane Technology Research
Centre (AMTEC), Universiti Teknologi
Malaysia, Skudai, Johor, Malaysia
2
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia
Air separation technology is used for the produc-
tion of oxygen, nitrogen, and rare gases that are
present in air such as argon and neon. There are
two fundamental approaches to air separation,
which are cryogenic and non-cryogenic pro-
cesses. The cryogenic process which is carried
out in distillation column has the capability to
deliver large and high purities of products,
while the non-cryogenic which is based on
absorption and membrane technologies is more
suitable for on-site production, which is most
common for small and medium throughputs.
Membrane technology for air separation has
developed rapidly in recent years. Polymeric and
ceramic membranes have been used commer-
cially for oxygen production. Polymeric mem-
branes operate based on the difference in rates
of diffusion of oxygen and nitrogen through a
membrane. Due to the smaller size of the oxygen
molecule, most membrane materials are more
permeable to oxygen than to nitrogen. Materials
such as polysulfone or acetate membranes make
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_13-2
it possible to permeable oxygen five times than of
nitrogen. Membrane units capable of producing
nearly 600 tonnes per day nitrogen have been
built (Castle 2002). A major benefit of polymeric
membrane separation is the simple, continuous
nature of the process and operation at near
ambient conditions (Smith and Klosek 2001);
however, the low separation factor of two to six
limits the polymeric membrane to produce
oxygen-enriched air rather than pure oxygen
(Zhu et al. 2008).
Production of pure oxygen from air can be
achieved by using ceramic membrane system at
elevated temperatures, typically in the range of
800–900  C (Hashim et al. 2011). The oxygen
transporting through this type of membrane is in
the form of oxygen ions instead of oxygen mole-
cules; therefore, the pure oxygen is obtained.
Enormous efforts have been directed to ceramic
membranes with mixed ionic–electronic
conducting (MIEC) characteristics. Among
them, perovskite-type (ABO3) ceramic mem-
branes exhibit the highest oxygen permeability
due to their high ionic and electronic conductiv-
ity. The perovskite oxide based on
La1 xAxCo1 yFeyO3 d achieved very high oxy-
gen permeation fluxes as reported by Teraoka
et al. (1985).
Interestingly, the oxygen separation from air
in MIEC ceramic membrane system requires nei-
ther electrodes nor an external circuit to operate.
As depicted in Fig. 1, the electronic conductivity
itself performs as an internal short circuit that
2 Air Separation

Air Separation,
Pressurized Oxygen
Fig. 1 Schematic ½O 2 + 2e − → O2−
air feed depleted air
representation of the
oxygen transport in MIEC MIEC
ceramic membrane ceramic
O2 - e- O2- e-
membrane

Oxygen rich O2− → ½O 2 + 2e − Sweep gas

stream

involves oxygen partial pressure gradient. The References

oxygen molecule permeates from the high oxy-
gen partial pressure side to the low oxygen partial
pressure side, while the overall charge neutrality
is maintained by counterbalancing the flux of
electrons (Liu and Gavalas 2005). Several indus-
trial gas companies are working on developing
ceramic membranes for oxygen separation from
air at high temperatures. Air Products and
Chemicals has developed an ion transport mem-
brane (ITM) system, which is based on patented,
high-temperature ceramic membranes for the
production of oxygen from air separation
(Hashim et al. 2011). Praxair is also working on
oxygen-conducting ceramic membrane systems
that are specially designed to separate oxygen
from air at elevated temperature environment
(Hashim et al. 2011).
Castle WF (2002) Air separation and liquefaction: recent
developments and prospects for the beginning of the
new millennium. Int J Refrig 25:158–172
Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep-
aration from air using ceramic-based membrane tech-
nology for sustainable fuel production and power
generation. Renew Sustain Energy Rev 15:1284–1293
Liu S, Gavalas GR (2005) Oxygen selective ceramic hol-
low fiber membranes. J Membr Sci 246:103–108
Smith AR, Klosek J (2001) A review of air separation
technologies and their integration with energy conver-
sion processes. Fuel Process Technol 70:115–134
Teraoka Y, Zhang HM, Furukawa S, Yamazoe N (1985)
Oxygen permeation through perovskite-type oxides.
Chem Lett 167:1743–1746
Zhu X, Sun S, He Y, Cong Y, Yang W (2008) New
concept on air separation. J Membr Sci 323:221–224
A
Alamine 336
Karel Friess
Department of Physical Chemistry, University of
Chemistry and Technology Prague, Prague,
Czech Republic
Synonyms
Alamine 3365; Alamine 336S; Farmin08;
Octanamine; Tricaprylamine; Tridioctylamine;
Tri-n-octylamine; Tri-n-caprylylamine;
Trioctylamine
The IUPAC systematic name is N,N-dioctyl-1-
octanamine (Fig. 1). Alamine 336 is colorless
(C24H51N, CAS Reg. No. 1116-76-3) or light
yellow liquid (mixture of Tri C8-10 Alkyl
Amines, C27H57N – CAS Reg. No. 57176-40-6,
produced by Cognis Corp., now part of BASF). If
released to air, estimated vapor pressure is about
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_15-1
0.007 Pa at 25  C. It is moderately toxic by
ingestion and intraperitoneal routes; when heated
to decomposition, it emits toxic vapors of NOx
(Zhu et al. 2012). Manufacturing of Alamine
336 is possible by catalytic amination of octanol
(Li et al. 2011) or by catalytic hydrogenation of
caprylonitrile (Lazier 1940). It is used as the
extractant for reactor fuel processing (Moyer
and McDowell 1981), for dye identification
(Puttemans et al. 1982), and for metal adsorption
(Tasker et al. 2003) and recovery from diluted
aqueous solutions (Kislik 2012; Coca et al. 1990;
Sun and Lee 2011). Mixtures of Alamine
336 with meta-xylene can be successfully applied
for extraction metal ions from their strong acidic
aqueous chloride solutions (Sayar et al. 2007).
Alamine 336 can be also used for specific extrac-
tions in biotechnology, e.g., separation of carbox-
ylic acids (Tamada et al. 1990; Yordanov and
Boyadzhiev 2004), and in supported liquid mem-
branes (San Román et al. 2010; Dżygiel and
Wieczorek 2010) (Table 1).
2 Alamine 336

Alamine 336,
Fig. 1 Schematic structure
of Alamine 336
N

Alamine 336, Table 1 Properties of Alamine 336 (Steele et al. 1996)

Molar mass 353.67 g
mol 1

Melting point 34.6 C

Boiling point 363.5 C
Density 0.818 g
cm 3 at 25  C
Viscosity 7.86
10 2
Pa
s at 34.6  C
Surface tension 3.48
10 2
N
m 1 at 34.6  C
Constant pressure heat capacity of liquid 750.8 J
mol 1
K 1 at 25  C
Solubility in chloroform 0.1 g
cm 3 at 25  C
Solubility in water 0.050 mg
dm 3 at 25  C

Cross-References Kislik VS (2012) Examples of application of solvent

extraction techniques in chemical, radiochemical, bio-
chemical, pharmaceutical, analytical separations, and
▶ Extraction wastewater treatment. In: Kislik VS (ed) Solvent
▶ Metal Adsorption and Recovery extraction – classical and novel approaches. Elsevier,
▶ Supported Liquid Membranes Amsterdam, pp 185–314
▶ Tertiary Amine Lazier WA (1940) Process for catalytic hydrogenation of
higher aliphatic nitriles. US Patent 2225059
▶ Water Treatment Li Y, Li Q, Zhi L, Zhang M (2011) Catalytic amination of
octanol for synthesis of trioctylamine and catalyst
characterization. Catal Lett 141:1635–1642
Moyer BA, McDowell WJ (1981) Factors influencing
References phase disengagement rates in solvent extraction sys-
tems employing tertiary amine extractants. Sep Sci
ChemSpider (CSID). http://www.chemspider.com/ Technol 16:1261–1289
Chemical-Structure.13591.html. Accessed 1 June National Institute of Standards and Technology (NIST)
2012 database. http://webbook.nist.gov. Accessed 1 June
Coca J, Díez FV, Morís MA (1990) Solvent extraction of 2012
molybdenum and tungsten by Alamine 336 and Puttemans ML, Dryon L, Massart DL (1982) Evaluation
DEHPA. Hydrometallurgy 25:125–135 of thin layer-, paper- and high performance liquid
Dżygiel P, Wieczorek PP (2010) Supported liquid mem- chromatography for the identification of dyes
branes and their modifications: definition, classifica- extracted as ion-pairs with tri-n-octylamine. J Assoc
tion, theory, stability, application and perspectives. In: Off Anal Chem 65:730–736
Kislik VS (ed) Liquid membranes. Elsevier, Amster- San Román MF, Bringas E, Ibañez R, Ortiz I (2010)
dam, pp 73–140 Liquid membrane technology: fundamentals and
Alamine 336
review of its applications. J Chem Technol Biotechnol
85:2–10
Sayar NA, Filiz M, Sayar AA (2007) Extraction of Zn
(II) from aqueous hydrochloric acid solutions into
Alamine 336–m-xylene systems. Modeling consider-
ations to predict optimum operational conditions.
Hydrometallurgy 86:27–36
Steele WV, Chirico RD, Knipmeyer SE, Nguyen A, Smith
NK, Tasker IR (1996) Thermodynamic properties and
ideal-gas enthalpies of formation for cyclohexene,
phthalan (2,5-dihydrobenzo-3,4-furan), isoxazole,
octylamine, dioctylamine, trioctylamine, phenyl
isocyanate, and 1,4,5,6-tetrahydropyrimidine. J Chem
Eng Data 41:1269-1284
3
Sun PP, Lee MS (2011) Separation of Pt(IV) and Pd
(II) from the loaded Alamine 336 by stripping. Hydro-
metallurgy 109:181–184
Tamada JA, Kertes AS, King CJ (1990) Extraction of
carboxylic acids with amine extractants. Ind Eng
Chem Res 29:1319–1326
Tasker PA, Plieger PG, West LC (2003) Metal complexes
for hydrometallurgy and extraction. In: McCleverty
JA, Meyer TJ (eds) Comprehensive coordination
chemistry II, vol 9. Elsevier: Oxford, UK,. pp 759–808
Yordanov B, Boyadzhiev L (2004) Pertraction of citric
acid by means of emulsion liquid membranes.
J Membr Sci 238:191–197
Zhu Y, Cao M, Ma X, Xu C, Wang X, Ren L, Hu C (2012)
Dalton Trans 41(10):2935–40
A
Alcohol and Water Separation
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Cross-linked poly(vinyl alcohol) (PVA) compos-
ite membranes have been used in commercial PV
plants for dehydration of ethanol beyond the
azeotrope. However aqueous ethanol solutions
that can be produced by bio-fermentation are
dilute (about 10 wt.%). Therefore, if ethanol/
water-selective membranes with high efficiency
can be prepared, the distillation process in the
first stage to obtain an azeotrope can be replaced
ethanol-/water-selective membrane which is very
advantageous for reduction of energy cost. There
are fewer reports on ethanol-/water-selective
membranes compared with those of water-/
ethanol-selective membranes. One reason why
the development of efficient high-performance
ethanol-/water-selective membranes is difficult
can be attributed to the fact that ethanol has a
larger molecular size than water and must be
preferentially permeated through the membrane.
In fact, permeation and separation in a
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_16-2
pervaporation (PV) process through dense mem-
branes are based on the solution-diffusion mech-
anism (Binding et al. 1961; Aptel et al. 1974).
Therefore, when it is required that ethanol mole-
cules with larger molecular size preferentially
permeate from an aqueous ethanol solution, it
cannot be expected to be separated by the diffu-
sion process. Consequently, only a difference of
solubility selectivity in the solution process in
which both ethanol and water components are
dissolved can contribute to the separation.
Figure 1 shows the ethanol concentration in the
permeate through a poly(dimethylsiloxane)
(PDMS) membrane during PV and that sorbed
into a PDMS membrane. These results support
the hypothesis that the difference in the solubility
of the permeants contributes to the ethanol/water
selectivity. PDMS membranes show high etha-
nol/water selectivity, but their mechanical
strength is weak, and it is difficult to prepare
thin membranes from PDMS. In order to obtain
both ethanol/water selectivity and mechanical
strength, graft copolymers composed of PDMS
macromonomer and vinyl monomers were
synthesized.
Graft copolymer membranes, which were
either ethanol or water selective, were prepared
by copolymerization of a dimethylsiloxane
2 Alcohol and Water Separation

100 100

ve
cur

EtOH in membrane (wt%)

80 80
EtOH in permeate (wt%)

ibrium
equl
id
or-liqu
vap
60 60

40 40

20 20

0
0 20 40 60 80 100
EtOH in feed solution (wt%)

Alcohol and Water Separation, Fig. 1 Permeation and Alcohol and Water Separation, Fig. 2 Effects of the
separation characteristics of aqueous ethanol solutions DMS content on the normalized permeation rate (○) and
through a PDMS membrane during PV separation factor (●) through the PMMA-g-PDMS mem-
brane during PV. Feed: aqueous solution of 10 wt.%
ethanol. Dashed line is the feed composition

(DMS) macromonomer with methyl methacry- the determination of the percolation transition of
late (MMA) (Miyata et al. 1995, 1996). Two the PDMS phase at a DMS content of about
glass transition temperatures (Tg) were observed 40 mol%. These results suggest that the continu-
at about 120  C and 127  C in the graft copol- ity of the PDMS phases in the microphase-
ymer membranes. Transmission electron separated PMMA-g-PDMS membranes directly
micrograph (TEM) demonstrated that the affects their ethanol/water selectivity for aqueous
PMMA-g-PDMS membranes showed ethanol solutions (Miyata et al. 1995, 1996).
microphase-separated structures. When an aque- In Table 1, the performance of the ethanol-/
ous solution of 10 wt.% ethanol was permeated water-selective polymer membranes is com-
through the PMMA-g-PDMS membranes by PV, pared. As can be seen in this Table, the addition
the ethanol concentration in the permeate and the of PFA-g-PDMS to the PTMSP membrane in PV
permeation rate increased drastically with the was very effective, the application of TDEV
DMS content in the copolymer. In particular, at method to the membrane separation technique
a DMS content of less than 40 mol%, water was also very interesting for the enhancement of
permeates preferentially from an aqueous solu- the ethanol/water selectivity for the ethanol/
tion of 10 wt.% ethanol, whereas membranes water mixtures, and in particular the application
with more than about 40 mol% of DMS are eth- of porous PDMS membrane to temperature-
anol/water selective, as shown in Fig. 2. The difference controlled evapomeation (TDEV)
change in the ethanol/water selectivity of the (Uragami 1998, 2005, 2006a, b, 2008, 2010,
PMMA-g-PDMS membranes can be explained 2011; Uragami and Shinomiya 1991, 1992;
by a microphase-separated polymer structure Uragami and Tanaka 1991, 1993, 1994; Uragami
using Maxwell’s model and a combined model et al. 2002; Uragami and Morikawa 1989) was a
consisting of both parallel and series expressions. very excellent performance for the ethanol/water
Furthermore, image processing of TEMs allowed mixtures.
Alcohol and Water Separation 3

Alcohol and Water Separation, Table 1 Performance of ethanol-/water-selective membranes

Feed Applied NPRa
(wt temperature aEtOH/ (kgmm
Membrane %) Method ( C) H2O (m2h) 1) References
PDMS 7 PV 25 11.8 2.1 Eustache and Histi (1981)
PTMSP 7 PV 25 11.2 1.1 Ishihara et al. (1986)
PTMSP 10 PV 30 12 4.5 Masuda et al. (1986)
PEA-g-PDMS/ 10 PV 40 20 24.1 Uragami et al. (2000);
PTMSPb Uragami and Shinomiya
(1991)
PPP-g-PDMS 7.28 PV 30 22.5 5.5 Nagase et al. (1989)
PSt-g-PhdFDA (7.6/ 8 PV 30 45.9 0.6 Ishihara and Matsui (1987)
12.4)
TFE/i-OcVE/C18VE 15 PV 50 7.13 5 Kashiwagi et al. (1988)
terpolymer (50/25/25)
Modified silicone 10 PV 40 3.65 11 Uragami and Shinomiya
(1991)
Modified silicone 10 TDEV 30/40 19.3 16.6 Miyata et al. (1996)
PDMS 10 PV 40 7.44 6.4 Miyata et al. (1995, 1996)
PDMS 10 TDEV 30/40 85.7 0.9 Uragami and
Shinomiya (1992)
PMMA-g-PDMS 10 PV 40 7.1 4.8 Miyata et al. (1996)
(34/66)
PMMA-g-PDMS 10 PV 40 8 5.1 Miyata et al. (1999a)
(27/73)
PMMA-g-PDMS 10 PV 40 6.8 3.5 Miyata et al. (1999b)
(38/62)c
PTMST 10 TDEV 0/40 77.5 38 Uragami (2010)
Porous PDMS 10 TDEV 0.5 23.1 1,250 Uragami (2008)
a
Normalized permeation rate
b
PFA-g-PDMS is 0.2 wt.%
c
Annealing is 120  C, 2 h

References Ishihara K, Matsui K (1987) Ethanol permselective poly-

Aptel P, Cuny J, Jozenfonvice J, Morel G, Neel J (1974)
Liquid transport through membranes prepared by
grafting of polar monomer onto poly(tetrafluor-
oethylene) films. II. Some factors determining
pervaporation rate and selectivity. J Appl Polym Sci
18:365
Binding RC, Lee RJ, Jennings JF, Mertic EC (1961) Sep-
aration of liquid mixtures by pervaporation. Ind Eng
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Eustache H, Histi G (1981) Separation of aqueous organic
mixtures by pervaporation and analysis by mass spec-
trometry or a coupled gas chromatograph-mass spec-
trometer. J Membr Sci 8:105
mer membranes 3. Pervaporation of ethanol water
mixture through composite membranes composited
of styrene fluoroalkyl acrylate graft copolymers and
cross-linked polydimethylsiloxane membrane. J Appl
Polym Sci 34:437
Ishihara K, Nagase Y, Matsui K (1986) Pervaporation of
alcohol/water mixtures through poly
[1-(trimethylsilyl)-1-propyne] membrane. Macromol
Chem Rapid Commun 7:43
Kashiwagi T, Okabe K, Okita K (1988) Separation of
ethanol from ethanol/water mixtures by plasma-
polymerized membranes from silicone compounds.
J Membr Sci 36:353
4 Alcohol and Water Separation
Masuda T, Tang B-Z, Higashimura T (1986) Ethanol-
water separation by pervaporation through
substituted-polyacetylene membranes. Polym J 18:565
Miyata T, Takagi T, Kadota T, Uragami T (1995) Char-
acteristics of permeation and separation for aqueous
ethanol solutions through methyl methacrylate-
dimethylsiloxane graft copolymer membranes.
Macromol Chem Phys 196:1211
Miyata T, Takagi T, Uragami T (1996) Microphase sepa-
ration in graft copolymer membranes with pendant
oligodimethylsiloxanes and their permselectivity for
aqueous ethanol solutions. Macromolecules 29:7787
Miyata T, Obata S, Uragami T (1999a) Morphological
effects of microphase separation on the
permselectivity for aqueous ethanol solutions of
block and graft copolymer membranes containing
poly(dimethylsiloxane). Macromolecules 32:3712
Miyata T, Obata S, Uragami T (1999b) Annealing effect
of microphase-separated membranes containing poly
(dimethylsiloxane) on their permselectivity for aque-
ous ethanol solutions. Macromolecules 32:8465
Nagase Y, Mori S, Matsui K (1989) Chemical modifica-
tion of poly(substituted-acetylene). 4. Pervaporation of
organic liquid water mixture through poly(1-phenyl-1-
propylene) polydimethylsiloxane graft copolymer
membrane. J Appl Polym Sci 37:1259
Uragami T (1993) Separation of aqueous organic liquid
solutions through polymer membranes. Desalination
90:325
Uragami T (1998) Structures and properties of membranes
from polysaccharide derivatives. In: Dumitriu S (ed)
Polysaccharide, structural diversity and functional ver-
satility. Marcer Dekker, New York/Basel/Hong Kong,
pp 887–924
Uragami T (2005) Structures and functionalities of mem-
branes from polysaccharide derivatives. In: Dumitriu
S (ed) Polysaccharide, structural diversity and func-
tional versatility, 2nd edn. Marcer Dekker, New York,
pp 1087–1122
Uragami T (2006a) Separation materials derived from
chitin and chitosan. In: Uragami T, Tokura S (eds)
Material science of chitin and chitosan. KODANSHA,
Springer, Berlin/Heiderberg/New York/Tokyo,
pp 113–163
Uragami T (2006b) Polymer membranes for separation of
organic liquid mixtures. In: Yampolskii Y, Pinau I,
Freeman BD (eds) Materials science of membranes
for gas and vapor separation. Wiley, Chichester,
pp 355–372
Uragami T (2008) Structural design of polymer mem-
branes for concentration of bio-ethanol. Polym
J 40:485
Uragami T (2010) Selective membranes for purification
and separation of organic liquid mixtures. In: Drioli E,
Giorno L (eds) Comprehensive membrane science and
engineering, vol 2, Membrane operations in molecular
separations. Elsevier, Amsterdam/Boston/Heidelberg/
London/New York/Oxford/Paris/San Diego/San
Francisco/Singapore/Sydney/Tokyo, pp 273–324
Uragami T (2011) Concentration of bio-ethanol through
cellulose ester membranes during temperature-
difference controlled evapomeation. Mater Sci Appl
2:1499
Uragami T (2012) Concentration of bio-ethanol through
poly[1-(trimethylsilyl)-1-propyne] membranes during
temperature-difference controlled evapomeation. 11th
World Filtration Congress & Exhibition, p 313
Uragami T, Morikawa T (1989) Permeation of ethanol
through polydimethyl siloxane membranes using
temperature-difference in membrane process of the
evapomeation method. Makromol Chem Rapid
Commun 10:287
Uragami T, Morikawa T (1992) Permeation and separa-
tion characteristics of alcohol-water mixtures through
dimethylsiloxane membrane by pervaporation and
evapomeation. J Appl Polym Sci 44:2009
Uragami T, Shinomiya H (1991) Concentration of aque-
ous alcoholic solutions through a modified silicone
rubber membrane by pervaporation and evapomeation.
Makromol Chem 192:2293
Uragami T, Tanaka Y (1991) Method of separating liquid
component from a solution containing two or more
liquid component. European Patent 0,346,739
Uragami T, Shinomiya H (1992) Concentration of aque-
ous dimethyl sulfoxide solutions through a chitosan
membrane by permeation with a temperature differ-
ence. J Membr Sci J Membr Sci 7:183
Uragami T, Tanaka Y (1993) Method of separating liquid
component from a solution containing two or more
liquid component. U.S. Patent 5,271,846
Uragami T, Tanaka Y (1994) Separation method for
mixed solutions. Japanese Patent 1,906,854
Uragami T, Doi T, Miyata T (1999) Control of
permselectivity with surface modifications of poly
[1-(trimethylsilyl)-1-propyne] membranes. Inter
J Adhes Adhes 19:405
Uragami T, Doi T, Miyata T (2000) Pervaporation prop-
erty of surface modified poly[1-(trimethylsilyl)-
1propyne] membranes. In: Pinnau I, Freeman BD
(eds) Membrane formation and modification, ACS
Symposium Series 744. American Chemical Society,
Washington, DC, pp 263–279
Uragami T, Tanaka Y, Nishida S (2002) Permeation and
separation under high temperature and high pressure
for ethanol/water vapors through cross-linked
quaternized chitosan composite membranes. Desalina-
tion 147:449
A
Alkaline Fuel Cells (AFCs)
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Alkaline fuel cell (AFC) is a fuel cell type which
utilizes alkaline electrolyte, usually potassium
hydroxide. It consumes hydrogen and oxygen
producing only water, heat, and electricity.
Depending on a concentration of potassium
hydroxide, AFC can operate at temperatures
between 60
C and 250
C. The fuel cell reactions
are as follows:
Anode : H2 þ 2OH ⇄ 2H2 O þ 2e
Cathode : 1⁄2 O2 þ 2e þ 2H2 O ⇄ 2OH
Overall reaction : H2 þ 1⁄2 O2 ⇄ H2 O
The main ionic charge carriers are OH ions
which mitigate from the cathode to the anode.
Water is formed at the anode side and has to be
removed from the system in order to prevent
KOH dilution. The AFC has improved cathode
performance compared to acidic fuel cells due to
more favorable oxygen reduction reaction kinet-
ics. For this reason, AFC can achieve higher
efficiency, i.e., higher voltage at comparable cur-
rent densities than other fuel cell types. It has
very long operating life time, e.g., 15,000 h
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_17-4
have been demonstrated (Cifrain and Kordesch
2003). Furthermore, alkaline conditions allow
application of nonprecious metal catalysts
which could reduce significantly the material
costs of this fuel cell. One of major disadvantages
of AFC is its low CO2 tolerance due to formation
of carbonates according to:
CO2 þ 2OH ⇄ CO3 2 þ H2 O
The carbonates have low solubility in strong alka-
line environments forming crystals, capable of
blocking of electrolyte pathways. The low CO2
tolerance and the application of liquid electrolyte
are two main hurdles for the broader commercial-
ization of these systems. However, due to its high
efficiency and high power density, AFC found
applications in aerospace industry, e.g., they
were employed on the Apollo missions as well
as on the Space Shuttle orbitals. For other exam-
ples of developed AFC systems, please see
Cifrain and Kordesch (2003) and G€ulzow (2012).
Hydrogen and oxygen gases in the AFC are
separated by a membrane. Usually permeable
membranes also called diaphragms have been
used (G€ulzow 2012). A common diaphragm
material up to 1980s was asbestos which due to
health and environmental concerns is nowadays
abandoned. Alternative materials are different
polymer materials like porous polyethylene
plates, nonwoven polypropylene, and similar.
Potassium hydroxide electrolyte wets the
2 Alkaline Fuel Cells (AFCs)
diaphragm pores in order to ensure its ionic con-
ductivity. For a good fuel cell performance, the
electrolyte resistance induced by diaphragm has
to be minimized. This resistance is influenced by
the thickness of the diaphragm material, its pore
size and tortuosity, and the KOH concentration.
Since liquid electrolyte causes some practical
problems in AFC usage, new developments go
into direction of alkaline polymer electrolyte
membranes which, in addition to separation, pos-
sesses ionic conductivity in the absence of liquid
electrolyte. Currently there is no long-term stable
membrane functioning without a liquid electro-
lyte phase.
References
Cifrain M, Kordesch K (2003) Hydrogen/oxygen (Air)
fuel cells with alkaline electrolytes. In: Vielstich W,
Gasteiger HA, Lamm A (eds) Handbook of fuel cells-
fundamentals, technology and applications,
vol 1, Fundamentals and survey of systems. Wiley,
Chichester, pp 267–280
G€
ulzow E (2012) Alkaline fuel cells. In: Stolten D,
Emonts B (eds) Fuel cell science and engineering:
materials, processes, systems and technology,
vol 1. Wiley-VCH, Weinheim, pp 97–129
A
Alumina Membranes
Bo Wang
Department of Chemical Engineering, Imperial
College London, London, UK
Alumina membranes are membranes made of
high-purity (mostly >97 %) aluminum oxides
(alumina). They belong to the categories of
ceramic membranes and in most cases,
microfiltration and ultrafiltration membranes.
Pure alumina membranes are predominant in all
kinds of commercial ceramic membranes, and
most other commercial ceramic membranes, if
using other materials as the separation coating,
are based on alumina membrane support.
Advantages and Disadvantages
Alumina membranes are chemically inert and
mechanically strong, and also thermally stable,
therefore they can be used under very harsh con-
ditions such as aggressive chemical environments
and elevated temperatures, making them versatile
in various industrial processes. Their strong
mechanical properties allow them to be operated
under high pressures and high feed flow rates to
achieve high productivity and to tolerate high
solid contents in the feed.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_18-1
The high fabrication cost is a major obstacle for
alumina membranes to expand its market share.
Although alumina is widely available, the com-
plicated fabrication process and high energy con-
sumption for sintering lift significantly the total
membrane cost, making it about one order of
magnitude higher than its polymeric counterparts.
However, because of much longer lifetimes and
higher fluxes of alumina membranes, the long-
term operating cost of alumina membrane plants
is comparable with polymeric membrane plants,
no mention there are many scenarios in which
only alumina/ceramic membranes can be used.
Membrane Designs and Fabrication
Most alumina membranes use asymmetric mem-
brane architectures. Coarse alumina particles are
used for the supporting layer to provide mechan-
ical strength, and the transport resistance in this
layer is usually low due to its big pore size; fine
alumina particles are coated on top of the support
to form a thin separating layer to reach desired
pore sizes and high fluxes; and depending on the
pore size difference between the top and the
supporting layer, one or few transition layers
might be used between the top and supporting
layers to avoid coating defects and to increase
adhesion between layers.
2 Alumina Membranes
Alumina membranes may adopt a tubular
shape, plate shape, or monolithic multichannel
design. The latest is the most commonly used
design in industry because it provides higher
membrane area per unit volume, therefore reduces
the size of the separation plant and operating
costs. Some commercial products can achieve an
area to volume ratio of 800 m2/m3 with the mono-
lithic design, which is comparable with spiral
wound polymeric membrane modules.
Fabrication of alumina membranes usually
involves several forming and sintering steps due
to their multilayer asymmetric membrane archi-
tectures, and the total production process is often
longer than 1 week. The supporting layer can be
formed by extrusion (for tubular or monolith
designs) or by pressing (for plate or disk designs),
followed by partial sintering at a high temperature
(up to 1600  C) to achieve a high strength and
porous structures. Transition layers and the top
layer then can be coated on the support, also
followed by sintering after each coating.
Depending on the pore size, two types of alumina
could be used for the top layer coating: for
microfiltration membranes whose pore size is
larger than 100 nm, a-alumina is used; for ultra-
filtration membranes whose pore size is smaller
than 100 nm, g-alumina or a mixture of a and g
types are often used.
There are also other fabrication techniques that
can produce unique alumina membranes, for
example, the anodic alumina membranes that
have straight cylindrical pores and asymmetric
alumina membranes made by single-step phase
inversion/sintering methods. These membranes
have shown good potential in filtration but have
not been widely accepted as a feasible replace-
ment of conventional alumina membranes yet.
Applications
Alumina membranes are widely used in water and
wastewater treatment, pharmaceuticals, food
processing, chemical processing, and others. Pro-
duction of drinking water and wastewater treat-
ment are the most important applications, which
occupy about half of the market share of alumina
membranes. The stable pore structure of alumina
membranes even under high pressures and abra-
sive conditions guarantees constant quality of the
permeate and makes it preferable in the scenarios
where quality control is crucial, such as in drink-
ing water production and food industry. And the
natural hydrophilic surface of alumina offers bet-
ter anti-fouling property than polymeric mem-
branes; therefore its usage in wastewater
treatment is expanding rapidly; and in some
other heavy-duty filtration processes such as
treating produced water from oil fields, alumina
membranes have been dominant.
Further Reading
Benfer S, Árki P, Tomandl G (2004) Ceramic membranes
for filtration applications – preparation and characteri-
zation. Adv Eng Mater 6(7):495–500
Lehman SG, Adham S, Liu L (2008) Performance of new
generation ceramic membranes using hybrid coagula-
tion pretreatment. J Environ Eng Manage 18(4):257–60
Ebrahimi M, Willershausen D, Ashaghi KS, Engel L,
Placido L, Mund P, Bolduan P, Czermak P (2010)
Investigations on the use of different ceramic mem-
branes for efficient oil-field produced water treatment.
Desalination 250(3):991–996
A
Anion-Exchange Membrane (AEM)
Mitsuru Higa
Graduate School of Science and Engineering,
Yamaguchi University, Ube, Yamaguchi, Japan
The anion-exchange membrane (AEM) is a
thin film with anion-exchange groups
(positively charged groups) and permeates anions
selectively. AEMs are classified according to the
species of the ion-exchange groups and materials
constituting the membrane and microstructure.
Anion-exchange groups are positively charged
groups: primary, secondary, and tertiary amino
groups, quaternary ammonium groups, tertiary
sulfonium groups, quaternary phosphonium
groups, cobalticinum groups, and other groups
that provide a positive fixed charge in aqueous
or mixed water and organic solvent solutions.
Based on the materials constituting membranes,
AEMs can be classified as (i) organic mem-
branes, (ii) inorganic membranes, and (iii) com-
posite membranes of inorganic ion exchangers
and organic polymers. AEMs are also classified
into two types by their microstructure: heteroge-
neous and homogeneous. Heterogeneous AEMs
consist of finely powdered anion exchanger and
an inert binder polymer. Various methods have
been reported for preparing homogeneous AEMs.
A typical example of a hydrocarbon AEMs is a
copolymer membrane composed of styrene and
divinylbenzene with benzyltrimethylammonium
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_23-1
groups. These membranes will be prepared, for
example, by the reaction of trimethylamine with a
copolymer membrane prepared from
chloromethylstyrene and divinylbenzene or by
alkylation with alkyl halide of a copolymer mem-
brane prepared from vinylpyridine and
divinylbenzene.
Though AEMs have been used in many fields,
most are used in electrodialysis, separation of
electrolysis, and solid polymer electrolytes for
fuel cells. The properties required depend on the
intended application of AEMs. Generally
required properties are (1) low electrical resis-
tance, (2) high transport number of anions,
(3) low diffusion coefficient of electrolytes,
(4) low osmotic water and low electroosmotic
water, (5) antifouling properties, (6) mechanical
strength, (7) dimensional stability, (8) high chem-
ical stability and durability, and (9) low cost (Sata
2004).
AEMs with low sulfate ion permeability have
been industrially used to prevent precipitation of
calcium sulfate in the AEMs and electrodialyzer.
A nitrate ion permselective AEM has been devel-
oped and has contributed to human health
because the concentrations of nitrate ions are
greatly increased in groundwater. To prepare
these functionalized AEMs, ordinary AEMs are
modified by suitable chemical or physical
methods. For example, most commercially avail-
able homogeneous AEMs are mainly cross-
linked with divinylbenzene. When the contents
of divinylbenzene increase or compact layers are
2 Anion-Exchange Membrane (AEM)
formed on the AEMs, the pore size of the mem-
brane decreases and the transport number of sul-
fate ions, which are bulky relative to chloride
ions, decreases.
Fouling of separation membranes is a com-
mon problem. AEMs are fouled by ionic mate-
rials of medium molecular weight such as ionic
surfactants having the charge opposite to the
fixed charged of the membrane. Almost all of
organic foulants in many effluent streams have
negative charges; hence, fouling of AEMs due to
deposition and/or adsorption of the foulants on/in
the AEM is one of the serious problems in their
applications. The pore size of the AEM is gener-
ally recognized to be about 1 nm; therefore, ions
of medium molecular weight permeate with dif-
ficulty through the membrane. Consequently, the
fouling can lead to an unacceptably high stack
resistance and replacement of membranes in an
electrodialysis system due to clogging of the
membrane pores with the medium molecular
weight ions. To alleviate the problem of organic
fouling, there are basically two methods on the
membrane side: first, to increase the pore size of
the membrane to allow easy permeation of large
ionic materials and, second, to prevent penetra-
tion of the materials into the membrane at the
membrane surfaces. There are two methods to
prevent penetration of large organic materials
into the membrane matrix: forming a thin
charged layer opposite in sign to the
ion-exchange groups of the membrane or forming
a very thin and dense layer on the membrane
surfaces.
Reference
Sata T (2004) Ion exchange membrane. The Royal Society
of Chemistry, Cambridge
A
Antoine Equation
Denis Roizard
Laboratoire Réactions et Génie des Procédés,
CNRS- Université de Lorraine, Nancy, France
Synonyms
Vapor Pressure-Temperature Relationship
History
Until the mid-nineteenth century, the prediction
of the saturated vapor pressure of a liquid mixture
or even of a pure liquid in relation with the
temperature was not accurate despite the phe-
nomena being studied long before the Middle
ages. The Antoine equation, which solves this
problem for pure components, is due to a French
engineer (Louis Charles Antoine, 1825–1897)
and was first published in “Annales de Physique
et de Chimie” in 1891 (Antoine 1891). Antoine
introduced an equation able to predict the vapor
pressure of pure liquids (vaporization) and solids
(sublimation). It is worth noting that this equation
is still widely used today because of its accuracy.
Wisniak (2001) has recently reviewed the histor-
ical development of the vapor pressure equations
from Dalton to Antoine.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_26-1
Phenomenon
The vapor pressure over a liquid is due to the
thermodynamic equilibrium between the gas
and the liquid states of the component, which
depends on the cohesive forces linking the mole-
cules. In a closed cell, the vapor pressure of a pure
component is a nonlinear relation of the temper-
ature: the more the component is volatile, the
more the vapor pressure is high.
Antoine Equation
For a given pure component in a closed cell, it
calculates the saturated vapor pressure P (mmHg)
with the temperature T (
C) as follows:
log10 P ¼ A  B=ðT þ CÞ (1)
with A, B, and C being the Antoine coefficients,
in mmHg and
C units, which are component-
specific constants; e.g., for water : A = 8.07131;
B = 1730.63 and C = 233.426 in the tempera-
ture range 1–99
C.
Other forms of the Antoine equation can be
deduced:
P ¼ 10ðAB=ðTþCÞÞ (2)
2 Antoine Equation

Antoine Equation, 180000

Fig. 1 Curves of P(sat) H2O
versus temperature; range 160000
50–150
C calculated with
the Antoine equation 600
140000
ZOOM
120000 400 0–100°C

P mmHg
100000 200

80000 00
100

60000

40000

20000

0
0 100 200 300 400
T °C

T ¼ B=ðA  log10 PÞ  C (3) assuming a temperature-independent heat of

vaporization.
These equations fit very well for experimental
vapor pressure data.
It is worth noting that the Antoine equation
Antoine Coefficients
can also be used at high pressure or near the
critical point. Indeed, for each component, two
Two systems of units can be used, either based on
sets of parameters can be used according to the
temperature and pressure, respectively, in
C and
considered temperature range, i.e., either up to
in mmHg or on K and Pa (SI system). Note that
the normal boiling point or from normal boiling
for historic reasons, the Antoine coefficients are
point to the critical point; in this last range, the
still normally given based on the CGS system.
Clausius-Clapeyron relation (Reid 1990) does
Conversion from the historical system unit to the
not apply properly. In the case of pure water, in
SI one can be made easily:
the temperature range 99–374
C, the dedicated
Antoine coefficients are A = 8.140191,
– B coefficient is the same in both systems;
B = 1810.94, and C = 244.485.
– To get A coefficient in SI, add 2.124903 to the
The extension (Wagner 1973) of the Antoine
historical A; this value corresponds the pres-
equation has been worked out to cover with a
sure unit modification, i.e., to log10 (101325/
single set of parameters the whole temperature
760).
range going from the critical point to the triple
– For C coefficient, subtract 273.15 to take into
point. This expression is required when compu-
account the modification of the
tational techniques must be used.
temperature unit.
On the other hand, a simplified equation using
only two parameters was known to evaluate the
The Antoine coefficients have been tabulated
vapor pressure; it was the August equation in
for most of pure compounds. They can be
which the parameter C is set to zero, thus
obtained from various sources, including web
Antoine Equation 3

Antoine Equation, Table 1 Example calculation of P(sat) H2O; range 50–150
C

T
C log10 (P) P mmHg T
C log10 (P) P mmHg
50 1.9652012 92.30 100 2.8832575 764.29
60 2.1732982 149.04 110 3.0320002 1076.47
70 2.3676788 233.17 120 3.1745848 1494.81
80 2.5496558 354.53 130 3.3093227 2038.56
90 2.7203796 525.27 140 3.4368443 2734.29
100 2.8808629 760.09 150 3.5577142 3611.72
A = 8.07131 B = 1730.63 C = 233.426 A = 8.140191 B = 1810.94 C = 244.485

access Data banks of Antoine Coefficients ▶ Clausius Clapeyron Equation

(visited June 2013). ▶ Vapor Pressure

Example Calculation References

This calculation has been done for water with the
coefficients: A = 8.07131, B = 1730.63, and
C = 233.426. The temperature validity range is
from 1
C to100
C.
– At T = 50
C: log10 (P) = 8.07131–1730.63/
(50 + 233.426) = 1.9652
– Hence, P(sat) H2O = 92 mmHg
The results shown in Fig. 1 and Table 1 corre-
spond to water vapor pressure calculated with the
respective sets of parameters of each domain with
the Eq. 1. The discontinuity at 100
C can be seen
in the Table 1.
Cross-References
▶ August Equation
Antoine C (1891) Annales de Physique et de Chimie 22:
281; ibid, Annales de Physique et de Chimie
(1892) 26: 426; Comptes Rendus Acad Sci (Paris)
(1888) 107: 1143
Data banks of Antoine Coefficients (visited June 2013)
http://webbook.nist.gov/ – http://booksite.elsevier.
com/9780080966595/content/Appendices/Appendix
%20C.pdf (free download) – http://www.eqi.ethz.ch/
fmi/xsl/eqi/eqi_property_details_en.xsl?node_id=
983 (directory for Physical Properties Sources) – -
Vapor-Liquid Equilibrium Data Collection,
DECHEMA Chemistry Data Series, Jurgen Gmehling
et al. (Frankfurt)
Reid CE (1990) Chemical thermodynamics. McGraw-
Hill, New York, p 73
Wagner W (1973) New vapour pressure measurements for
argon and nitrogen and an new method for establishing
rational vapour pressure equations. Cryogenics
13(8):470–482
Wisniak J (2001) Historical development of the vapor
pressure equation from Dalton to Antoine. J Phase
Equilib 22–6:622–630. doi:10.1007/s11669-001-
0026-x1143
A
Aptamers
Thomas Schäfer
Institute for Polymer Materials (Polymat),
University of the Basque Country (UPV/EHU),
Donostia-San Sebastián, Spain
Aptamers (from Latin aptus, to fit) are artificial
ligands binding with high affinity and specificity
to their cognate target, selected through a
Darwinian-like evolution method referred to as
SELEX. Aptamers generally consist of structured
single-strand nucleic acid molecules such as
RNA and ssDNA; however, dsDNA and peptide
aptamers have been described as well (Colas
et al. 1996; Patel et al. 1997).
Aptamers can be selected against virtually any
target and under nonphysiological conditions
because no animal host is required. Hitherto,
aptamers were selected against a broad range of
target molecules, such as amino acids, peptides,
proteins, drugs, organic and inorganic molecules,
or even whole cells, with affinities often compa-
rable to those of monoclonal antibodies.
The binding proprieties of aptamers are due to
the formation of specific aptamer-target com-
plexes stabilized by non-covalent interactions.
The latter are a combination of van der Waals
forces, hydrogen bonds, and electrostatic interac-
tions. Binding of an aptamer to its cognate target
can trigger an adaptive folding in which the target
promotes and stabilizes the secondary and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_27-3
tertiary structures of aptamers. The dynamic con-
formations of free aptamers, consisting of labile
knots, loops, and stems, turn into stable architec-
tures within the aptamer-target complexes where
noncanonical base pairing along with
intermolecular interactions creates unique bind-
ing pockets. Hence, along with a remarkable
affinity, aptamers are generally characterized by
high specificity. One of the most noteworthy
examples is the anti-theophylline aptamer which
can discriminate between theophylline and caf-
feine, two related molecules that only differ by a
methyl group of the imidazole ring, having about
11,000 times higher affinity for the former. Sim-
ilarly, aptamers have been reported to discrimi-
nate between enantiomers, macromolecules,
proteins, and whole cells.
Apart from their high affinity and specificity,
aptamers possess unique chemical and biochem-
ical characteristics which clearly set them apart
from other receptors. For example, aptamers are
exceptionally stable: they may undergo denatur-
ation, but the process is fully reversible within
minutes; hence, temperature changes or long-
term storage does not affect their functionality.
Furthermore, the well-known chemistry of
aptamers allows for site-directed chemical mod-
ifications and competitive production costs. New
functional groups can be introduced a
priori – within the SELEX process – using mod-
ified nucleic acid libraries or a posteriori modify-
ing a selected DNA/RNA through chemical
synthesis. While the first approach relies on the
2 Aptamers
compatibility of the modification adopted with
the enzymatic amplification necessary for selec-
tion, the latter approach is streamlined by detailed
knowledge of the structure of both the aptamer
and the aptamer-target complex. Since their first
appearance in the early 1990s, aptamers have
received constantly increasing attention,
reflected in their use as diagnostic reagents and
therapeutic compounds.
References
Colas P, Cohen B, Jessen T, Grishina I, McCoy J, Brent
R (1996) Genetic selection of peptide aptamers that
recognize and inhibit cyclin-dependent kinase
2. Nature 380(6574):548–550
Patel DJ, Suri AK, Jiang F, Jiang L, Fan P, Kumar RA,
Nonin S (1997) Structure, recognition and adaptive
binding in RNA aptamer complexes. J Mol Biol
272(5):645–664
A
Aptamer Membrane
Functionalization
Thomas Schäfer
Institute for Polymer Materials (Polymat),
University of the Basque Country (UPV/EHU),
Donostia-San Sebastián, Spain
Aptamer Membrane Functionalization. Aptamers
can be incorporated into adequate porous mem-
brane structures in order to obtain stimulus-
responsive membranes whose permeability is
modulated via a molecular recognition event.
The concept relies on the fact that aptamers can
recognize very specifically a molecular target,
upon which a significant conformational change
can occur if the aptamer is designed accordingly.
In this sense, aptamer-modified membranes fol-
low the concept “structure determines separa-
tion.” The stimulus-responsive membranes so
obtained therefore do not require a bulk stimulus,
such as a change in temperature or pH, which
makes them particularly interesting for being
employed in biomedical separations or
DNA-based nanodevices (Bhattacharyya
et al. 2013). Incorporating the aptamer into an
adequate porous structure, the aptamer conforma-
tional change upon target recognition can give rise
to a hindered pore flow, modulating in this way
the overall membrane permeability. Aptamer-
target interactions can be highly specific, target
concentration dependent, and do not involve the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_28-1
formation of chemical bonds but are physical. As a
consequence, membranes functionalized with
aptamers change their permeability depending on
the target concentration and in a reversible manner.
Figure 1 depicts the concept of a membrane pore
functionalized with a DNA-aptamer hairpin struc-
ture which changes its conformation upon a molec-
ular stimulus such as adenosine 50 -monophosphate
(AMP). In the absence of the target AMP, the
aptamer-functionalized membrane pores remain
open and the membrane permeability maximum.
Upon interaction with AMP, the aptamer undergoes
a conformational change which significantly
reduces the pore flow and, hence, overall membrane
permeability.
For the conformational change to take effect,
the pore diameter needs to be of the same order of
magnitude. Therefore, mesoporous structures are
preferably employed that furthermore possess a
high degree of isoporosity. Aptamer-modulated
pore flow has been thoroughly studied for
mesoporous particles that are used as controlled
delivery devices (Özalp and Schäfer 2011). Fig-
ure 2 shows the immobilization strategy for mod-
ifying mesoporous silica particles with aptamers
and Fig. 3 the concept of how such an aptamer can
serve as a reversibly opening “lid” in order to
liberate cargo molecules upon target recognition
(here: ATP).
A key parameter for the functioning of
aptamer-functionalized membranes is the fine-
tuning of the pore size within which the aptamer
conformational change takes place. Pores too
2 Aptamer Membrane Functionalization

Aptamer Membrane Functionalization, Fig. 1 Scheme of a stimulus-responsive aptamer-functionalized membrane

c
a

3. Amino functionalized
Aptamer

100 nm 10 nm HN

b 120 O

100 2. GMBS crosslinker

O
80
Intensity

N
O
60

40
S
1. Thiol Addition
20 via silanization

0 Si
O O
150 160 170 180 190 200 210 220 O
Average Size (nm) Silica Surface

Aptamer Membrane Functionalization, Fig. 2 Mesoporous particles (a), their size distribution (b), and the
functionalization of mesoporous silica with an aptamer (c)

large would not result in any aptamer-modulated
permeability, while pores too narrow would hin-
der the aptamer from freely changing its confor-
mation. It could be shown that the thickness
change of a DNA-aptamer hairpin film amounts
up to about 2 nm upon interaction with the target
(Serrano-Santos et al. 2012). Hence, mesoporous
structures with a pore diameter between 2 and
3 nm have been found to be a suitable base mate-
rial for aptamer-functionalized particles and mem-
branes (Özalp and Schäfer 2011).
Aptamer Membrane Functionalization 3

Aptamer Membrane Functionalization, change upon target recognition (b), and function to release
Fig. 3 Sequence of a DNA-aptamer hairpin that binds in a reversible, specific, and concentration-dependent fash-
selectively to ATP (a), scheme of its conformational ion cargo molecules (c)

References Özalp VC, Schäfer T (2011) Aptamer-based switchable

Bhattacharyya D, Schäfer T, Wickramasinghe RR, Daunert
S (eds) (2013) Responsive membranes and materials.
Wiley, Hoboken
nanovalves for stimuli-responsive drug delivery.
Chem Eur J 11:9893–9896
Serrano-Santos MB, Llobet E, Özalp VC, Schäfer T (2012)
Characterization of structural changes in aptamer films
for controlled release nanodevices. Chem Commun
48:10087–10089
A
Aptamer Screening
Thomas Schäfer
Institute for Polymer Materials (Polymat),
University of the Basque Country (UPV/EHU),
Donostia-San Sebastián, Spain
Aptamer screening or selection, also called sys-
tematic evolution of ligands by exponential
enrichment (SELEX), is a combinatorial chemis-
try method by which aptamers (single-stranded
DNA or RNA) are selected. SELEX is an evolu-
tionary method driven by the binding of oligonu-
cleotide sequences to a specific target based on
their particular tridimentional structure, which
confers high affinity and specificity. The selec-
tion process starts with a random oligonucleotide
library consisting of a random region flanked by
fixed primer regions required for PCR amplifica-
tion. The random region confers outstanding var-
iability, derived from the number of possible
sequences in the library.
The variability of the library can be calculated
with the expression 4n, where 4 is the number of
possibilities at each position (A, T, C, or G) and
n is the length of the random region. SELEX
allows the screening of oligonucleotide libraries
against a given target (i.e., protein, small
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_29-3
molecules, or even whole cells) by an iterative
process that involves (i) library/target interaction,
(ii) selection of the sequences that bind to the
target and removal of no binders, (iii) enrichment
of the selected sequences by PCR, and (iv) after
several screening rounds, cloning and sequencing
to identify individual sequences. Finally, bioin-
formatic analysis is required to determine the
most promising motifs or sequences. Next, the
candidate sequences are evaluated to confirm
their binding capability. SELEX technology
could be compared to antibody production; how-
ever, SELEX offers interesting features that over-
come some limitations of the antibody
production, such as fast in vitro performance, no
need for cells or animals, ease of selection under
physiological or nonphysiological conditions, no
limitation for target selection, and batch-to-batch
reproducibility.
Since the first report of SELEX in 1992 by two
independent groups (Tuerk and Gold 1990;
Ellington and Szostak1990), several modifica-
tions of the standard method have been reported
to improve its performance. Nowadays, a signif-
icant number of aptamers have been selected and
used as recognition molecules for environmental,
food, diagnosis, and therapeutic applications
(Fig. 1).
2 Aptamer Screening

Aptamer Screening,
Library Design by regions
Fig. 1
fixed random fixed Cloning, Sequencing
and Bioinformatics

Library
Interaction
Library/Target
Target

iteration
Selection of Target
Binders

Removal of
no binders

Enrichment of
selected binders

References Tuerk C, Gold L (1990) Systematic evolution of ligands

by exponential enrichment: RNA ligands to bacterio-
Ellington AD, Szostak W (1990) In vitro selection of RNA phage T4 DNA polymerase. Science 249:505–510
molecules that bind specific ligands. Nature
346:818–822
A
Aquaporins (AQPs) or Water
Channels
Fabio Bazzarelli and Lidietta Giorno
Institute on Membrane Technology, ITM,
National Research Council of Italy, Rende (CS),
Calabria, Italy
Aquaporins (AQPs) or water channels are a
family of integral membrane proteins that form
hydrophilic pores in the cellular membrane. They
are involved in the water transport through the
membrane.
All cells depend on their ability to maintain
water homeostasis. This is achieved through the
action of aquaporins, membrane-bound water
channels that facilitate water flow across cellular
membrane along osmotic gradients, while
excluding the passage of ions and protons. It is
required for maintenance of the membrane poten-
tial and intracellular pH. As with any membrane
transport facilitator, aquaporins have evolved to
be highly selective for their transported substrate
without binding water so strongly that transport is
inhibited. On the basis of their selectivity,
aquaporins can be divided into two groups: the
ordinary aquaporins, permeable to water only,
and aquaglyceroporins which also permit trans-
port of small solutes such as glycerol and urea.
A number of other compounds have also been
reported to be transported through aquaporins,
including CO2, NH3, and arsenite (Kreida and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_30-1
Tornroth-Horsefield 2015). AQPs are transmem-
brane channels; thus the ability of a molecule to
cross an AQP channel depends on its own char-
acteristics (size, polarity, charge) and on the fea-
tures of the AQP involved (Di Giorgio
et al. 2014). They have a similar basic structure;
AQPs are monomers of about 30 kDa and, in
general, contain six membrane-spanning helical
segments and two shorter helical segments that
do not span the entire membrane. The AQPs
generally form stable tetramers in membranes,
although each monomer contains a separate
water pore. High-resolution structural data show
that the membrane-spanning helical domains sur-
round cytoplasmic and extracellular vestibules
that are connected by a narrow aqueous pore.
Structural data and molecular dynamics simula-
tions suggest that water molecules move through
this narrow aqueous pore and that steric and elec-
trostatic factors are responsible for the water
selectivity of AQPs. The pore is less constricted
in the aquaglyceroporins than in the water-
selective AQPs (diameter of 3.4 Å versus 2.8 Å,
respectively) and is lined by more hydrophobic
residues (Papadopoulos and Verkman 2013). An
important property of aquaporin-mediated water
transport is its ability to be regulated in response
to cellular or environmental signals. This is
achieved by controlling water transport at the
individual protein level through a conformational
change, so-called gating, or by altering the
aquaporin density of a particular membrane.
These proteins are present in all kingdoms of
2 Aquaporins (AQPs) or Water Channels
life, demonstrating their central role in
maintaining normal physiology of all organisms.
The first member of this family, AQP1, was iden-
tified in erythrocytes in 1991. This discovery led
to homology cloning of hundreds of AQPs homo-
logues from throughout the animal and plant
kingdoms, as well as from lower organisms.
In humans there have been identified
13 aquaporins (AQP0–12) with specific organ,
tissue, and cellular localization. Thus, different
members of the AQPs family are expected to
function in virtually all physiological processes
that involve water transport across the
membrane.
The AQPs are expressed in many cell types
involved in fluid transport, including epithelia
and endothelia in the kidney, lung, exocrine
glands, eyes, and gastrointestinal tract. However,
aquaporins are also expressed in cells that do not
have an obvious role in fluid transport, such as
erythrocytes and some leukocytes, adipocytes,
and muscle. In addition, these are also expressed
in astrocytes throughout the central nervous sys-
tem and in supportive cells. Aquaporins have
been linked to a number of pathological condi-
tions, including brain edema, renal disease, obe-
sity, and cancer, raising their attractiveness as
drug targets.
Given the key role played by aquaporins in the
kidney, for recovering water permeated together
with other ions and molecules through the first
part of the glomerulus, they have been investi-
gated for developing biohybrid membranes able
to desalinate seawater. The biohybrid membranes
containing aquaporins showed very high water
selectivity and permeability. Technological chal-
lenges for productive application include
biohybrid membrane preparation on a large
scale, aquaporin stability under operating condi-
tions or during membrane module cleaning, and
maintenance operation. Development of syn-
thetic water channels mimicking aquaporins is a
new strategy under investigation. Highly selec-
tive and permeable water channels are very inter-
esting for the development of seawater
desalination plant operating with very low energy
input.
References
Di Giorgio J, Soto G, Alleva K, Jozefkowicz C,
Amodeo G, Muschietti JP, Ayub ND (2014) Prediction
of aquaporin function by integrating evolutionary and
functional analyses. J Membr Biol 247:107–125
Kreida S, Tornroth-Horsefield S (2015) Structural insights
into aquaporin selectivity and regulation. Curr Opin
Struct Biol 33:126–134
Papadopoulos MC, Verkman AS (2013) Aquaporin water
channels in the nervous system. Nat Rev Neurosci
14:265–277
A
Atomic Force Microscopy (AFM)
Nidal Hilal and Daniel Johnson
Centre for Water Advanced Technologies and
Environmental Research (CWATER), College
of Engineering, Swansea University, Swansea,
Wales, UK
The atomic force microscope is a versatile tool
increasingly used for the physical characteriza-
tion of surfaces and is of great interest for the
visualization and analysis of process surfaces
including those of membranes used for filtration.
It is capable of resolving features from the
micrometer down to the subnanometer scale and
can operate in air and liquid environments,
allowing membranes to be studied in environ-
ments matching those encountered during their
operation (Hilal et al. 2004; Hilal and Johnson
2010), which allows assessment of effects of, for
instance, pH, ionic strength, and effects of addi-
tives on membrane structure, a feature not avail-
able with other high resolution imaging
applications. In addition, the surface needs no
special preparation, providing it remains clear
of unwanted contamination, and does not need
to be electrically conductive, limitations found
with some imaging techniques.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_34-1
The AFM consists of a sharpened probe
mounted at the end of a flexible cantilever. The
tip of the probe is then used to “feel” the under-
lying membrane surface, producing a three-
dimensional map of the sample topography.
There are three basic imaging modes: contact
mode, where the tip maintains constant contact
with the surface, while feedback loops adjust its
height to maintain cantilever deflection and
hence force; tapping mode, where the cantilever
is vibrated close to the resonant frequency and
intermittently contacts the surface with decreased
lateral forces compared with contact mode; and
noncontact mode in which the probe tip interacts
with attractive forces very close to the surface but
is kept away from hard repulsive interactions.
Noncontact mode is capable of extremely high
resolution but is the most difficult to attain in
practice. From the imaging data, several quanti-
tative parameters of interest to membrane tech-
nologists can be obtained including: surface
roughness, pore size, pore-size distribution, as
well as showing in fine detail the morphology of
fouled and unfouled membrane surfaces and the
effects of chemical modification of membrane
surfaces (Johnson et al. 2012; Kochkodan
et al. 2013). Figure 1 shows a typical image of a
cyclopore microfiltration membrane and a
resulting pore-size distribution (Bowen
et al. 1996; Bowen and Hilal 2009). There are a
2 Atomic Force Microscopy (AFM)

Atomic Force
Microscopy (AFM),
mm
Fig. 1 3D image of
0.20
cyclopore microfiltration
0.10
membrane and pore-size
0.00
distribution for same
membrane obtained by 3
AFM
2
mm

1
3
2
0 1 mm
0

25

20

15
% of pores

10

0
0.10 0.15 0.20 0.25 0.30 0.35
Pore size, µm

large number of expansions for AFM instruments
allowing many other modes allowing mapping of
electrical and electrochemical, mechanical, adhe-
sive, frictional and magnetic properties of sur-
faces of interest.
As well as providing this information, the
AFM probe can be used as a force sensor by
moving the probe into and out of contact with
the sample surface and monitoring deflection in
the microcantilever arm. Through careful calibra-
tion of the system this deflection can be converted
into force, directly measuring the interaction
force as a function of probe tip – sample separa-
tion distance (Gibson et al. 2004). This allows the
detection of DLVO, hydrophobic, hydrostatic
and steric interactions, membrane stiffness, and
adhesion forces. The sharp tip may be replaced by
a colloidal particle, which may be functionalized
to simulate any of a number of potential mem-
brane foulants allowing quantitative measure-
ments of foulant rejection and attachment
forces. This makes possible the direct quantifica-
tion of membrane fouling properties of different
materials under a range of environmental condi-
tions and with only a relatively small sample of
membrane needed.
References
Bowen WR, Hilal N (eds) (2009) Atomic force micros-
copy in process engineering. Butterworth-Heineman,
Oxford
Bowen WR, Hilal N et al (1996) Atomic force microscope
studies of membranes: surface pore structures of
cyclopore and anopore membranes. J Membr Sci
110(2):233–238
Atomic Force Microscopy (AFM)
Gibson CT, Johnson DJ et al (2004) Method to determine
the spring constant of atomic force microscope canti-
levers. Rev Sci Instrum 75(2):565–567
Hilal N, Johnson DJ (2010) The use of atomic force
microscopy in membrane characterisation. In:
Drioli E, Giorno L (eds) Comprehensive membrane
science and engineering. Elsevier Science, Oxford,
pp 521–538
Hilal N, Al-Zoubi H et al (2004) A comprehensive review
of nanofiltration membranes: treatment, pretreatment,
3
modelling and atomic force microscopy. Desalination
170:281–308
Johnson DJ, Al-Malek SA et al (2012) Atomic force
microscopy of nanofiltration membranes: effect of
imaging mode and environment. J Membr Sci
389:486–498
Kochkodan V, Johnson DJ et al (2013) Polymeric mem-
branes: surface modification for minimizing (bio)col-
loidal fouling. Adv Colloid Interface Sci (in press).
doi:10.1016/j.cis.2013.05.005
A
Atomistic Simulations Methods
Elena Tocci
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rande (CS), Italy
Atomistic Simulations
Atomistic simulations are theoretical and compu-
tational modeling tools for interpreting what hap-
pens at the atomic scale in solids, liquids,
molecules and plasmas. Atomistic simulations,
such as phonon calculations, free-energy optimi-
zations (molecular mechanics), molecular
dynamics (MD), Monte Carlo simulations, and
crystal structure prediction, are used to interpret
existing experimental data and predict new phe-
nomena and to provide a way forward where
experiments are not yet possible, e.g., under
extreme conditions or at atomistic size- and time-
scales which are difficult to detect directly (Allen
and Tildesley 1989; Haile 1992; Frenkel and Smit
2002; Leach 2001; Brenner 2000; Allen 2004;
Tocci and Pullumbi 2011).
Molecular modeling is primarily a tool for
calculating the energy of a given molecular struc-
ture, and the goal is to understand and model the
motion of each atom in the material.
Different levels of atomistic simulations exist,
ranging from quantum mechanical models to sta-
tistical methods. This means solving numerically
the classical or quantum mechanical microscopic
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_36-1
equations for the motion of interacting atoms or
even deeper – electrons and nuclei.
Quantum mechanical (QM) or ab initio
methods describe matter at the electronic level,
considering the fundamental particles, electrons
and protons. The equation from which molecular
properties can be derived is the Schrodinger
equation, and various approximations must be
introduced in order to extend the utility of the
method to polyatomic systems.
Atomistic methods are used to compute
molecular properties, which do not depend on
electronic effects; the whole atom is modeled
just as a soft sphere and obeys the laws of statis-
tical mechanics. Atomistic simulation utilizes
analytic potential energy expressions
(sometimes referred to as empirical or classical
potentials) to describe the systems.
The analytic potential energy functions are
simplified mathematical expressions that attempt
to model interatomic forces arising from the
quantum mechanical interaction of electrons
and nuclei. Their use is dictated by the need to
model systems with sizes and/or timescales that
exceed available computing resources, required
for quantum calculations, which give no account
of the complex electronic structure of atoms.
Forces between atoms are derived from empir-
ical interatomic potentials that are obtained from
fitting material properties (e.g., lattice constant,
elastic constants, vacancy formation energy, etc.)
from experimental data or QM calculations. They
may depend on the distance between atoms,
2 Atomistic Simulations Methods


angles between bonds, angles between ! ! !
V nonbonded r 1 , r 2 , . . . , r N
planes, etc.
X
!  XX
! ! 
The general form of the total potential of the ¼ v ri þ w r i, r j þ . . .
N-atom system describes types of interactions, i i j⊳i
bonded and non-bonded, and can be written as:

!

 X
 The v r i term represents an externally applied
! ! ! !
V r 1 , r 2 , . .. , r N ¼ V 1 r i potential field and describes external force fields
X
 X
 (e.g., gravitational field) and external
! ! ! ! !
þ V2 r i, r j þ V3 r i, r j, r k þ . . . constraining fields (e.g., the “wall function” for
i, j⊳i i, j⊳i, k⊳j
particles in a chamber). The pair potential

  
! !
The part of the potential energy V representing w r i , r j ¼ w r ij neglect three-body (and
bonding interactions will include terms of the higher order) interactions.
following kind: The Lennard-Jones potential is the most com-
monly used form:
1X r  2
V intramolecular ¼ K r ij  r eq 
 
2 bonds ij1 s 12
s6
wLJ ðr Þ ¼ 4e 
1 X y  2 r r
þ K ijk yijk  yeq
2
bend
where s is the diameter and e is the depth of the
angles
potential energy well. If electrostatic charges are
1 X X f, m
  present, the appropriate Coulomb potentials are
þ K ijkl 1 þ cos mfijkl  gm
2 m added:
torsion
angles
Q1 Q2
wCoulomb ðr Þ ¼
The “bonds” 4pe0 r
  typically involve the separation
 ! !
r ij ¼  r i  r j  between adjacent pairs of atoms where Q1, Q2 are the charges and e0 the permit-
in a molecular framework, and a harmonic form tivity of the free space.
with specified equilibrium separation has been To be effective, an analytic potential energy
used, although this is not the only possible type. function must possess the following critical
The “bend angles” yijk are between successive properties:
! ! ! !
bond vectors such as r i  r j and r j  r k and
involve three atom coordinates. Usually this Flexibility: A potential energy function must be
bending term is quadratic in the angular displace- sufficiently flexible that it accommodates as
ment from the equilibrium value, although peri- wide a range as possible of fitting data.
odic functions are also used. The “torsion angles” Accuracy: A potential should be able to accu-
fijkl are defined in terms of three connected rately reproduce properties of interest as
bonds; hence four atomic coordinates are used. closely as possible.
The part of the potential energy V representing Transferability: A potential function should be
non-bonded interactions between atoms is tradi- able to study a variety of properties for
tionally split into one-body, two-body, three- which it was not fit.
body terms: Computational efficiency: Evaluation of the
function should be relatively efficient
depending on quantities such as system sizes
and timescales of interest, as well as available
computing resources.
Atomistic Simulations Methods
The major methods are molecular mechanics
(MM), molecular dynamics (MD), Monte Carlo
(MC), and additionally, there is a whole range of
hybrid techniques which combine features from
both MD and MC methods.
References
Allen MP (2004) Introduction to molecular dynamics
simulation computational soft matter: from synthetic
polymers to proteins. In: Attig N, Binder K,
Grubmuller H, Kremer K (eds) Lecture notes, John
von Neumann Institute for computing, Julich, NIC
series, vol 23, ISBN 3-00-012641-4, pp 1–28
3
Allen MP, Tildesley DJ (1989) Computer simulation of
liquids. Clarendon Press, Oxford
Brenner DW (2000) The art and science of an analytic
potential. Phys Status Solidi B 217:23
Frenkel D, Smit B (2002) Understanding molecular sim-
ulation: from algorithm to applications, 2nd edn. Aca-
demic, San Diego
Haile JM (1992) Molecular dynamics simulation. Wiley,
Chichester
Leach AR (2001) Molecular modelling: principles and
applications, 2nd edn. Prentice Hall, Harlow
Tocci E, Pullumbi P (2011) Chapter 1: Multi-scale molec-
ular modeling approaches for designing/selecting
polymers used for developing novel membranes. In:
Drioli E, Barbieri G (eds) Membrane engineering for
the treatment of gases: gas-separation problems with
membranes. The Royal Society of Chemistry, Cam-
bridge, UK, pp 1–28
A
Autothermal Reforming
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
Autothermal reforming or oxidative steam
reforming is a combination of conventional
steam reforming of the fuel (endothermic reac-
tion) with the partial oxidation of a small amount
of the fuel (exothermic reaction) in order to
achieve an autothermal reaction that proceeds
without external input of energy (Chang
et al. 2010; Tiemersma et al. 2012).
The most studied autothermal reforming is the
conversion of methane to hydrogen (Gallucci
et al. 2009). The overall chemical reactions tak-
ing place in the autothermal reforming of meth-
ane include steam reforming (Eq. 1), water gas
shift (Eq. 2), and total oxidation (Eq. 3). The
energy generated by the oxidation reaction and
WGS is used for the SMR:
CH4 þ H2 O Ð CO þ 3H2
CO þ H2 O Ð CO2 þ H2
CH4 þ 2O2 ! CO2 þ 2H2 O
This reaction system can be carried out efficiently
in a membrane reactor as the extraction of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_39-3
hydrogen during the reaction shifts the equilib-
rium reactions toward completion at moderate
temperatures, and thus the extent of oxidation
reaction to achieve autothermal reforming is
moderate.
One of the problems of autothermal reforming
carried out in membrane reactors is the mismatch
between the oxidation reaction rate and the
reforming reaction rate. The oxidation is often
much faster than the reforming, and for this rea-
son in packed bed membrane reactors, a high-
temperature region is obtained at the beginning
of the bed followed by a low-temperature region
at the end of the bed. This could cause problems
to the membranes that could be damaged by high
temperatures while not working properly (low
flux – see Richardson equation) at lower temper-
atures (Tiemersma et al. 2006; Gallucci et al.
2010).
To circumvent these problems, fluidized bed
membrane reactors are often proposed for this
kind of reaction system, as the solid circulation
inside the reactor allows a virtually isothermal
condition even in case of highly exothermic
reactions.
(1) Examples of autothermal reforming (ATR)
(or oxidative steam reforming) reactions also
(2) include the ATR of ethanol and methanol or the
ATR of naphtha (Lin et al. 2010; Tosti et al. 2010;
(3) Moreno and Wilhite 2009). All these reactions
have been successfully tested in membrane reac-
tors for pure hydrogen production.
2 Autothermal Reforming
References
Chang H-F, Pai W-J, Chen Y-J, Lin W-H
(2010) Autothermal reforming of methane for produc-
ing high-purity hydrogen in a Pd/Ag membrane reac-
tor. Int J Hydrog Energy 35(23):12986–12992,
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record.url?eid=2-s2.0-78049471869&partnerID=40
&md5=631e9a956f70441c60cc3fb3987ed76c
Gallucci F, Van Sint Annaland M, Kuipers JAM
(2009) Autothermal reforming of methane with inte-
grated CO2 capture in novel fluidized bed membrane
reactors. Asia Pac J Chem Eng 4(3):334–344.
doi:10.1002/apj
Gallucci F, Van Sintannaland M, Kuipers JAM
(2010) Theoretical comparison of packed bed and flu-
idized bed membrane reactors for methane reforming.
Int J Hydrog Energy 35(13):7142–7150, Retrieved
from http://www.scopus.com/inward/record.url?eid=
2-s2.0-77954826477&partnerID=40&md5=569ec26
bf526471832579c3f965b1d90
Lin W-H, Liu Y-C, Chang H-F (2010) Autothermal
reforming of ethanol in a Pd-Ag/Ni composite membrane
reactor. Int J Hydrog Energy 35(23):12961–12969,
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url?eid=2-s2.0-78049467904&partnerID=40&md5=
0048616ca9b8d29ade703c2eea0ab1bf
Moreno AM, Wilhite BA (2009) Autothermal hydrogen
generation from methanol in a ceramic microchannel
network. In: Conference proceedings – 2009 AIChE
annual meeting, 09AIChE. Retrieved from http://www.
scopus.com/inward/record.url?eid=2-s2.0-779522829
00&partnerID=40&md5=0650ebd8cd9440d3ac32e03
b4f859c7d
Tiemersma TP, Patil CS, Sint Annaland MV, Kuipers
JAM (2006) Modelling of packed bed membrane reac-
tors for autothermal production of ultrapure hydrogen.
Chem Eng Sci 61(5):1602–1616, Retrieved from
http://www.scopus.com/inward/record.url?eid=2-s2.0-
30344455632&partnerID=40&md5=9fb77a0611e8e6
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Tiemersma TP, Kolkman T, Kuipers JAM, van Sint
Annaland M (2012) A novel autothermal reactor con-
cept for thermal coupling of the exothermic oxidative
coupling and endothermic steam reforming of methane.
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aa2f96c86792bc
A
Azeotropic Distillation
Alessandra Criscuoli
Institute of Membrane Technology (ITM-CNR),
Rende, CS, Italy
Azeotropic distillation is a particular type of dis-
tillation by which it is possible to separate azeo-
tropes (Perry and Green 1984). Azeotropes are
mixtures of two or more substances that boil
together at a constant temperature. It is, therefore,
impossible to separate them directly by distilla-
tion, because a distillate of the same composition
of the liquid feed is produced. Azeotropic distilla-
tion is based on the addition of a compound that
acts on the volatility of the substances contained
into the azeotrope, so that a new azeotrope, made
of the substances present in the starting azeotrope
and the added compound, is formed. The new
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_40-3
azeotrope can be, then, removed by distillation,
and a residual highly rich in one of the substances
is obtained. A typical example is the distillation of
mixtures of water-ethanol. By classic distillation,
the distillate contains 95 % of alcohol (pure boil-
ing temperature, 78.4  C) and 5 % of water (pure
boiling temperature, 100  C), and no further incre-
ments in ethanol purity can be reached, because
this mixture boils, as a unique compound, at
78.17  C. However, if benzene or cyclohexane is
added to the mixture, a ternary azeotrope is formed
that incorporates all the water and has a lower
boiling point than ethanol. Therefore, if the distil-
lation is now carried out, the new azeotrope will be
recovered as distillate, while practically pure eth-
anol is produced as residue (see Fig. 1). Besides
azeotropic distillation, other methods can be
also employed for the separation of azeotropes
and, in particular, membrane operations like
pervaporation and membrane distillation.
2 Azeotropic Distillation

Ternary
azeotrope

Benzene or
cyclohexane

+ Ternary azeotrope
+ ethanol Distillation

Water-ethanol
azeotrope

Ethanol

Azeotropic Distillation, Fig. 1 Azeotropic distillation of water-ethanol

References

Perry RH, Green D (1984) Perry’s chemical engineers’

handbook. McGraw-Hill, Singapore
B
Bacteria and Spore Removal
Karin Schroen
Laboratory of Food Process Engineering,
Wageningen University and Research Centre,
Wageningen, The Netherlands
Bacteria can be of great influence on many pro-
cesses, be it in, for example, food, pharma, fer-
mentation, or water production. Obviously,
bacteria (and their spores) can be removed by
heat treatment or addition of specific components
that inhibit their growth or even kill them, but the
downside of this is that the product properties will
be influenced and this is mostly undesirable. In
this respect, membrane microfiltration could be
an interesting alternative when used for cold ster-
ilization. If the bacterial count is not too high and
other components are sufficiently smaller, the
removal of bacteria and spores can rather easily
be carried out using dead-end microfiltration.
When the size of bacteria and other compo-
nents overlap, this separation is far from straight-
forward. An illustrative example can be found in
dairy separation, in which cold sterilization of
“milk” has been reported. The components that
are most important for this separation are the milk
fat globules (cream; typical sizes from 0.1 to
15 mm), bacteria (0.5–5 mm), and casein micelles
(20–300 nm). Since cream and bacteria overlap in
size, the cream is first removed by centrifugation.
The resulting skim milk receives the cold
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_41-5
sterilization treatment. Various researchers have
investigated how far the bacterial count could be
reduced as listed in Table 1.
From the table, it is clear that a variety of
membranes and process conditions have been
used, ranging from very high to low cross-flow
velocities, and application of a uniform trans-
membrane pressure or frequent back pulsing.
These conditions are clearly aiming at processing
under very different conditions, where frequent
back pulsing will control the amount of deposited
material, the uniform transmembrane pressure
concept aims at stable filtration conditions along
the length of the membrane. All approaches have
shown interesting results; the log reductions that
can be achieved are around 4 (10,000-fold reduc-
tion), although it should be noted that these
values are not as high as obtained after regular
heat treatment.
The highest log reduction (6.6, which is higher
than for regular pasteurization) was claimed for
microsieves, which are silicon plates with very
uniform pores prepared by laser interference
lithography (Van Rijn and Elwenspoek 1995).
Although the bacterial reduction was measured
for dead-end filtration using a 0.5 mm microsieve
and SMUF (simulated ultrafiltrate) spiked with
Bacillus subtilis, it is expected that the high log
count reduction is a result of its narrow pore size
distribution of the microsieve.
In case of the uniform transmembrane pres-
sure concept, reduction of bacteria and spores by
microfiltration is carried out near the critical
2 Bacteria and Spore Removal

Bacteria and Spore Removal, Table 1 Comparison of cold sterilization results from various sources
Process conditions cross-flow/pressure, Log
Membrane type and flux UTP, back pulsing reduction Source
Ceramic 1.4 mm; 1.4•10 4
m/s 50 kPa, 7.2 m/s UTP, skim milk Above 3.5 Saboya and Maubois
2000
Reversed asymmetric 0.87 mm; 0.5–1 m/s; back pulsing frequency Between Guerra et al. 1997
1.4•10 4 m/s 0.2–1 s 1, skim milk 4 and 5
Microsieve 0.5 mm Dead-end filtration of spiked SMUF 6.6 Van Rijn and
Kromkamp 2001
Bactocatch: ceramic 6–8 m/s, skim milk, UTP Holm et al. 1989
membranes

pressure, at which the amount of particles that is References

carried toward that membrane by permeate is
counterbalanced by the amount of particles dif-
fusing away from the membrane to the feed solu-
tion. We expect that this can be even taken one
step further, as indicated in the work of van
Dinther et al. (2011), in which particles that
size-wise correspond to milk fat globules and
bacteria were reported to be separated by fluid
skimming and lift effects. For this to occur, first a
nonporous channel is used to induce particle
migration after which in a porous area the small
particles that are situated close to the wall can
specifically be removed. This process has not
been demonstrated at large scale, but it holds
great promise since it would allow for direct
separation of bacteria from full milk without the
need of centrifugation. Besides, the separation is
no longer determined by the pore size of the
membrane; metal sieves from SPG Veco with
uniform pores of around 20 mm were used, but
by the process conditions that determine which
part of the feed is removed.
Guerra A, Jonsson G, Rasmussen A, Waagner Nielsen E,
Edelsten D (1997) Low cross flow velocity
microfiltration of skim milk for removal of bacterial
spores. Int Dairy J 7:849
Holm S, Malmberg R, Svensson K (1989) Method and
plant producing milk with low bacterial content. WO
Patent 8:601–687
Saboya LV, Maubois JL (2000) Current developments of
microfiltration technology in the dairy industry. Lait
80:541
Van Dinther AMC, Schroën CGPH, Boom RM
(2011) High-flux membrane separation using fluid
skimming dominated convective fluid flow. J Membr
Sci 371(1–2):20
Van Rijn CJM, Elwenspoek MC (1995) Micro filtration
membrane sieve with silicon micro machining for
industrial and biomedical applications. In: Proceed-
ings of micro electro mechanical systems (MEMS),
Amsterdam, p 83
Van Rijn CJM, Kromkamp J (2001) Method for filtering
milk. WO Patent 0,209,527. http://www.spgveco.com/
precision+metal/applications/filtration. Accessed July
2012
B
Bacterial Biofilm Formation
Lidietta Giorno and Napoleone D’Agostino
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, University
of Calabria, Rende (CS), Italy
Synonyms
Bacterial biofilm; Bacterial adhesion; Biofouling
Biofilms were observed as early as 1674, when
Antonie van Leeuwenhoek used his primitive but
effective microscope to describe aggregates of
“animalcules” that he scraped from human tooth
surface (Costerton 1999). Since then, more accu-
rate descriptions of biofilms are made. Bacteria
generally exist in one of two types of population:
planktonic, freely existing in bulk solution, and
sessile, as a unit attached to a surface or within
the confines of a biofilm (Garrett et al. 2008).
Biofilm is a result of many complicated steps.
It includes the formation of a conditioning film on
a material’s surface, the movement of bacteria, an
attachment process, the growth on material sur-
faces, and the breakdown finally. For bacteria, the
advantages of biofilm formation are numerous.
These advantages include: protection from anti-
biotics (Godberg 2002), disinfectants (Peng et al.
2002), and dynamic environments (Chen et al.
1998).
Over the past few decades, biofilm growth has
been observed in many industrial and domestic
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_42-1
domains. Many industries suffer the ill effects of
biofilm growth of one type or another, which can
result in heavy costs in cleaning and mainte-
nance. Biofilms occurring in membrane systems
may cause severe loss performance and the use of
costly cleaning procedures to maintain output and
quality. The fouling is often so severe that accept-
able operation cannot be maintained and mem-
brane replacements are needed. It is necessary to
understand the biofilm formation mechanism
with the aim to propose a solution to contrast
this fouling.
Bacteria are capable of colonizing almost any
surface and have been found at extreme condi-
tions such as temperatures from 12  C to 110  C
and pH values between 0.5 and 13.
Biofilm growth occurs by physical, chemical,
and biological processes. Fletcher described the
accumulation of microorganisms on a collecting
surface as a process of three stages:
(i) adsorption, or the accumulation of an organ-
ism on a collector surface, i.e., substrate
(deposition); (ii) attachment, or the consolidation
of the interface between an organism and a col-
lector, often involving the formation of polymer
bridges between the organism and collector; and
(iii) colonization, or growth and division of
organisms on the collector’s surface. Although
useful as a snapshot of biofilm growth, this type
of profile is limited when considering the inti-
mate processes of cell–substrate/cell–cell inter-
action. Characklis and Marshal later described an
eight-step process which included the formation
2 Bacterial Biofilm Formation
of an initial conditioning layer, reversible and
irreversible adhesion of bacteria, and the eventual
detachment of cells from a mature biofilm for
subsequent colonization.
Anything that may be present within the bulk
fluid can through gravitational force or move-
ment of flow settle onto a substrate and become
part of a conditioning layer. This layer modifies
substrata facilitating accessibility to bacteria.
Surface charge, potential, and tensions can be
altered favorably by the interactions between
the conditioning layer and substrate. The sub-
strate provides anchorage and nutrients
augmenting growth of the bacterial community.
Initially, planktonic microbial cells are
transported from bulk liquid to the conditioned
surface either by physical forces or by bacterial
appendages such as flagella. The reversible
adsorption of a fraction of the cells reaching the
surface normally occurs. Local environmental
variables which contribute to bacterial adhesion
are factors such as available energy, surface func-
tionality, bacterial orientation, temperature, and
pressure conditions. If repulsive forces are
greater than the attractive forces, the bacteria
will detach from the surface. The probability of
this phenomenon occurs is higher before the for-
mation of the conditioning layer. The activation
energy for desorption of bacteria is low and so it
is likely to occur, underlining the weakness of the
bonds. Physical forces associated to bacterial
adhesion include the van der Waals forces, steric
interactions, and electrostatic (double layer)
interaction, collectively known as the DVLO
(Derjaguin, Verwey, Landau, and Overbeek)
forces, which originally described the interaction
of a colloidal particle with a surface (Rutter and
Vincent 1980). According to this theory, the total
interaction between a surface and a particle is the
summation of their van der Waals and Coulomb
interactions. Since the van der Waals attractive
force is dominant in the vicinity of a surface,
particles adhere irreversibly because they cannot
separate from the surface by Brownian motion. In
contrast, the Coulomb interaction becomes dom-
inant at a distance away from the surface because
the van der Waals force decreases sharply with
distance. Other interactions that DVLO theory
takes into consideration are hydrophobic–hy-
drophilic and osmotic (Chang and Chang 2002)
and have also been described in terms of thermo-
dynamic interaction (Gallardo-Moreno et al.
2002).
In real time, a number of the reversibly
adsorbed cells remain immobilized and become
irreversibly adsorbed. It has been argued that the
physical appendages of bacteria (flagella, fim-
briae, and pili) overcome the physical repulsive
forces of the electrical double layer (De Weger
1987). Subsequently, the appendages make con-
tact with the bulk lattice of the conditioning layer
stimulating chemical reactions such as oxidation
and hydration and consolidating the
bacteria–surface bond. Some evidence has
shown that microbial adhesion strongly depends
on the hydrophobic–hydrophilic properties of
interacting surfaces (Liu et al. 2004).
As the stationary cells divide (binary divi-
sion), daughter cells spread outward and upward
from the attachment point to form clusters. Typ-
ically, such interactions and growth within the
developing biofilm form into a mushroom-like
structure. This structure is believed to allow the
passage of nutrients to bacteria deep within a
biofilm. After an initial stage, a rapid increase in
population is observed, otherwise described as
the exponential growth phase. This depends on
the nature of the environment, both physically
and chemically. The rapid growth occurs at the
expense of the surrounding nutrients from the
bulk fluid and the substrate. At this stage the
physical and chemical contribution to the initial
attachment ends and the biological processes
begin to dominate. Excretion of polysaccharide
intercellular adhesin (PIA) polymers and the
presence of divalent cations interact to form
stronger bonding between cells (Dunne 2002).
Differential gene expression between the two
bacterial states (planktonic/sessile) is in part
associated to the adhesive needs of the popula-
tion. For example, the production of surface
appendages is inhibited in sessile species as
motility is restricted and no longer necessary.
Simultaneously, expression of a number of
genes for the production of cell surface proteins
and excretion products increases. Surface
Bacterial Biofilm Formation
proteins (porins), such as Opr C and Opr E, allow
the transport of extracellular products into the
cell and excretion materials out of the cell, e.g.,
polysaccharides (Hancock et al. 1990). The struc-
ture of many Gram-negative bacterial polysac-
charides is relatively simple, comprising either
homopolysaccharides or heteropolysaccharides
(Sutherland 2001). These molecules impart
mechanical stability and are pivotal to biofilm
adhesion and cohesion and evasion from harsh
dynamic environmental conditions. They consol-
idate the biofilm structure. Hall-Stoodley and
Stoodley identified the differences in gene
expression of planktonic and sessile cells, and
as many as 57 biofilm-associated proteins were
not found in the planktonic profile.
The stationary phase of growth describes a
phase where the rate of cell division equals the
rate of cell death. At high cell concentration, a
series of cell signaling mechanisms are employed
by the biofilm, and this is collectively termed
quorum sensing (Bassler 1999). Quorum sensing
describes a process where a number of
autoinducers (chemical and peptide signals in
high concentrations, e.g., homoserine lactones)
are used to stimulate genetic expression of both
mechanical and enzymatic processors of algi-
nates, which form a fundamental part of the extra-
cellular matrix. The death phase sees the
breakdown of the biofilm. Enzymes are produced
by the community itself which break down poly-
saccharides holding the biofilm together, actively
releasing surface bacteria for colonization of
fresh substrates. Alginate lyase produced by
Pseudomonas fluorescens and Pseudomonas
aeruginosa, N-acetyl-heparosan lyase by
Escherichia coli, and hyaluronidase by Strepto-
coccus equi are examples of the enzymes used in
the breakdown of the biofilm matrix (Sutherland
1999). Simultaneously, the operons coding for
flagella proteins are upregulated so that the
organisms have the apparatus for motility and
the genes coding for a number of porins are
downregulated, thus completing a genetic cycle
for biofilm adhesion and cohesion.
Changes in pH can have a marked effect on
bacterial growth and as such are frequently
exploited in the production of detergents and
3
disinfectants used to kill bacteria. Bacteria pos-
sess membrane-bound proton pumps which
extrude protons from the cytoplasm to generate
a transmembrane electrochemical gradient
(Rowland 2003), i.e., the proton motive force.
The passive influx of protons in response to the
proton motive force can be a problem for cells
attempting to regulate their cytoplasmic pH
(Booth 1985). Large variations in external pH
can overwhelm such mechanisms and have a
biocidal effect on the microorganisms. Bacteria
respond to changes in internal and external pH by
adjusting the activity and synthesis of proteins
associated with many different cellular processes
(Olsen 1993). Studies have shown that a gradual
increase in acidity increases the chances of cell
survival in comparison to a sudden increase by
rapid addition of HCl (Li 2001). This suggests
that bacteria contain mechanisms in place which
allow the bacterial population to adapt to small
environmental changes in pH. However, there are
cellular processes which do not adapt to pH fluc-
tuations so easily. One such process is the excre-
tion of exopolymeric substances
(polysaccharides). Optimum pH for polysaccha-
ride production depends on the individual spe-
cies, but it is around pH 7 for most bacteria.
Both mixed species and pure culture biofilms
behave like viscoelastic fluids. Biofilms exhibit
both irreversible viscous deformation and revers-
ible elastic response and recoil (Ohashi and
Harada 2004). Extracellular polymeric sub-
stances like alginate, xanthan, and gellan gum
aggregate due to hydrogen bonding to form
highly hydrated viscoelastic gels (Stoodley et al.
1999). The presence of acetylated uronic acids in
the bacterial alginate of P. aeruginosa biofilms
increases its hydration capacity. These properties
provide the biofilm with mechanical stability
(Stoodley et al. 2002).
The matrix formed by EPS responds to stress
by exhibiting (i) elastic tension due to a combi-
nation of polymeric entanglement, entropic, and
weak hydrogen bonding forces; (ii) viscous
damping due to polymeric friction and hydrogen
bond breakage; and (iii) alignment of the poly-
mers in the shear direction (Klapper et al. 2002).
Such properties change with increased
4 Bacterial Biofilm Formation
temperature. Increasing the temperature of poly-
saccharides produces a gel-like substance which
gradually increases in strength until a critical
point is reached. At the critical point the gel
forms a solution (Villain-Simonnet et al. 2000).
Such behavior affects the viscosity of the poly-
saccharides which can affect biofilm adherence.
The optimum temperature for a microorganism is
associated with an increase in nutrient intake
resulting in a rapid formation of biofilm
(Stepanovic et al. 2003). Enzymes are responsi-
ble of nutrient metabolism; then the formation of
a biofilm is dependent on the presence and reac-
tion rates of enzymes. Temperature influences the
reaction rate of enzymes having an impact on the
development of the cells. Optimum temperatures
result in the healthy growth of bacterial
populations. Temperatures away from the opti-
mum negatively influence bacterial enzyme reac-
tion rates, and a reduction of bacterial growth
efficiency occurs. Fletcher reported the effect of
temperature on attachment of stationary phase
cells. Findings showed that a decrease in temper-
ature reduced the adhesive properties of a marine
Pseudomonad. It is believed that the effect was
due to a decrease in the bacterial surface polymer
at lower temperatures as well as effects such as
reduced surface area. However, Herald and
Zottola observed that the presence of bacterial
surface appendages was dependent on tempera-
ture. At 35  C cells were shown to have a single
flagellum, while at 21  C they had two to three
flagella, and at 10  C, cells exhibited several
flagella. This may suggest that the initial interac-
tion between the bacteria and substrate may
increase with a lowering of temperature, increas-
ing the likelihood of adhesion. Perhaps the more
uniform properties of polysaccharides at lower
temperatures increase the possibility of biofilm
adhesion, because many microbial polysaccha-
rides undergo transition from an ordered state at
lower temperatures and in the presence of ions to
a disordered state at elevated temperature under
low ionic environments (Nisbet et al. 1984).
Although there is plenty of information
describing the effect of temperature on bacterial
growth in culture, the effect of temperature on the
removal of adhered microorganisms is not so well
documented. The reports available describe fairly
radical effects of temperature on adhered bacte-
ria. Marion-Ferey et al. observed the effect of
high temperatures (80–90  C) on the removal of
biofilms. It was discovered that these tempera-
tures were not effective for biofilm removal due
to “baking effects” at high temperature, appar-
ently increasing the adherent nature of the biofilm
to the surface.
References
Bassler BL (1999) How bacteria talk to each other: regu-
lation of gene expression by quorum sensing. Curr
Opin Microbiol 2:582–587
Booth IR (1985) Regulation of cytoplasmic pH in bacteria.
Microbiol Rev 49:359–378
Chang YI, Chang PK (2002) The role of hydration force
on the stability of the suspension of Saccharomyces
cerevisiae – application of the extended DLVO theory.
Colloids Surf A Physicochem Eng Asp 211:67–77
Characklis WG, Marshal KC (1990) Biofilms. Wiley,
New York
Chen MJ, Zhang Z, Bott TR (1998) Direct measurement of
the adhesive strength of biofilms in pipes by microma-
nipulation. Biotechnol Tech 12:875–880
Costerton JW (1999) Introduction to biofilm. Int
J Antimicrob Agents 11:217–221
De Weger LA, van der Vlugt C, Wijfjes AHM et al (1987)
Flagella of a plant-growth-stimulating Pseudomonas
fluorescens strain are required for colonization of
potato roots. J Bacteriol 169:2769–2773
Dunne WM (2002) Bacterial adhesion: seen any good
biofilms lately? Clin Microbiol Rev 15:155–166
Fletcher M (1977) The effects of culture concentration and
age, time, and temperature on bacterial attachment to
polystyrene. Can J Microbiol 23:1–6
Fletcher M (1980) Microbial adhesion to surfaces. Ellis
Horwood, Chichester
Gallardo-Moreno AM, Gonzalez-Martin ML, Perez-
Giraldo C et al (2002) The measurement temperature:
an important factor relating physicochemical and
adhesive properties of yeast cells to biomaterials.
J Colloid Interface Sci 271:351–358
Garrett TR, Bhakoo M, Zhang Z (2008) Bacterial adhe-
sion and biofilms on surfaces. Prog Nat Sci
18:1049–1056
Godberg J (2002) Biofilms and antibiotic resistance: a
genetic linkage. Trends Microbiol 10:264
Hall-Stoodley L, Stoodley P (2002) Developmental regu-
lation of microbial biofilms. Curr Opin Biotechnol
13:228–233
Hancock REW, Siehnel R, Martin N (1990) Outer mem-
brane proteins of Pseudomonas. Mol Microbiol
4:1069–1075
Bacterial Biofilm Formation
Herald PJ, Zottola EA (1988) Attachment of Listeria
monocytogenes to stainless steel surfaces at various
temperatures and pH values. J Food Sci 53:1549–1552
Hiemenz PC, Rajagopalan R (1997) Principles of colloid
and surface chemistry. Marcel Dekker, New York
Klapper I, Rupp CJ, Cargo R et al (2002) Viscoelastic fluid
description of bacterial biofilm material properties.
Biotechnol Bioeng 80:289–296
Li Y (2001) Cell density modulates acid adaptation in
Streptococcus mutans. J Bacteriol 183:6875–6884
Liu Y, Yang S, Xu H et al (2004) The influence of cell and
substratum surface hydrophobicities on microbial
attachment. J Biotechnol 110:251–256
Marion-Ferey K, Pasmore M, Stoodley P et al (2002) Bio-
film removal from silicone tubing: an assessment of
the efficacy of dialysis machine decontamination pro-
cedures using an in vitro model. J Hosp Infect
53:64–71
Marshall KC, Stout R, Mitchell R (1971) Mechanism of
the initial events in the sorption of marine bacteria to
surfaces. J Gen Microbiol 68:337–348
Nisbet BA, Sutherland IW, Bradshaw IJ et al (1984)
XM-6: a new gel-forming bacterial polysaccharide.
Carbohydr Polym 4:377–394
Ohashi A, Harada H (2004) Adhesion strength of biofilm
developed in an attached-growth reactor. Water Sci
Technol 29:281–288
Olsen ER (1993) Influence of pH on bacterial gene expres-
sion. Mol Microbiol 8:5–14
5
Peng JS, Tsai WC, Chou CC (2002) Inactivation and
removal of Bacillus cereus by sanitizer and detergent.
Int J Food Microbiol 77:11–18
Rowland BM (2003) Bacterial contamination of dental
unit waterlines: what is your dentist spraying into
your mouth? Clin Microbiol Newsl 25:73–77
Rutter PR, Vincent B (1980) Microbial adhesion to sur-
faces. Ellis Horwood, London
Stepanovic S, Cirkovic I, Mijac V et al (2003) Influence of
the incubation temperature, atmosphere and dynamic
conditions on biofilm formation by Salmonella
spp. Food Microbiol 20:339–343
Stoodley P, Lewandowski Z, Boyle J et al (1999) Struc-
tural deformation of bacterial biofilms caused by short-
term fluctuations in fluid shear: an in situ investigation
of biofilm rheology. Biotechnol Bioeng 65:83–92
Stoodley P, Cargo R, Rupp CJ et al (2002) Biofilm mate-
rial properties as related to shear-induced deformation
and detachment phenomena. J Ind Microbiol
Biotechnol 29:361–367
Sutherland IW (1999) Polysaccharases for microbial
exopolysaccharides. Carbohydr Polym 38:319–328
Sutherland IW (2001) Microbial polysaccharides from
Gram-negative bacteria. Int Dairy J 11:663–674
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bacterial exopolysaccharide (YAS34). II. Influence of
thermal treatments on the conformation and structure.
Int J Biol Macromol 27:77–87
S
Silicalite Membrane
Tsuneji Sano
Department of Applied Chemistry, Hiroshima
University, Graduate School of Engineering,
Higashi-Hiroshima, Japan
Zeolites are a class of crystalline aluminosilicates
with highly regular and open microporous struc-
tures. More than 200 types of zeolite frameworks
have been identified by the Structure Commis-
sion of the International Zeolite Association.
Zeolite membranes combine the great advantages
of inorganic membranes, such as temperature
stability and resistance against solvents, with the
molecular sieving effect. Zeolite silicalite (MFI,
where the three characters indicate the frame-
work type) with Si/Al ratio of 1 is well known
as a hydrophobic zeolite. Figure 1 shows the
framework structure of MFI zeolite
(International Zeolite Association Web site
2013). There are two channel systems: a straight

ðWeight of permeate, kgÞ
Flux kg=m2 h ¼
ðMembrane area, m2 Þ  ðPermeation time, hÞ
Separation factor aðROH=H2 OÞ ¼
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_43-1
channel running to (010) with ten-membered ring
openings of 5.3  5.6 Å and a sinusoidal channel
parallel to the (100) with ten-membered ring
openings of 5.1  5.5 Å.
Silicalite membrane was prepared as a self-
standing polycrystalline film at first and was very
fragile (Sano et al. 1991). Therefore, the silicalite
membranes are crystallized on porous supports
such as sintered stainless steel disc or alumina
disc(tube) with an average pore diameter of 0.5 
2 mm. Colloidal silica is added to a stirred mixture
of tetrapropylammonium bromide (TPABr) and
sodium hydroxide in solution, to give a hydrogel
with a composition of 0.1 TPABr-0.05 Na2O-
SiO2-80H2O. The hydrogel is transferred to a
stainless steel autoclave and kept at 170  C for
48 h. The separation performances can be evalu-
ated by pervaporation measurements using vari-
ous aqueous alcohol solutions as a feed. Flux and
separation factor a(ROH/H2O) are calculated
from following equations:
(1)
½CROH =CH2 O Permeate
(2)
½CROH =CH2 O Feed
2 Silicalite Membrane
where the CROH and CH2 O are the volume frac-
tions of alcohols and water, respectively.
Figure 2 shows scanning electron micrographs
(SEM) of the outer surface and cross-section of
the membrane on the stainless steel support (Sano
et al. 1994). The surface is formed of an aggre-
gate of crystals of 10  30 mm and the growth on
the support led to a randomly grown crystalline
layer. The average thickness of the silicalite layer
was confirmed by Si line analysis using energy-
dispersive X-ray analysis (EDX). The organic
amine used in the silicalite synthesis as a template
remains in the channels of silicalite crystals. In
order to use the membrane as the separation
membrane, the amine must be removed from the
channels by certain procedures. As the silicalite
Silicalite Membrane, Fig. 1 Framework structure of
silicalite (MFI) zeolite (IZA web. 2013)
Silicalite Membrane,
Fig. 2 SEM images of (a) a b
outer surface and (b) cross-
section of silicalite
membrane on stainless steel
support (Reproduced from
Sano et al. (1994) with the
permission of Elsevier)
membrane experiences the irregular stresses that
arise from a difference in the thermal expansion
between the support and the silicalite crystals or
from removal of volatile materials from the zeo-
lite framework, cracks are easily formed within
the membrane during the treatment process.
Therefore, pretreatment conditions of mem-
branes affect strongly the separation perfor-
mance. As listed in Table 1 (Sano et al. 1994),
the silicalite membrane after air-drying at 100  C
(containing TPA+) shows a very low flux com-
bined with a low separation factor below 1, indi-
cating that there is no cracks and pores between
silicalite grains within the membrane before the
pretreatment. However, in the case of the mem-
brane after the thermal treatment, the flux and the
separation factor increase with an increase in the
treatment temperature and period. The membrane
calcined at 500  C to remove the template
completely shows the high flux combined with
the higher separation factor. The membrane
changes from the water-selective membrane to
the ethanol-selective one by decreasing the
amount of TPA+ occluded in the zeolite frame-
work, and the separation of ethanol/water takes
place by transport through the zeolite channels.
Figure 3 displays effects of the feed temperature
on the separation factor and the flux for various
alcohol/water mixtures (Sano et al. 1994). The
high separation factor is obtained for 1-propanol/
water mixture, although the flux is very low. On
25 μm 250 μm
Silicalite Membrane 3

Silicalite Membrane, Table 1 Influence of pretreatment conditions on pervaporation performance of silicate mem-
brane (Reproduced from Sano et al. (1994) with the permission of Elsevier)
Treatment condition Flux (kg/m2 h) Separation factor a (EtOH/H2O)

Air-drying 100 C 12 h 0.00303 0.38
In vacuum 300  C 6h 0.00840 0.58
In vacuum 380  C 6h 0.0394 7.8
Calcination 500  C 20 h 0.760 58
Feed temperature: 60  C
Feed ethanol concentration: 5 vol.%

2 100

MeOH
80 1-PrOH
1.5 Separation factor α (ROH/H2O)
Flux (kg/m2h)

60
EtOH
1
EtOH 2-PrOH
40

0.5
20 MeOH
2-PrOH

1-PrOH
0 0
20 30 40 50 60 70 20 30 40 50 60 70
Feed temperature (°C) Feed temperature (°C)

Silicalite Membrane, Fig. 3 Pervaporation flux and separation factor a for various alcohol/water mixtures
(Reproduced from Sano et al. (1994) with the permission of Elsevier). Feed alcohol concentration: 1 mol%

the other hand, the higher flux and the lower
separation factor are obtained for methanol/
water mixture. This can be explained by the dif-
ferences in the molecular size and the interaction
between alcohol and silicalite, methanol being
the smallest and the most polar molecule in the
group of alcohols tested here.
References
International Zeolite Association Web site (2013) http://
www.iza-online.org/
Sano T, Kiyozumi Y, Kawamura M, Mizukami F,
Takaya H, Mouri T, Inaoka W, Toida Y,
Watanabe M, Toyoda K (1991) Preparation and char-
acterization of ZSM-5 zeolite film. Zeolites
11:842–845
Sano T, Hasegawa M, Kawakami Y, Kiyozumi Y,
Yanagishita H, Kitamoto D, Mizukami F (1994)
Potentials of silicalite membrane for the separation of
alcohol/water mixture. Stud Surf Sci Catal
84:1175–1182
B
Batch Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Batch diafiltration refers to a pressure-driven
membrane filtration process in which a diluant
(pure solvent) is added into the feed tank in order
to enhance the degree of separation of
macrosolutes from microsolutes. In batch
diafiltration, in contrast to continuous
diafiltration, the retentate stream is recirculated
to the feed tank, and only the permeate stream is
collected separately. During the operation,
solute-free diluant is introduced into the feed
tank to replace solvent losses as schematically
illustrated in Fig. 1. The requirement for an effec-
tive separation is the utilization of a membrane
which highly retains the macrosolute but perme-
able for the microsolute. Thus, depending on the
application, microfiltration, ultrafiltration,
nanofiltration, or even reverse osmosis mem-
branes can be applied.
In its strict, original sense, the term batch
diafiltration refers to a process that aims at
removing the microsolutes from the process
liquor. The standard way of achieving this puri-
fication goal is to employ a constant-volume
diafiltration (CVD) process that is probably the
most common type of batch diafiltration. In CVD,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_45-6
the feed volume is kept constant by continuously
adding a diluant at a rate equal to the
permeation rate.
It should be pointed out that the removal of
microsolutes and the concentration of
macrosolutes (i.e., the reduction of the volume
of process liquor) are both required for most
applications. The term batch diafiltration, in its
broader sense, may stand for a batch filtration
process that is designed to achieve the twin objec-
tives of concentrating and purifying a multi-
solute system according to a specific diluant uti-
lization strategy. In this context, batch
diafiltration is a complex process that may
involve a sequence of consecutive operational
steps.
A straightforward way of achieving the dual
objectives of concentration and fractionation is to
combine CVD with concentration mode opera-
tional steps (i.e., in which no diluant is added into
the feed tank). A so constructed typical three-step
process, also referred to as traditional diafiltration
(TD), involves the following phases:
(i) concentration mode to achieve an intermediate
macrosolute concentration, (ii) constant-volume
diafiltration to “wash out” the microsolute by a
pure solvent introduced into the system, and (iii)
further concentration to the final desired
macrosolute concentration. Beside TD, a number
of alternative strategies have been proposed.
These include the sequential dilution diafiltration
(SDD), intermittent feed diafiltration (IFD),
variable-volume diafiltration (VVD),
2 Batch Diafiltration
Batch Diafiltration,
Diluant u(t)
Fig. 1 Schematic
representation of batch
diafiltration configuration
pre-concentration combined with variable-
volume diafiltration (CVVD), and dynamic-
volume diafiltration (DVD).
Diafiltration techniques differ in controlling
the addition of the diluant in terms of quantity
and duration. The differences between the vari-
ous operations are best described by the propor-
tionality factor a (i.e., the ratio of diluant flow d(t)
to permeate flow q(t)) as a function of operation
time (Foley 2006). For instance, TD process is
characterized with a sequence a(t) = {0, 1, 0}
with two unknown switching times at the end of
the first and of the second time interval. Simi-
larly, CVVD process has two phases with con-
stant a levels a(t) = {0, a1} and an unknown
switching time. Table 1 shows the diluant control
strategies applied in batch processing. Note that
the best time-varying profile of diluant addition
needs not necessarily be one of the arbitrarily
predefined profiles. The diafiltration process,
that is, designed by the evaluation of the optimal
time-varying profile of the diluant flow, is
referred to as dynamic-volume diafiltration
(Paulen et al. 2012).
The governing differential equations for a
generalized batch diafiltration process are given
as
dci ci q
¼ ðRi  aÞ, ci ð0Þ ¼ ci0 , i ¼ 1, 2
dt V with the high concentration at the
dV
¼ ða  1Þq, V ð0Þ ¼ V 0 :
dt
where ci is the solute concentration in the feed
tank, Ri the rejection of component i, and
Retentate Permeate q(t)
Feed
V represents the feed tank volume. This initial
value problem describes the evolution in time of
the feed volume and the feed concentration of any
solute under the assumption that the diluant is
solute-free and the feed tank is well-mixed.
Note that the time-dependent variables (i.e., per-
meate flux and the solute rejections) are, in a
general case, a function of feed concentrations
and may vary with operation conditions
(temperature, pressure, cross-flow velocity, etc.).
The unique feature of realizing both concen-
tration and fractionation puts membrane filtration
in an attractive position and compares favorably
with other separation methods or even with a
sequence of consecutive unit operations. In com-
parison with continuous processes, batch opera-
tions are especially suited to small-scale
operations, require less expensive automatic con-
trols, and enable a reduced membrane area in
order to reach the target (Baker 2004). Most
batch plants operate under constant mechanistic
membrane pressure adjusted simply by the
retentate valve. There exist, however, other
types of process control strategies in engineering
practice, such as constant flux or constant wall
concentration control (van Reis et al. 1997).
These are normally employed when unfavorable
side effects (e.g., enhanced fouling or product
quality deterioration) occur that can be associated
membrane wall.
Batch Diafiltration 3

Batch Diafiltration, Table 1 Diluant utilization strategies in batch diafiltration

Name a - strategy
Constant-volume dilution a¼1
Traditional diafiltration a ¼ f0, 1, 0g
Variable-volume diafiltration a ¼ const, 0 < a < 1
Preconcentration with variable-volume diafiltration a ¼ f0, a1 g, a1 ¼ const, 0 < a1 < 1

Intermittent feed diafiltration a ¼ ð0, amax Þn , 0

Sequential dilution diafiltration a ¼ ðamax , 0Þn
Dynamic-volume diafiltration a ¼ aðtÞ 0  aðtÞ  amax
n number of repetition

References Paulen R, Fikar M, Foley G, Kovács Z, Czermak P (2012)

Optimal feeding strategy of diafiltration buffer in batch
Baker R (2004) Membrane technology and applications. membrane processes. J Membr Sci 411–412:160–172
Wiley, Chichester van Reis R, Goodrich EM, Yson CL, Frautschy LN,
Foley G (2006) Ultrafiltration with variable volume Whiteley R, Zydney AL (1997) Constant Cwall ultra-
diafiltration: a novel approach to water saving in filtration process control. J Membr Sci
diafiltration processes. Desalination 130(1–2):123–140
199(1–3):220–221
B
Beer Clarification
Frank Lipnizki
Alfa Laval Copenhagen, Søborg, Copenhagen,
Denmark
In the traditional brewing process, the beer is
clarified after fermentation and before maturation
to remove mainly the remaining yeast but also
microorganisms and haze. The conventional pro-
cess for beer clarification is the combination of a
high-speed separator followed by diatomaceous
earth (DE)/kieselguhr filtration which is
complemented in some cases by second filtration
with PVP (polyvinylpyrrolidone) to obtain a very
clear beer. The major challenge of the conven-
tional process is related to the DE filtration
because the DE can vary in quality and is prob-
lematic for handling and disposal since it is haz-
ardous plus DE filtration generates large amounts
of effluent. Alternatively, from its introduction in
2001 (Buttrick 2007) cross-flow microfiltration
has established itself in the brewing industry
with over 50 breweries worldwide adopting this
DE-free beer filtration. Generally, three concepts
are currently used in the industry:
1. Beer Membrane Filtration (BMF) by Pentair
(previously Norit) – a system based on hollow
fiber microfiltration cartridges without a high-
speed separator as pretreatment
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_46-1
2. PROFi Membrane System by Pall and GEA
Westfalia – a combination of hollow fiber
microfiltration system with a high-speed sep-
arator as pretreatment
3. AlfaBright system by Alfa Laval and
Sartorius – a process based on the combination
of cassette microfiltration system with a high-
speed separator as pretreatment
The membranes established for beer filtration
are all polymeric microfiltration membranes
based on polyethersulfone with 0.5–0.65 mm
pores and beer capacities of 0.5 1.0 hl/(m2 h)
(Buttrick 2007). The resulting beer quality from
the membranes is similar or improved compared
to the DE filtration; in Table 1 a comparison
between beer filtered by DE and microfiltration
membranes is given. Other membranes, e.g.,
ceramic membranes, have been tested for beer
filtration but so far have not established them-
selves on the market. The key difference between
the three concepts is the use of a high-speed
separator as pretreatment. In the BMF system a
retentate tank is used to collect the beer solids,
while both the PROFi and the AlfaBright systems
are using high-speed separators as pretreatment
before the membrane to remove the beer solids
and thus eliminating the need for a retentate tank.
The systems can be typically run in batch or
continuous operation depending on the size and
requirements of the individual brewery. In batch
operation, the complete system shifts from filtra-
tion into cleaning mode after each batch. Plants
2 Beer Clarification

Beer Clarification, Table 1 Comparison of key parameters of beer filtered with DE filtration and microfiltration
(Lipnizki 2005)
Beer before filtration Beer after DE filtration Beer after microfiltration
Original extract [%] 11.40 11.37 11.39
Alcohol [%] 3.84 3.83 3.84
Color [EBC] 7.20 6.70 7.00
Viscosity [MPas] 1.62 1.57 1.56
Turbidity at 0  C [EBC] 32.00 0.53 0.41

with continuous operation are arranged in skids/ References

blocks and use sequential cleaning which allows
for some skids/blocks to be in standby cleaning
mode, while other blocks are in filtration mode.
The major challenges for cross-flow membrane
beer filtration are the relatively high investment
costs and complexity of the process when com-
pared to DE filtration and the increasing avail-
ability of alternative DE-free filter aids.
Buttrick P (2007) Filtration – the facts. Brewer Distiller
Int 3(12):12–19
Lipnizki F (2005) Optimisation and integration of mem-
brane processes in the beverage industry, 10th edn.
Aachener Membran Kolloquium, Aachen, 16.-
17.03.2005
B
Beer Dealcoholization
Frank Lipnizki
Alfa Laval Copenhagen, Søborg, Copenhagen,
Denmark
In the last decades the demand for low alcohol
and alcohol-free drinks increased, e.g., in Ger-
many the annual consumption of alcohol-free
drinks nearly doubled from 130.4 l per person in
1980 to 248.2 l person in 1999, while the annual
consumption of alcoholic drinks declined from
179.5 to 156.3 l during the same period (Gebhardt
2001). Conventionally beer can be dealcoholized
by distillation, but additionally the membrane
process reverse osmosis and dialysis have
established themselves for the partial dealcoho-
lization of beer by eight to ten times. The key
advantage of membrane processes over distilla-
tion is that beer can be dealcoholized at low
temperatures typically 78  C to minimize the
effect of temperature on the beer flavor resulting
in high-quality low alcohol beer, which can be
bottled after final sterile filtration.
Reverse osmosis is typically carried out in
spiral wound modules, and the dealcoholization
process based on reverse osmosis can be divided
into four individual operations which are typi-
cally carried out in batch mode:
1. Pre-concentration: In this step the volume of
the feed beer is reduced. The beer is passed
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_47-1
through the membrane modules and is then
recycled to the batch tank. The
permeate – water and alcohol – is removed
from the process, while retentate, concen-
trated beer and flavors, is returned to the
batch tank.
2. Diafiltration: This step is similar to the
pre-concentration step but diafiltration
water – desalted and deoxygenized water – is
added to wash out the alcohol. The amount of
diafiltration water added balances the amount
of permeate removed from the process, and
thus, the level in the batch tank remains con-
stant. This operation is continued until the
desired alcohol concentrations in the beer are
achieved.
3. Alcohol adjustment: In this step, the taste and
alcohol content is fine-tuned by addition of
desalted and deoxygenized water.
4. Posttreatment: In order to give the beer its
specific character and to balance taste losses
due to removal of the taste carrier alcohol, the
CO2 levels can be adjusted, and hop extract,
syrup, or other flavor enhancers are added.
As an alternative to reverse osmosis, dialysis
can be used for the dealcoholization of beer.
Commonly, hollow fiber modules are used for
dialysis allowing the beer to flow on one side of
the membrane and water as dialysate on the other
side. The process is normally operated in counter-
current flow to maximize the concentration gra-
dient over the dialysis membrane and thus the
2 Beer Dealcoholization
driving force of the dialysis process. The dialy-
sate is constantly recycled over a steam stripping
column to remove the alcohols, thus maintaining
the driving force of the process while minimizing
the dialysate consumption. In addition, in order to
minimize CO2 losses, the feed pressure should be
selected close to the CO2 saturation pressure, and
small amounts of the CO2 should be added to the
dialysate (Branyik et al. 2012).
Furthermore, osmotic distillation for beer
dealcoholization (Russo et al. 2013) and
pervaporation for aroma recovery can be consid-
ered as part of the beer dealcoholization process
(del Olmo et al. 2012), but so far these processes
are not commercialized.
References
Branyik T, Silva DP, Baszczynski M, Lehnert R, Almeida
e Silva JB (2012) A review of methods of low alcohol
and alcohol-free beer production. J Food Eng
2012(108):493–506
del Olmo A, Blanco CA, Palacio L, Prádanos P,
Hernández A (2012) Setting up of a method of
pervaporation for improving alcohol-free beer.
Euromembrane, London, pp 23–27
Gebhardt W (2001) Weltforum der Wein- und
Saftbereitung. F&S Filtrieren Separieren 15(5):229
Russo P, Liguori L, Albanese D, Crescitelli A, Di Matteo
M (2013) Investigation of osmotic distillation tech-
nique for beer dealcoholization. CEt Chem Eng
Trans 32:1735–1840
B
Beer Maturation
Frank Lipnizki
Alfa Laval Copenhagen, Søborg, Copenhagen,
Denmark
In the beer production process, the clarified and
cooled wort from the brewhouse is transferred
together with yeast to the fermentation tanks for
the primary fermentation which converts the fer-
mentable sugar into alcohol and CO2. The
resulting “green beer” undergoes a second
fermentation – beer maturation – under addition
of sugar or fresh yeasted wort. During the matu-
ration, the residual fermentable sugars in the
“green beer” will be converted to alcohol and
the beer will be saturated with CO2. After the
fermentation, the beer is clarified and stored in
the bright beer cellar. Remaining in the fermen-
tation tanks are tank bottoms – a mixture of
settled yeast cells and beer – which are equal
approx. 1.5–2.0 % of the fermentation tank vol-
ume. In the past this beer in the tank bottom
would be considered lost since it could not be
added to the main beer stream. However, using
microfiltration with tubular ceramic membranes
or plate-and-frame modules with polymeric
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_48-2
membranes, it is possible to recover a high-
quality beer which can be blended with the main
beer stream going toward clarification and stor-
age. Using microfiltration membranes with pores
of 0.4–0.5 mm, it is possible to retain the yeast and
allow the beer to pass the membrane without any
major impact on the quality of the beer. In this
process, the yeast in the tank bottoms is concen-
trated from 7 % to 10 % DM to approx. 20 % DM
and thus 50–70 % of the beer in the tank bottoms
can be recovered. The yield of recovered extract
and alcohols can be further maximized if
diafiltration water is added. Recovering beer
from tank bottoms can increase the output of an
average brewery by 1 % of its annual production
or 24,000 hl extra for a brewery with an annual
output of 2 million hl (Lipnizki 2005). The amor-
tization for a microfiltration beer recovery unit is
typically 1–2 years.
Reference
Lipnizki F (2005) Optimisation and integration of mem-
brane processes in the beverage industry, 10. Aachener
Membran Kolloquium, 16.-17.03.2005: preprints. -
Aachen, Mainz, 2005. - 3-86130-409-0.
B
Benzene and Cyclohexane
Separation
Tadashi Uragami
Kansai University, Organization for Research
and Development of Innovative Science and
Technology (ORDIST), Suita, Osaka, Japan
Benzene/Cyclohexane Separation
In the petrochemical industry, the separation of
benzene (Bz) and cyclohexane (Chx) is the most
important and difficult processes. Chx is pro-
duced in benzene hydrogenation units under Ni
or Pd catalyst. The unreacted Bz is remained in
the reaction mixture and must be removed to
produce pure Chx. The separation of benzene
and Chx is very difficult by a conventional distil-
lation because close-boiling point mixtures are
formed in the entire range of their compositions.
At present, azeotropic distillation and extractive
distillation are applied to this separation. These
distillations, however, are complex and need high
energy consumption. In the industry of Chx pro-
duction, the conventional Bz/Chx separation pro-
cesses are strongly required. Therefore, many
studies have investigated the PV properties of
polymer membranes for Bz/Chx separation.
Pervaporation (PV) is a promising membrane
technique for the separation of organic/organic
mixtures, as PV can be used to separate organic
liquid mixtures such as azeotropic and close-
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_49-1
boiling point mixtures. The separation mecha-
nism in PV is not based on only relative volatility
of components in distillation but on the differ-
ence in sorption and diffusion properties of the
feed substances.
Figure 1 illustrates the principles of PV. In this
separation process, when a liquid mixture is fed
to the upstream side of a polymer membrane and
the downstream side is evacuated, a component
in the feed mixture can preferentially permeate
through the membrane. In a PV process, differ-
ences between the solubility and diffusivity of the
mixture components in the polymer membrane
and the relative volatility of the permeants deter-
mine the permeability and selectivity (Binding
et al. 1961; Aptel et al. 1974). In general, PV
exhibits the following characteristics (Uragami
2006, 2010):
1. Selective transport across the nonporous
membrane is achieved by a three-step process
of solution, diffusion, and evaporation.
2. Because the driving force for permeation is the
vapor pressure for each component rather than
total system pressure, this method is effective
for separation of organic liquid mixtures with
high osmotic pressure.
3. PV can be applied to the separation and con-
centration of mixtures that are difficult to sep-
arate by distillation. For example, it is useful
for the separations of azeotropic mixtures,
close-boiling point mixtures, and structural
isomers.
2 Benzene and Cyclohexane Separation

temperature and the LCP membrane exhibited

selectivity for the aromatic hydrocarbons. The
permeation rate and selectivity of the LCP mem-
brane for each mixture decreased with increasing
molecular size of the aromatic hydrocarbon in the
binary feed mixture (Inui et al. 1998). When
Bz/Chx mixtures were permeated through
nematic and smectic side-chain liquid-crystalline
polymer (n- and s-LCP) membranes under vari-
ous conditions during PV, the n- and s-LCP mem-
branes exhibited Bz/Chx selectivity. The
selectivity of the n-LCP membrane changed
from solubility-selectivity controlled to
Benzene and Cyclohexane Separation,
diffusion-selectivity controlled upon the state
Fig. 1 Principle of pervaporation (PV)
transformation of the membrane, induced by an
increase in the permeation temperature. In con-
4. PV can be used for the removal of certain
trast, the selectivity of the s-LCP membrane was
components in equilibrium reactions.
governed by diffusion selectivity regardless of
5. Polymer membrane compaction, a frequent
the state of this membrane. At low permeation
problem in high-pressure gas separations, is
temperatures, the n-LCP membrane in the liquid-
not encountered in PV because the feed pres-
crystalline state exhibited lower permeability but
sure is typically low.
higher selectivity than the s-LCP membrane.
However, at high permeation temperatures, the
A side-chain liquid-crystalline polymer (LCP)
relationship between the permeability and
was synthesized by the addition of mesogenic
Bz/Chx selectivity of the n-LCP and s-LCP mem-
monomer to poly(methylsiloxane) with a Pt cat-
branes in the liquid-crystalline state was
alyst. When Bz/Chx mixtures were permeated
reversed. These results are a result of differences
through the LCP membranes by PV at various
in the chemical and physical structure of the
temperatures, the permeation rate increased with
n-LCP and s-LCP membranes (Inui et al. 1998).
increasing benzene concentration in the feed
The PV properties of a series of cross-linked
solution and permeation temperature. Although
4,40 -hexafluoro-isopropylidene dianhydride
the LCP membranes exhibited Bz/Chx selectiv-
(6FDA)-based copolyimide membranes for the
ity, the mechanism responsible for the perme-
separation of Bz/Chx mixtures were investigated
ation and separation of the Bz/Chx mixtures was
(Ren et al. 2001). The glassy, highly rigid
different in the glassy, liquid-crystalline state
copolyimides were obtained by polycondensa-
versus the isotropic state of the LCP membranes.
tion of 6FDA with various diamines. To obtain
These results suggest that the Bz/Chx selectivity
high permeability as well as high selectivity, a
was moderately influenced by the change in LCP
combination of the diamines 2,3,5,6-tetramethyl-
membrane structure (i.e., a state transformation).
1,4-phenylene diamine (4MPD), 4,40 hexafluoro-
The balance between the orientation of the
isopropylidiene dianiline (6FpDA), and
mesogenic groups and the flexibility of the silox-
3,5-diaminobenzoic acid (DABA) as monomers
ane chain is very important with respect to per-
with a crosslinkable group was used. Cross-
meability and Bz/Chx selectivity (Inui
linking is necessary to prevent undesirable swell-
et al. 1997, 1998). When benzene/cyclohexane,
ing effects, which generally occur with
toluene/cyclohexane, and o-xylene/cyclohexane
non-cross-linked polyimides, especially if high
mixtures were subjected to PV through an LCP
benzene concentrations are reached during
membrane in the liquid-crystalline state, the per-
PV. The degree of cross-linking was kept con-
meation rate increased with increasing
stant at 20 %, whereas the ratio of the diamine
Benzene and Cyclohexane Separation
monomers 6FpDA and 4MPD was varied. The
PV experiments were performed at 60  C, using
Bz/Chx mixtures with benzene concentrations
covering the entire concentration range. All of
the cross-linked polymers had excellent chemical
and thermal stability in the PV experiments. In all
cases, conditioning of the membrane samples
with pure benzene was a suitable pretreatment
to enhance the permeation rate without decreas-
ing the Bz/Chx selectivity significantly. For the
most promising membrane material, 6FDA-
4MPD/DABA of 4:1 cross-linked with ethylene
glycol, the PV experiments were performed with
a benzene/cyclohexane feed mixture of 50/50
(w/w) over a temperature range between 60  C
and 110  C to determine the effect of temperature
on the separation characteristics.
References
Aptel P, Cuny J, Jozenfonvice J, Morel G, Neel J (1974)
Liquid transport through membranes prepared by
grafting of polar monomer onto poly(tetrafluor-
oethylene) films. II. Some factors determining
pervaporation rate and selectivity. J Appl Polym Sci
18:365
3
Binding RC, Lee RJ, Jennings JF, Mertic EC (1961) Sep-
aration of liquid mixtures by pervaporation. Ind Eng
Chem 53:47
Inui K, Miyata T, Uragami T (1997) Permeation and
separation of benzene/cyclohexane mixtures through
liquid-crystalline polymer membranes. J Polym Sci
Part B Polym Phys 35:699
Inui K, Miyata T, Uragami T (1998a) Effect of permeation
temperature on permeation and separation of a ben-
zene/cyclohexane mixture through liquid-crystalline
polymer membranes. J Polym Sci Part B Polym Phys
36:281
Inui K, Miyata T, Uragami T (1998b) Permeation and
separation of binary organic mixtures through a
liquid-crystalline polymer membrane. Macromol
Chem Phys 199:589
Inui K, Okazaki K, Miyata T, Uragami T (1998c) Effect of
mesogenic groups on characteristics of permeation and
separation for benzene/cyclohexane mixtures of side-
chain liquid-crystalline polymer membranes. J Membr
Sci 143:93
Ren J, Standt-Bickel C, Lichtenthaler R (2001) Separation
of aromatics/aliphatics with crosslinked 6FDA-based
copolyimides. Sep Purif Technol 22–3:31
Uragami T (2006) Polymer membranes for separation of
organic liquid mixtures. In: Yanpolskii Y, Pinnau I,
Freeman BD (eds) Materials science of membranes for
gas and vapor separation. Wiley, Chichester,
pp 355–372
Uragami T (2010) Selective membranes for purification
and separation of organic liquid mixtures. In: Drioli E,
Georno L (eds) Comprehensive membrane science and
engineering, volume 2 membrane operations in molec-
ular separations. Elsevier, Amsterdam, pp 273–324
B
Biodegradable Membrane
Isabel Coelhoso1, Filomena Freitas2, Vitor D.
Alves3 and Maria A. M. Reis2
1
LAQV- REQUIMTE, Departamento de
Quı́mica, Faculdade de Ciencias e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
2
UCIBIO-REQUIMTE, Departamento de
Quı́mica, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
3
LEAF – Linking Landscape, Environment,
Agriculture and Food, Instituto Superior de
Agronomia, Universidade de Lisboa, Lisboa,
Portugal
Biodegradable membranes consist of thin-film-
like structures usually applied as separating
selective barriers and support devices. These
structures are generally composed of biodegrad-
able polymers, complemented with additives,
such as plasticizers, emulsifiers, and cross-
linking agents. To be considered biodegradable,
all membrane components must be degraded by
the action of microorganisms and converted into
water, carbon dioxide and/or methane, and new
cell biomass.
The wide range of polymers used in the devel-
opment of biodegradable membranes enables the
production of structures with quite diverse prop-
erties, finding applications in different areas. It is
interesting to note that some of them, beyond
being biodegradable, are also biocompatible
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_51-2
and/or edible, extending their use to the fields of
biomedicine and edible coatings for food
products.
Biodegradable polymers obtained by chemical
synthesis have been used, for example, in food
packaging materials (Siracusa et al. 2008) and
medical applications (e.g., fracture fixation, den-
tal orthopedic implants, artificial skin, suture
anchors, drug delivery) (Yen et al. 2009;
Armentano et al. 2010; Bettahalli et al. 2011).
They have also been applied for separation of
organic mixtures by pervaporation (Zereshki
et al. 2010, 2011).
They include the following:
(i) Polyglycolic acid (PGA), an aliphati-
c–aromatic copolymer, which combines
the excellent material properties of aromatic
polyethylene terephthalate and the biode-
gradability of aliphatic polyesters. It is pro-
duced by a polycondensation reaction of
glycol and aliphatic dicarboxylic acids,
which may be obtained from renewable
resources.
(ii) Polylactic acid (PLA), a thermoplastic ali-
phatic polyester obtained from polymeriza-
tion of the lactic acid monomer produced by
microbial fermentation.
(iii) Polycaprolactone (PCL), a thermoplastic
polymer obtained by chemical synthesis
using nonrenewable resources
(petrochemical derivatives).
2 Biodegradable Membrane
Among the biodegradable polymers produced
by microbial fermentation, polysaccharides (e.g.,
pullulan, hyaluronan, gellan, GalactoPol,
curdlan, bacterial alginate, bacterial cellulose)
(Freitas et al. 2011) and polyesters (e.g.,
polyhydroxyalkanoates) have been applied in
films and edible coatings (e.g., pullulan, gellan)
(Nieto 2009; Alves et al. 2011). Both microbial
polysaccharides and polyesters show a wide
range of properties that may be tuned by manip-
ulating the bioreaction conditions. Polyhydrox-
yalkanoates show a wide range of applications,
such as in industry (e.g., packaging, waterproof
paperboard), medicine (e.g., bone plates,
osteosynthetic materials, surgical sutures, and
dressing materials for surgery), and agriculture
(e.g., mulch films) (Philip et al. 2007).
The polymers recovered from natural products
generally used to produce biodegradable mem-
branes include polysaccharides (e.g., starch, cel-
lulose, pectin, alginate, carrageenan, chitosan)
and proteins (e.g., gelatin/collagen, soy protein,
gluten). These polymers are widely used to
develop edible coatings for food products and
biodegradable films intended for food packaging
(Nieto 2009). Chitosan, alginate, and collagen are
also referred to be applied in tissue engineering
(Eisenbarth 2007).
Polysaccharide-based membranes, such as
chitosan and sodium alginate, have received
much attention for solvent dehydration by
pervaporation, due to their good film-forming
properties, chemical resistance, and high
permselectivity for water (Chapman et al. 2008;
Yu et al. 2006).
References
Alves VD, Ferreira AR, Costa N, Freitas F, Reis MAM,
Coelhoso IM (2011) Characterization of
biodegradable films from the extracellular polysaccha-
ride produced by Pseudomonas oleovorans grown on
glycerol byproduct. Carbohydr Polym 83:1582–1590
Armentano I, Dottori M, Fortunati E, Mattioli S, Kenny
JM (2010) Biodegradable polymer matrix
nanocomposites for tissue engineering: a review.
Polym Degrad Stab 95:2126–2146
Bettahalli N, Steg H, Wessling M, Stamatialis D (2011)
Development of poly(L-lactic acid) hollow fiber mem-
branes for artificial vasculature in tissue engineering
scaffolds. J Membr Sci 371:117–126
Chapman PD, Oliveira T, Livingston AG, Li K (2008)
Membranes for dehydration of solvents by
pervaporation. J Membr Sci 318:5–37
Eisenbart E (2007) Biomaterials for tissue engineering.
Adv Eng Mat 9:1051–1060
Freitas F, Alves VD, Reis MAM (2011) Advances in
bacterial exopolysaccharides: from production to bio-
technological applications. Trends Biotechnol
29:388–398
Nieto MB (2009) Structure and function of polysaccharide
gum-based edible films and coatings. In: Embuscado
ME, Huber KC (eds) Edible films and coatings for food
applications. Springer, New York, pp 57–112
Philip S, Keshavarz T, Roy I (2007) Polyhydrox-
yalkanoates: biodegradable polymers with a range of
applications. J Chem Technol Biotechnol 82:233–247
Siracusa V, Rocculi P, Romani S, Rosa MD (2008) Biode-
gradable polymers for food packaging: a review.
Trends Food Sci Technol 19:634–643
Yen C, He H, Lee LJ, Winston Ho WS (2009) Synthesis
and characterization of nanoporous polycaprolactone
membranes via thermally- and nonsolvent-induced
phase separations for biomedical device application.
J Membr Sci 343:180–188
Yu L, Dean K, Li L (2006) Polymer blends and compos-
ites from renewable resources. Prog Polym Sci
31:576–602
Zereshki S, Figoli A, Madaeni SS, Simone S, Jansen JC,
Esmailinezhad M, Drioli E (2010) Poly(lactic acid)/
poly(vinyl pyrrolidone) blend membranes: effect of
membrane composition on pervaporation separation
of ethanol/cyclohexane mixture. J Membr Sci
362:105–112
Zereshki S, Figoli A, Madaeni SS, Galiano F,
Esmailinezhad M, Drioli E (2011) Pervaporation sep-
aration of ethanol/ETBE mixture using poly(lactic
acid)/poly(vinyl pyrrolidone) blend membranes.
J Membr Sci 373:29–35
B
Biodegradable Organic Matter
Isabel Coelhoso1, Filomena Freitas2, Vitor D.
Alves3 and Maria A. M. Reis2
1
LAQV-REQUIMTE, Departamento de
Química, Faculdade de Ciencias e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
2
UCIBIO-REQUIMTE, Departamento de
Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
3
LEAF – Linking Landscape, Environment,
Agriculture and Food, Instituto Superior de
Agronomia, Universidade de Lisboa, Lisboa,
Portugal
Biodegradable organic matter is organic material,
plant, and animal matter with origin in living
organisms, which can be converted by the action
of microorganisms to water, carbon dioxide,
and/or methane and biomass.
Organic materials can be used to obtain bio-
degradable polymers which are classified
according to the method of production or their
source (Fig. 1):
– Polymers directly extracted or removed from
biomass such as polysaccharides and proteins
– Polymers produced by classical chemical syn-
thesis starting from renewable bio-based
monomers such as polylactic acid (PLA)
– Polymers produced by microorganisms or
genetically modified bacteria such as
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_52-1
polyhydroxyalkanoates, bacterial cellulose,
xanthan, and pullulan (Mensitier et al. 2011)
Polysaccharides are the most abundant mac-
romolecules in the biosphere. These complex
carbohydrates constituted of monosaccharides
joined together by glycosidic bonds are often
one of the main structural elements of plant and
animal exoskeleton (e.g., cellulose, carrageenan,
chitin) or have a key role in the plant energy
storage (e.g., starch).
Cellulose and starch are of prime interest as
biopolymers because of their availability and
rather low cost. A variety of polysaccharides
and their derivatives, besides starch and cellulose
derivatives, have been used as biodegradable
membrane-forming matrixes, including alginate,
pectin, carrageenan, chitin, and various gums.
Several protein sources have been proposed
for the preparation of biopolymers, in particular,
cereal proteins which are available in large
amounts as by-products arising from agricultural
and biofuel processing activities such as ethanol
production. These protein-rich products include
spent grain from the brewing and distilling indus-
tries, cereal bran streams from milling, and pro-
tein residues from starch extraction activities
(Mensitier et al. 2011).
Microbial biopolymers are naturally synthe-
sized by microorganisms with different functions
in the microbial cell, including intracellular car-
bon or energy storage reserves (e.g., glycogen,
2 Biodegradable Organic Matter

Biodegradable
Polymers

Biopolymers Polymers
(renewable resources) (fossil resources)

PCL
Extracted from Biomonomer Produced by
Biomass Synthesis Microorganisms
PGA

PLA PHA PBSA

Proteins Polysaccharides

Pullulan

Whey protein Pectin

Glucan
Casein Carrageenan

Soy protein Starch

Gluten Cellulose

Biodegradable Organic Matter, Fig. 1 Biodegradable polymers

polyesters), structural cell wall components (e.g.,
chitin, b-glucans), and extracellular biopolymers
(e.g., exopolysaccharides), often secreted as pro-
tective mechanisms in response to environmental
conditions (Rehm 2010).
A wide range of agro-food and industrial
wastes/by-products have been proposed as alter-
native substrates for the production of microbial
biopolymers, including molasses, cheese whey,
palm date syrup, olive mill wastewater (OMW),
glycerol by-product from the biodiesel industry,
corn-steep liquor, spent malt grains, apple and
grape pomaces, citrus peels, peach pulp, used
oils, and several acid-hydrolysate wastes (e.g.,
melon, watermelon, cucumber, tomato, rice),
among others (Freitas et al. 2011; Verlinden
et al. 2011).
The microbial biopolymers produced include
polysaccharides, polyamides, polyesters, and
polyanhydrides. Depending on their composition
and molecular weight, they have properties
ranging from rheology modifiers to bioplastics,
which makes them useful in many industrial
applications (e.g., agro-food, cosmetics, pharma-
ceutical, textile) (Rehm 2010).
References
Freitas F, Alves VD, Reis MAM (2011) Advances in
bacterial exopolysaccharides: from production to bio-
technological applications. Trends Biotechnol
29(8):388–398
Mensitieri G, Di Maio E, Buonocore G, Nedi I,
Oliviero M, Sansone L, Iannace S (2011) Processing
and shelf life issues of selected food packaging mate-
rials and structures from renewable resources. Trends
Food Sci Technol 22:72–80
Rehm BHA (2010) Bacterial polymers: biosynthesis,
modifications and applications. Nat Rev Microbiol
8:578–592
Verlinden RAJ, Hill DJ, Kenward MA, Williams CD,
Piotrowska-Seget Z, Radecka IK (2011) Production
of polyhydroxyalkanoates from waste frying oil by
Cupriavidus necator. AMB Express 2011:1–11
B
Biogas
Ivo Vankelecom1 and Muhammad Waqas
Anjum2
1
Centre for Surface Chemistry and Catalysis, KU
Leuven, Heverlee, Leuven, Belgium
2
School of Chemical & Materials Engineering,
National University of Science & Technology,
Islamabad, Pakistan
Fossil fuels are still the primary source of energy
by preference. However, as fossil fuels become
more and more expensive with the possibility of
depletion of resources, the quest for alternate
sources of energy is gaining attention. In this
whole situation, anaerobic digestion of biological
resources and biological waste could be a prom-
ising alternative energy carrier.
Natural gas normally consists of 90–95 %
methane, but in biogas this composition is
reduced to 50–65 % making it a low-grade natu-
ral gas which is the product of neutral decompo-
sition of organic substance of animal or plant
origin due to anaerobic bacterial activity. The
plants used for biogas production are normally
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_54-1
referred to as anaerobic digesters or anaerobic
fermenters. The resources used for biogas pro-
duction include kitchen waste, dry poultry drop-
pings and animal excrements, remnants of food
processing, and slaughterhouse leftovers. Four
ingredients needed for biogas production are
organic matter, bacteria, anaerobic conditions,
and heat. In a controlled reaction system, the
gaseous mixture thus produced can contain up
to 70 % of biohydrogen and biomethane, respec-
tively, that can be used for commercial applica-
tions (Harold 2007).
The anaerobic digestion process can be classi-
fied into different sets of complex reactions, as
shown in Fig. 1. Production of biohydrogen and
biomethane from organic wastes consists of
mainly three steps including hydrolysis,
acetogenesis, and methanogenesis. Organic sub-
strates can be converted to biogas by a diverse
group of microbes using multienzyme
(cellulases, amylases, lipases, proteases, etc.)
systems.
Organic material is fed into digesters after
grinding to an appropriate size. In the digesters,
these substrates are heated and agitated leading to
2 Biogas
Biogas, Fig. 1 Schematic
diagram of the anaerobic
digestion process for biogas
generation (Modified from
Basu et al. 2010)
Acetate
production of biogas which is collected in a bio-
gas container. This gas is fed into an electric
generator which produces electricity and heat.
Biohydrogen generated in fermentation pro-
cesses (e.g., anaerobic fermentation, photofer-
mentation, dark fermentation) has hydrogen and
carbon dioxide as major ingredients. On the other
hand, biomethane produced by anaerobic diges-
tion of biological wastes has 38–40 % carbon
dioxide with smaller amounts of hydrogen sulfide
along with trace amounts (ppm) of hydrogen,
nitrogen, oxygen, and volatiles with 55–60 %
methane as a major part (Rasi et al. 2007). Biogas
has a calorific value of 35–44 kJ g 1, which is
comparatively higher than other energy resources
like petrol, diesel, or LPG and solid fuels like
coal, charcoal wood, etc. Biogas is a potential
source of environmentally benign, clean, and
Organic matter
(OM)
Hydrolysis
(Soluble OM)
Fermentation
(Fatty acids)
Methanogenesis H2 + C2
CH4 + CO2
cheap alternative energy. However, the presence
of incombustible and acid gases, like CO2, not
only reduces its calorific value, but their corro-
sive nature restricts its transportation. One of the
many trace components includes silicone
containing compounds. Commonly occurring
siloxanes in biogas are known as volatile methyl
siloxanes (VMS) that include cyclic tri-, tetra-,
and pentasiloxane, as well as linear di-, tri-,
tetrasiloxane. After combustion, undesirable
microcrystalline quartz and pentasiloxane are
produced as they cause the wear & tear of engines
and turbines. Purified biogas can be used as a feed
to fuel cells or for domestic applications and
power generation. Figure 2 represents the possi-
ble applications of biogas (Basu et al. 2010).
Biogas 3

Hydrogen production Fuel cell

Gasification
Bio Gas

Combined Cycle ELectricity Generation

Thermal power

Anaerobic digesstion/ Hydro

Methane Gas engines/Fuel cell
gasifiction

Biogas, Fig. 2 Possible applications of biogas as energy resource (Modified from Basu et al. 2010)

References opportunities 3–4. http://www.londonswineconference.

S. Basu, A.L. Khan, A. Cano-Odena, C. Liu,
I.F.J. Vankelecom, Membrane-based technologies for
biogas separations. Chem Soc Rev 39, 750–768 (2010)
Harold House (2007) Proceeding for London Swine
conference-today’s challenges. Tomorrow’s
ca/proceedings/2007/LSC2007_HHouse.pdf. Accessed
29 Jan 2013.
S. Rasi, A. Veijanen, J. Rintala, Trace compounds of
biogas from different biogas production plants. Energy
32, 1375–1380 (2007)
B
Biogas Recovery
Ivo Vankelecom
Centre for Surface Chemistry and Catalysis,
KU Leuven, Leuven (Heverlee), Belgium
The constant increase in energy demand, coupled
with the depletion of fossil fuels, is a concern that
cannot be ignored in the industrial and highly
populated world of today (Basu et al. 2010). Bio-
gas production is a very promising source of
renewable energy that still offers further exploi-
tation of its potential (Scholz et al. 2013). Essen-
tially, microbially controlled biogas production is
an already existing part of the global carbon
cycle, releasing an estimated 590–800 million
tons of methane to the atmosphere (Bond and
Templeton 2011). Current biogas recovery sys-
tems seek to exploit these processes in order to
produce energy from sewage wastewater, animal
manure, crop straws, or mixed agricultural wastes
(Chen et al. 2012; Rasi et al. 2011). Usually, a
system for biogas recovery consists of four com-
ponents: a collection system which helps transfer
the biogas source to the anaerobic digester, the
anaerobic digester in which the methane produc-
tion takes place, a biogas collection system pro-
viding piping of biogas to a combustion device,
and a gas use device where biogas is combusted
to produce heat or electricity (Agstar 2011).
Alternatively, the produced biogas can be used
on site as fuel for automotives or can be injected
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_55-3
in the natural gas grid. In this case, the gas must
be upgraded to natural gas standards, namely,
98 % methane content (AEBIOM 2009).
Although the composition of biogas varies
significantly depending on many factors such as
the type of digester, the average values are
reported to range between 50 % and 70 % meth-
ane and 30–50 % carbon dioxide, as well as
hydrogen sulfide, sulfur compounds, siloxanes,
and aromatic and halogenated compounds (Rasi
et al. 2007). Upgrading (purification) of biogas is
highly beneficial in terms of increasing the
amount of methane per unit volume of biogas,
which equals an increase in its calorific value. In
addition to the obvious need for removal of car-
bon dioxide as the major pollutant, the trace com-
pounds have the potential to trigger ozone
depletion and the greenhouse effect, reduce the
quality of local air due to formation of volatile
organic compounds (VOCs), and so
on. Moreover, sulfur compounds corrode pipe-
lines and combustion engines, while silicon com-
pounds oxidize and are deposited on engine parts
(Rasi et al. 2007). Currently, biogas upgrading is
largely achieved through amine scrubbing where
carbon dioxide is absorbed into an amine solu-
tion, water scrubbing where carbon dioxide is
absorbed to water at elevated pressures, and pres-
sure swing adsorption where pressure of the gas
mixture is changed to induce adsorption and
desorption of one gas species. These technologies
are in general more energy intensive and pollut-
ing than membrane technology (Basu et al. 2010;
2 Biogas Recovery
AEBIOM 2009; Scholz et al. 2013). Polymeric
membranes have gained a share in the separations
market, as opposed to the inorganic membranes
which are expensive and brittle. Some commer-
cial polymeric membranes such as SEPAREX
(cellulose acetate) of UOP and polydimethyl
siloxane (PDMS) have already proven or were
reported to operate successfully in separation of
carbon dioxide or siloxanes and VOCs, respec-
tively. However, the separation of hydrogen sul-
fide still remains a difficult and interesting issue
for membrane research. Mixed matrix mem-
branes composed of inorganic particles distrib-
uted throughout a polymeric matrix are
promising alternatives thoroughly investigated
for these separations (Basu et al. 2010).
References
Agstar-EPA (2011). Market opportunities for biogas
recovery systems at U.S. Livestock Facilities. http://
epa.gov/agstar/documents/biogas_recovery_systems_
screenres.pdf. Accessed 31 Jan 2013
Basu S, Khan AL, Cano-Odena A, Lui C, Vankelecom IFJ
(2010) Membrane-based technologies for biogas sep-
arations. Chem Soc Rev 39(2):750–768
Bond T, Templeton MR (2011) History and future of
domestic biogas plants in the developing world.
Energy Sustain Dev 15(4):347–354
Chen L, Lixin Z, Changshan R, Fei W (2012) The progress
and prospects of rural biogas production in China.
Energy Policy 51:58–63
European Biogas Association-AEBIOM (2009). A biogas
road map for Europe. http://www.aebiom.org/IMG/
pdf/Brochure_BiogasRoadmap_WEB.pdf. Accessed
31 Jan 2013
Rasi S, Veijanen A, Rintala J (2007) Trace compounds of
biogas from different biogas production plants. Energy
32(8):1375–1380
Rasi S, Läntelä J, Rintala J (2011) Trace compounds
affecting biogas energy utilization – a review. Energy
Convers Manag 52(12):3369–3375
Scholz M, Melin T, Wessling M (2013) Transforming
biogas into biomethane using membrane technology.
Renew Sust Energ Rev 17:199–212
B
Biohybrid Artificial Liver (BAL)
Sabrina Morelli
National Research Council of Italy, Institute on
Membrane Technology, ITM-CNR, Rende, CS,
Italy
A biohybrid artificial liver (BAL) is a bioartificial
device which consists of functional liver cells
supported by an artificial cell culture material. It
incorporates hepatocytes into a bioreactor in
which the cells are immobilized, cultured, and
induced to perform the hepatic functions by
processing the blood or plasma of liver failure
patients. BAL provides temporary support for
patients waiting for an allogeneic liver transplant,
and since the liver can regenerate, the temporary
support provided by BAL may allow time for
liver regeneration.
The bioreactor is an important component of
BAL, because it determines the viability and
function of the hepatocytes within it. A success-
ful and clinically effective bioreactor should
mimic the structure of the liver and provide an
in vivo-like microenvironment for the growth of
hepatocytes, thereby maintaining the cells’ via-
bility and function to the maximum extent. The
important issues are the choice of cell sources and
the design of the bioreactor (Ding and Shi 2011).
The cell sources provide liver-specific functions,
such as detoxification, drug metabolism, and pro-
tein synthesis, while the bioreactors maintain the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_56-3
viability and function of cells. More efforts are
now underway in search for the best cell resource
and best design of bioreactors.
Considering the several functions that the liver
performs, the bioreactor for BAL devices has to
ensure the rapid detoxification of neural and
hepatic toxins, the return of liver-specific
hepatotrophic factors, as well as liver-specific
coagulation factors, back into patient’s blood,
and the maintenance of liver cell detoxification
and synthetic functions until liver tissue regener-
ation or organ transplantation.
One of the most promising bioreactors is the
membrane bioreactor. Polymeric membranes in
flat and hollow fiber configuration with different
morphology and chemical–physical properties
have been used in BAL devices (De Bartolo and
Bader 2001; Kamlot et al., 1996; Kasuya and
Tanishita 2012). Most of the extracorporeal
BALs have not only used cellulose and
polysulfone derivatives but also native and mod-
ified polypropylene membranes. Morphological
(e.g., pore size, pore size distribution, and rough-
ness) and physicochemical membrane properties
(e.g., surface charge, wettability, and surface free
energy) affect all the adhesion and metabolic
functions of hepatocytes.
Hepatocytes have been cultured in membrane
bioreactors in different configurations: between
flat sheet membranes in a sandwich configura-
tion; in the lumen of hollow fiber membranes
entrapped in a collagen layer; in the shell of
hollow fiber membranes in monolayer,
2 Biohybrid Artificial Liver (BAL)
aggregate, or spheroid structure and attached to
microcarriers; in a network of hollow fiber mem-
branes with different functions; in a spirally
wound device in which hollow fibers are used to
provide oxygen to the cells; in multibore capil-
laries; microencapsulated and in an oxygen-
permeable membrane rotating system under
microgravity conditions.
Several designs of BAL devices that are dif-
ferent in configuration, cell source, and culture
technique have currently undergone clinical trials
(Morelli et al. 2010).
References
De Bartolo L, Bader A (2001) Review of a flat membrane
bioreactor as a bioartificial liver. Ann Transplant
6:40–46
Ding YT, Shi XL (2011) Bioartificial liver devices: per-
spectives on the state of the art. Front Med 5:15–19
Kamlot A, Rozga J, Watanable FD, Demetriou AA (1996)
Review: Artificial liver support systems. Biotechnol
Bioeng 50:382–391
Kasuya J, Tanishita K (2012) Microporous membrane-
based liver tissue engineering for the reconstruction
of three-dimensional functional liver tissues in vitro.
Biomatter 2:290–295
Morelli S, Salerno S, Piscioneri A, Campana C, Drioli E,
De Bartolo L (2010) Membrane bioreactors for regen-
erative medicine: an example of the bioartificial liver.
Asia Pac J Chem Eng 5:146–159
B
Biohybrid Artificial Liver (BAL)
Systems
Sabrina Morelli
National Research Council of Italy, Institute on
Membrane Technology, ITM-CNR, Rende,
CS, Italy
A biohybrid artificial liver (BAL) system is an
artificial extracorporeal supportive device which
represents an important therapeutic strategy for
patients with acute liver failure.
Generally, a BAL system consists of func-
tional liver cells supported by an artificial cell
culture material. In particular, it incorporates
hepatocytes into a bioreactor in which the cells
are immobilized, cultured, and induced to per-
form the hepatic functions by processing the
blood or plasma of liver failure patients. The
BAL system acts as a bridge for the patients
until a donor organ is available for transplanta-
tion or until liver regeneration. The development
of a BAL system involves many design consider-
ations. It must provide (1) an adhesion support to
the cells; (2) adequate mass transfer of oxygen,
nutrients, and toxic substances from the blood or
plasma of patients to the cell compartments and
proteins, catabolites, and other specific com-
pounds produced by cells from the cell compart-
ment to the blood or plasma;
(3) immunoprotection of cells; and (4) biocom-
patibility. BAL devices are classified by the cell
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_57-3
source, the type of culture system for the hepato-
cytes, and the configuration of the bioreactor.
Several BAL systems have been evaluated
preclinically in in vitro experiments and in large
animal models of liver failure (Morelli
et al. 2010). Currently, different types of BAL
devices are in various stages of clinical evalua-
tion, and some of them are listed in Table 1 (van
de Kerkhove et al. 2004).
Many of these devices use hollow fiber mem-
branes (HFMs) as supports for the cultured hepa-
tocytes and as immunoselective barriers between
the plasma of the patients and the hepatocytes
used in the bioreactor. Membranes also permit
the transport of nutrients and metabolites to
cells and the transport of catabolites and specific
metabolic products to the blood. In the membrane
bioreactors, mass transfer is determined by the
molecular weight cutoff (MWCO) or pore diam-
eter of the membrane and occurs by diffusion
and/or convection in response to existing trans-
membrane concentration or pressure gradients.
Most of the bioreactors for BAL systems use
membranes with MWCO ranging from 70 to
100 kDa that allow the transport of serum albu-
min but exclude proteins with high MW such as
immunoglobulins and cells.
One of the first clinical devices using HFMs
was developed by Sussman and coworkers,
namely, the extracorporeal liver-assist device
(ELAD) in which the human hepatocytes were
located outside the hollow fiber and blood flows
through the lumen of the hollow fibers. This
2 Biohybrid Artificial Liver (BAL) Systems
Biohybrid Artificial Liver (BAL) Systems, Table 1 Membrane BAL systems in clinical evaluation
Bioreactor
BAL system configuration
Kiil dialyzer bioartificial liver Plate
ELAD Hollow fiber
Amphioxus Cell Technology
LLS Hollow fiber
Charite, Humboldt University,
Germany
HepatAssist Hollow fiber
Circe Biomedical
AMC-BAL Spirally wound
University of Amsterdam
BLSS Hollow fiber
Excorp Medical Inc.
BAL TECA Corp. Hollow fiber
device was commercialized by Amphioxus Cell
Technologies (Sussman et al. 1992). HepatAssist
Circe Biomedical is the most clinically advanced
system of its kind. It is an extracorporeal cell-
based bioartificial liver device, based on the use
of an open membrane hollow fiber bioreactor
(Demetriou et al. 1995). In this system, hepato-
cytes are loaded into the extracapillary space, and
the patient’s plasma flows through the capillary
lumina of membranes. A more complex system is
the liver support system (LSS) or the modular
extracorporeal liver system (MELS) which con-
sists of a bioreactor with four interwoven inde-
pendent capillary membrane systems that serve
different functions (Gerlach et al. 1994). The
BLSS is a hollow fiber device that uses porcine
hepatocytes embedded in a collagen matrix
(Patzer et al. 2002). The Academic Medical Cen-
ter Bioartificial Liver (AMC-BAL) developed by
Flendrig et al. uses a three-dimensional, spirally
wound, nonwoven polyester matrix for hepato-
cyte attachment with integrated hollow fibers for
oxygen delivery to the cells (Flendrig et al. 1997).
Another BAL system that is currently in clinical
testing is a bioreactor from TECA Corp. in which
a polysulfone membrane compartmentalizes por-
cine hepatocytes (Ding et al. 2003).
Membrane References
Cellulose Matsumura
et al. (1987)
Cellulose acetate Sussman
et al. (1992)
Polyamide Gerlach
Polyethersulfone et al. (1994)
Polypropylene
Polysulfone Demetriou
et al. (1995)
Nonwoven polyester matrix, Flendrig
polypropylene et al. (1997)
Cellulose acetate Patzer et al. (2002)
Polysulfone Ding et al. (2003)
References
Demetriou AA, Rozga J, Podesta L, Lepage E, Woolf G,
Vierling J, Makowka LE, Moscioni AD, Hoffman A,
McGrath M, Kong L, Rosen H (1995) Early clinical
experience with a hybrid bioartificial liver. Scand
J Gastroenterol 208:111–117
Ding YT, Qiu YD, Chen Z, Xu QX, Zhang HY, Tang Q,
Yu DC (2003) The development of a new bioartificial
liver and its application in 12 acute liver failure
patients. World J Gastroenterol 9:829–832
Flendrig LM, la Soe JW, Jorning GG, Steenbeek A,
Karlsen OT, Bovee WM, Ladiges NC, Te Velde AA,
Chamuleau RA (1997) In vitro evaluation of a
novel bioreactor based on an integral oxygenator
and a spirally wound nonwoven polyester matrix for
hepatocyte culture as small aggregates. J Hepatol
26:1379–1392
Gerlach JC, Encke J, Hole O, Muller C, Ryan CJ, Neuhaus
P (1994) Bioreactor for larger scale hepatocyte in vitro
perfusion. Transplantation 58:984–988
Matsumura KN, Guevara GR, Huston H, Hamilton WL,
Rikimaru M, Yamasaki G, Matsumura MS
(1987) Hybrid bioartificial liver in hepatic failure:
preliminary clinical report. Surgery 101:99–103
Morelli S, Salerno S, Piscioneri A, Campana C, Drioli E,
De Bartolo L (2010) Membrane bioreactors for regen-
erative medicine: an example of the bioartificial liver.
Asia Pac J Chem Eng 5:146–159
Patzer JF, Mazariegos GV, Lopez R (2002) Preclinical
evaluation of the Excorp Medical, Inc, bioartificial
liver support system. J Am Coll Surg 195:299–310
Biohybrid Artificial Liver (BAL) Systems 3

Sussman NL, Chong MG, Koussayer T, He DE, Shang van de Kerkhove MP, Hoekstra R, Chamuleau RAFM,
TA, Whisennand HH, Kelly JH (1992) Reversal of van Gulik TM (2004) Clinical application of
fulminant hepatic failure using an extracorporeal bioartificial liver support systems. Ann Surg
liver assist device. Hepatology 16:60–65 240:216–230
B
Biohybrid Membrane Systems
Sabrina Morelli
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
Biohybrid membrane systems are engineered
systems based on the combination of biological
units, cells, or tissues, immobilized on an artifi-
cial structure, the membrane. In these systems,
membranes act as instructive materials which are
capable of supporting tissue/organ formation.
Cells have to make an intimate contact with the
surface of the membrane but also to develop close
cell-cell connections, which is a precondition for
their survival and high functional activity.
Among polymeric materials, membranes in
flat and hollow fiber configuration are the most
attractive in the use of biohybrid systems for their
characteristics of stability, biocompatibility, and
selective permeability. Polymeric membranes
could mimic the extracellular matrix with which
cells interact allowing the organization of the
cells into a three-dimensional architecture. The
membranes are able to modulate the adhesion,
proliferation, and differentiation of cells which
are fundamental processes for tissue regeneration
by governing the mass transfer of molecules that
generate a precisely controlled microenviron-
ment that mimic the specific features of in vivo
environments.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_58-3
Biohybrid membrane systems are successfully
applied in the field of tissue engineering and
regenerative medicine (Morelli et al. 2009). For
the development of functional biohybrid mem-
brane systems, a number of issues need to be
addressed: morphological, physicochemical,
mechanical, and transport properties of the mem-
brane, the optimal density of immobilized cells,
the interaction of cells with the membrane, the
differentiation of cells, as well as the mainte-
nance of viability and metabolic functions
in vitro membrane constructs.
Different types of biohybrid membrane sys-
tems have been proposed for the reconstruction
and/or regeneration of many organs and tissues
(e.g., the pancreas, liver, kidney, skin, and bone
Scharp et al. 1994; Saito et al. 2006; De Bartolo
et al. 2009; Ding and Shi 2011; Gentile
et al. 2011).
Currently, biohybrid membrane systems are
also developed for the creation of a biomimetic
microenvironment for neural tissue engineering
since they may be used for the in vitro simulation
of human brain functions. Semipermeable hollow
fiber membranes are widely used as guidance
channels in promoting in vitro and in vivo neuro-
nal regeneration (Zhang et al. 2005; Morelli
et al. 2010, 2012).
Generally, biohybrid membrane systems
could not only have a role in the replacement of
injured organ or tissue but also accelerate the
development of new drugs that may cure patients
as an alternative to animal experimentation.
2 Biohybrid Membrane Systems
References
De Bartolo L, Salerno S, Curcio E, Piscioneri A, Rende M,
Morelli S, Tasselli F, Bader A, Drioli E (2009) Human
hepatocyte functions in a crossed hollow fiber mem-
brane bioreactor. Biomaterials 30:2531–2543
Ding YT, Shi XL (2011) Bioartificial liver devices:
perspectives on the state of the art. Front Med
5:15–19
Gentile P, Chiono V, Tonda-Turo C, Ferreira AM,
Ciardelli G (2011) Polymeric membranes for guided
bone regeneration. Biotechnol J 6:1187–1197
Morelli S, Salerno S, Piscioneri A, Rende M, Campana C,
Drioli E, De Bartolo L (2009) Membranes in regener-
ative medicine and tissue engineering. In: Drioli E,
Giorno L (eds) Membrane operations: innovative sep-
arations and transformations. Wiley VCH, Verlag
GmbH & Co. KGaA, Weinheim, pp 433–446
Morelli S, Salerno S, Piscioneri A, Papenburg BJ, Di
Vito A, Giusi G, Canonaco M, Stamatialis D,
Drioli E, De Bartolo L (2010) Influence of micro-
patterned PLLA membranes on outgrowth and orien-
tation of hippocampal neurites. Biomaterials
31:7000–7011
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C,
Tasselli F, di Vito A, Giusi G, Canonaco M, Drioli E,
De Bartolo L (2012) Flat and tubular membrane sys-
tems for the reconstruction of hippocampal neuronal
network. J Tissue Eng Regen Med 6:299–313
Saito A, Aung T, Sekiguchi K, Sato Y, Vu DM, Inagaki M,
Kanai G, Tanaka R, Suzuki H, Kakuta T (2006) Pre-
sent status and perspectives of bioartificial kidneys.
J Artif Organs 9:130–135
Scharp DW, Swanson CJ, Olack BJ, Latta PP, Hegra OD,
Doherty EJ, Gentile FT, Flavin KS, Ansara MF, Lacy
PE (1994) Protection of encapsulated human islets
implanted without immunosuppression in patients
with type I or type II diabetes and in nondiabetic
control subjects. Diabetes 43:1167–1170
Zhang N, Yan H, Wen X (2005) Tissue-engineering
approaches for axonal guidance. Brain Res Rev
49:48–64
B
Biosurfactant
Frederico de Araujo Kronemberger
COPPE – Chemical Engineering Program,
Federal University of Rio de Janeiro (UFRJ), Rio
de Janeiro, RJ, Brazil
A biosurfactant (also called microbial surfactant)
can be defined as a surfactant compound pro-
duced by microorganisms. Since surfactants are
amphiphilic compounds, presenting both hydro-
philic and hydrophobic moieties, they tend to
move toward the interfaces, reducing the surface
and/or interfacial tensions. These properties
make surfactants excellent detergency, emulsi-
fier, foaming, and dispersing agents (Mukherjee
and Das 2010). Biosurfactants can be categorized
mainly by their chemical composition and their
microbial origin, being classified as glycolipids,
lipopeptides and lipoproteins, phospholipids and
fatty acids, polymeric surfactants, and particulate
surfactants, and they are produced by a great
variety of microorganisms, either secreted extra-
cellularly or attached to parts of cells (Desai and
Banat 1997). The biosurfactants have several
advantages over chemically synthesized surfac-
tants such as lower toxicity, higher biodegrad-
ability, and effectiveness at extreme
temperatures or pH values, besides presenting
high surface activity and low critical micelle con-
centration values emerging as promising substi-
tutes of the latter (Vaz et al. 2012).
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_61-1
Concerning the oil industry, biosurfactants
can be used in the bioremediation of oil pollut-
ants, in the enhanced oil recovery (reducing the
capillary forces that retain the oil in the reservoir
rock), in the treatment of oily sludges, and in the
cleanup of storage tanks. They can also be
applied in the pharmaceutical (due to their anti-
microbial activity) and agricultural sectors (for
the hydrophilization of heavy soil), as a pesticide,
and in the food industry (Mukherjee and Das
2010; Banat 1995; Freire et al. 2009). They can
also be used in the effluent treatment, for metal
ion removal from aqueous solutions (Ramani
et al. 2012) and to enhance the water/oil interac-
tion in the degradation of high fat content efflu-
ents (Damasceno et al. 2012).
Regarding membrane separation processes,
biosurfactants can be used in the micellar
enhanced ultrafiltration, in which small contami-
nants, like heavy metal ions, are bound onto
larger surfactant micelle complexes. These ions
associated with surfactant macromolecules can
be easily retained by an ultrafiltration membrane
module. El Zeftawy and Mulligan (2011) inves-
tigated the use of rhamnolipid biosurfactants
(glycolipids) in the micellar enhanced ultrafiltra-
tion of cadmium, copper, nickel, lead, and zinc
ions with polysulfone hollow-fiber ultrafiltration
membranes with molecular weight cutoff of
10,000 and 30,000. The authors reported nearly
complete rejection of the ions, considering a feed
concentration of 5 mg.L 1, when using a
rhamnolipid solution above its critical micelle
2 Biosurfactant
concentration with both membranes. Even when
increasing the metal ion content up to 50 mg.L 1,
the biosurfactant concentration could be adjusted
to enable their complete rejection, with a perme-
ate flux up to 200 L.h 1.m 2.bar 1. Hong
et al. (1998) also reported the ultrafiltration of
copper, zinc, cadmium, and nickel ions using a
polycarboxylic acid-type biosurfactant. The
author used flat-sheet cellulose acetate mem-
branes with molecular weight cutoff of 1,000
and 3,000, but the biosurfactant was not as effec-
tive as the rhamnolipid reported by El Zeftawy
and Mulligan (2011), leading to lower rejection
values.
Another interesting application of
biosurfactant was reported by Qin et al. (2012).
These authors used rhamnolipid biosurfactants to
enhance the frying oil degradation and to reduce
the membrane fouling in a submerged membrane
bioreactor, and an increase from 66 % up to 91 %
in the oil removal efficiency was reported. The
antifouling property of the biosurfactant was also
confirmed.
Besides, the biosurfactants could be used to
replace their chemically synthesized counterparts
in several other membrane processes, like the
micellar enhanced ultrafiltration of aromatic
alcohols and in the emulsion liquid membranes,
used to remove and/or purify metal ions, dyes,
lignosulfonate, and lactic acid.
References
Banat IM (1995) Biosurfactants production and possible
uses in microbial enhanced oil recovery and oil pollu-
tion remediation: a review. Bioresour Technol 51:1–12
Damasceno FRC, Cammarota MC, Freire DMG
(2012) The combined use of a biosurfactant and an
enzyme preparation to treat an effluent with a high fat
content. Colloid Surf B 95:241–246
Desai JD, Banat IM (1997) Microbial production of sur-
factants and their commercial potential. Microbiol
Mol Biol R 61:47–64
El Zeftawy MAM, Mulligan CN (2011) Use of
rhamnolipid to remove heavy metals from wastewater
by micellar-enhanced ultrafiltration (MEUF). Sep
Purif Technol 77:120–127
Freire DMG, Araujo LV, Kronemberger FA, Nitschke
M (2009) Biosurfactants as emerging additives in
food processing. In: Passos ML, Ribeiro CP (eds)
Innovation in food engineering: new techniques and
products, Contemporary Food Engineering Series.
CRC Press, Boca Raton, pp 685–705
Hong J, Yang S, Lee C, Choi Y, Kajiuchi T (1998) Ultra-
filtration of divalent metal cations from aqueous solu-
tion using polycarboxylic acid type biosurfactant.
J Colloid Interf Sci 202:63–73
Mukherjee AK, Das K (2010) Microbial surfactants and
their potential applications: an overview. In: Sen R -
(ed) Biosurfactants, vol 672, Advances in experimen-
tal medicine and biology series. Springer Science
+Business Media, LLC, New York, pp 54–64
Qin L, Zhang G, Meng Q, Zhang H, Xu L, Lv B (2012)
Enhanced submerged membrane bioreactor combined
with biosurfactant rhamnolipids: performance for fry-
ing oil degradation and membrane fouling reduction.
Bioresour Technol 126:314–320
Ramani K, Chandan Jain S, Mandal AB, Sekaran G (2012)
Microbial induced lipoprotein biosurfactant from
slaughterhouse lipid waste and its application to the
removal of metal ions from aqueous solution. Colloid
Surf B 97:254–263
Vaz DA, Gudiña EJ, Alameda EJ, Teixeira JA, Rodrigues
LR (2012) Performance of a biosurfactant produced by
a Bacillus subtilis strain isolated from crude oil sam-
ples as compared to commercial chemical surfactants.
Colloid Surf B 89:167–174
B
Biosurfactant Production
Frederico de Araujo Kronemberger
COPPE - Chemical Engineering Program,
Federal University of Rio de Janeiro (UFRJ), Rio
de Janeiro, RJ, Brazil
A biosurfactant can be defined as a surfactant
compound produced by microorganisms. The
biosurfactants have several advantages over
chemically synthesized surfactants such as
lower toxicity, higher biodegradability, and
effectiveness at extreme temperatures or pH
values, besides presenting high-surface activity
and low-critical micelle concentration values
emerging as promising substitutes of the latter
(Vaz et al. 2012). In the present moment, the
biosurfactants still present high production costs
in comparison to the chemically synthesized sur-
factants. That is mainly the result of the low
productivity of the microbial strains and the inef-
ficient methodology of the bioprocessing. The
technological improvement of the production
process is essential (Kronemberger et al. 2008).
In order to decrease the production costs, the
scale-up of the whole production process, includ-
ing upstream and downstream, should be
developed.
One of the bottlenecks of the biosurfactant
production relies on the fact that most of them
are obtained through aerobic bioreactions. The
use of the conventional submerged aeration can
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_62-1
lead to the formation of very stable foams, caus-
ing serious operational problems. In order to
overcome that difficulty, a nondispersive oxygen-
ation process using membrane contactors can be
applied (Kronemberger et al. 2008, 2012; Gruber
and Chmiel 1991). Kronemberger et al. (2008)
investigated the rhamnolipid-type biosurfactant
production in bioreactors with a nondispersive
oxygenation device, obtaining productivities
higher to the ones observed in shake flasks. This
system was then successfully used in a fed-batch
experiment, in order to assess the potential of a
long-term production (Kronemberger
et al. 2010). Coutte et al. (2010) reported a similar
system for the production of lipopeptide
biosurfactants, comparing internal and external
nondispersive oxygenation.
Several authors have been investigating the
recovery of biosurfactants, mainly surfactin,
using ultrafiltration. Chen et al. (2008a) reported
the flux decline in the ultrafiltration of surfactin
using cellulose ester and polyethersulfone mem-
branes with 100,000 Da of molecular weight cut-
off, and the latter was recommended as the best
one for this kind of experiment, even though the
biosurfactant recovery was a little lower. Isa
et al. (2007) investigated a two-step ultrafiltration
recovery system for surfactin. In the first step
ultrafiltration, surfactin was retained by
polyethersulfone or regenerated cellulose mem-
branes at above its critical micelle concentration.
In the second step, with the same kind of mem-
branes, after the disruption of the micelles by the
2 Biosurfactant Production
addition of methanol, the purified surfactin was
recovered in the permeate. Chen et al. (2008b)
also reported the surfactin recovery, but using
ammonium sulfate salting out, ultrafiltration,
nanofiltration, and their hybrid process. The com-
bination of salting out and ultrafiltration was
selected due to the reduction of the fouling in
the membranes used.
Another point of view should be the whole
integrated production system supported by mem-
brane processes. A system described by Coutte
et al. (2013) comprises the nondispersive oxygen-
ation of a bioreactor for the production of
surfactin and the continuous cell removal and
product separation using microfiltration and
ultrafiltration modules, respectively. A pilot
scale system, designed for the production of
rhamnolipid-type biosurfactants, with 200 L of
useful volume was also described (Kronemberger
et al. 2012). It comprises microfiltration modules
for fresh medium sterilization, nondispersive
oxygenation, another set of microfiltration mod-
ules with self-backwashing for cell retention, and
a reverse osmosis unit used to concentrate the
product and to recover the water as the permeate
stream, enabling its reuse and minimizing the
effluents.
References
Chen H, Chen Y, Juang R (2008a) Flux decline and mem-
brane cleaning in cross-flow ultrafiltration of treated
fermentation broths for surfactin recovery. Sep Purif
Technol 62:47–55
Chen H, Chen Y, Juang R (2008b) Recovery of surfactin
from fermentation broths by a hybrid salting-out and
membrane filtration process. Sep Purif Technol
59:244–252
Coutte F, Lecouturier D, Yahia SA, Leclère V, Béchet M,
Jacques P, Dhulster P (2010) Production of surfactin
and fengycin by Bacillus subtilis in a bubbleless
membrane bioreactor. Appl Microbiol Biotechnol
87:499–507
Coutte F, Lecouturier D, Leclère V, Béchet M, Jacques P,
Dhulster P (2013) New integrated bioprocess for the
continuous production, extraction and purification of
lipopeptides produced by Bacillus subtilis in mem-
brane bioreactor. Process Biochem 48:25–32
Gruber T, Chmiel H (1991) Aerobic production of
biosurfactants avoiding foam problems. In: Reuss M,
Knackmuss HJ, Chmiel H, Gilles ED (eds) Biochem-
ical Engineering-Stuttgart. Fischer Verlag, Stuttgart,
pp. 212–215
Isa MHM, Coraglia DE, Frazier RA, Jauregi P (2007)
Recovery and purification of surfactin from fermenta-
tion broth by a two-step ultrafiltration process.
J Membr Sci 296:51–57
Kronemberger FA, Santa Anna LMM, Fernandes ACLB,
Menezes RR, Borges CP, Freire DMG (2008) Oxygen-
controlled biosurfactant production in a bench scale
bioreactor. Appl Biochem Biotechnol 147:33–45
Kronemberger FA, Borges CP, Freire DMG (2010) -
Fed-batch biosurfactant production in a bioreactor.
Int Rev Chem Eng 2:513–518
Kronemberger FA, Freire DMG, Castro AM, Santa Anna
LMM, Borges CP (2012) System for obtaining biolog-
ical products. Patent WO2012/079138 A1
Vaz DA, Gudiña EJ, Alameda EJ, Teixeira JA, Rodrigues
LR (2012) Performance of a biosurfactant produced by
a Bacillus subtilis strain isolated from crude oil sam-
ples as compared to commercial chemical surfactants.
Colloids Surf B 89:167–174
E
Electrodialysis with Bipolar
Membranes
Heiner Strathmann
Institute for Chemical Technology, Stuttgart
University, Stuttgart, Germany
The conventional electrodialysis can be com-
bined with bipolar membranes and utilized to
produce acids and bases from the corresponding
salts. A bipolar membrane is a laminate of an
anion on a cation-exchange layer. In this process
monopolar cation- and anion-exchange mem-
branes are installed together with bipolar mem-
branes in alternating series in an electrodialysis
stack as illustrated in Fig. 1 which shows a typical
repeating unit of an electrodialysis stack with
bipolar membranes is composed of three cells,
two monopolar membranes and a bipolar mem-
brane. The outer cells of the repeating unit are fed
with a salt solution, the inner cells with water, or a
diluted acid and base. When an electrical poten-
tial gradient is applied across a repeating unit,
protons and hydroxide ions which are generated
in the bipolar membrane generate with the cat-
ions and anions removed from the salt solution,
an acid and a base on either side of the bipolar
membrane. The process design is closely related
to that of the conventional electrodialysis using
the sheet flow stack concept (Liu et al. 1977;
Simons 1993).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_64-1
The utilization of electrodialysis with bipolar
membranes to produce acids and bases from the
corresponding salts is economically very attrac-
tive and has a multitude of interesting potential
applications in the chemical industry as well as in
biotechnology and water treatment processes. Its
key component is the bipolar membrane. The
bipolar membrane schematically illustrated in
Fig. 2 consists of a laminate of an anion- and a
cation-exchange membrane with a 4–5 nm thick
catalytic transition layer in between. In Fig. 2 this
transition layer has been artificially magnified.
Water is diffusing through both membrane layers
into the transition layer where it gets electro-
catalytically dissociated into H+- and OH
-ions,
which migrate toward cathode and anode into the
outer solutions.
The energy required for the water dissociation
can be calculated from the Nernst equation for a
concentration chain between solutions of differ-
ent pH-values. It is given by:
DG ¼ FD’ ¼ 2:3RTDpH
Here DG is the Gibbs free energy and DpH and
D’ are the pH-value and the potential difference
between the two solutions separated by the bipo-
lar membrane. For 1 mol/L acid and base in the
two phases separated by the bipolar membrane,
DG is 0,022 kWh/mol and D’ is ca. 0,83 V at
25  C. Compared to the ohmic potential drop over
the membranes, the required potential drop for
water splitting in the transition layer is much
2 Electrodialysis with Bipolar Membranes

Base Acid Base Acid

Repeating
cell unit
cm bpm am cm bpm am
– + – + – + – +
– + – + – + – +
– + – + – + – +
– M + + – + – + – +
–
–
+ –
+ – H+ + M+ – M+ + – H+ +
+
+ – + – +
– + – + – + –
+ – + –
− + − – OH− + – +
+
–
– −
+ – X + X – + –
– OH + – + – + – +
– + – + – + – +
– + – + – + – − +
– + – + – + – X +
– + – + – + – +
– + – + – + – +
– + – + – + – +

Salt solution Salt solution Salt solution

Electrodialysis with Bipolar Membranes, cell unit consisting of a cation-exchange membrane (cm),
Fig. 1 Schematic drawing illustrating the principle of a bipolar membrane (bpm), and an anion-exchange mem-
the electrodialytic production of an acid and a base from brane (am)
the corresponding salt with bipolar membranes. Repeating

contains a bipolar membrane, a cation- and an

Cation-exchange Anion-exchange anion-exchange membrane. The bipolar mem-
layer layer brane is rather expensive, and its useful life time
as well as that of the anion-exchange membrane
is rather limited in strong bases. The operating
H2O – + H2O
– + costs in electrodialysis with bipolar membranes
Cathode – + Anode
– + are strongly determined by the energy require-
H+ – +
OH– ments which are composed of the energy required
– +
– +
– + for the water dissociation in the bipolar mem-
brane and the energy necessary to transfer the
Bipolar membrane
salt ions from the feed solution and protons and
Electrodialysis with Bipolar Membranes, hydroxide ions from the transition region of the
Fig. 2 Schematic drawing illustrating the electrodialytic bipolar membrane into the acid and base solu-
water dissociation in a bipolar membrane with water dif-
tions. The energy consumption due to the
fusing into the reaction region between the cation- and
anion-exchange layers of the membrane and protons and pumping of the solutions through the stack can
hydroxide migrate to the corresponding electrode generally be neglected. Since bipolar membranes
became available as commercial products, a large
more pronounced. The determination of the costs number of applications have been identified and
for the production of acids and bases from the studied on a laboratory or pilot plant scale. How-
corresponding salts follows the same general pro- ever, in spite of the obvious technical and eco-
cedure as applied for the cost calculation in elec- nomical advantages of the technology, large-
trodialysis desalination. The overall costs are the scale industrial plants are still quite rare
investment-related costs and the operating costs. (Gineste et al. 1996). The main reasons for the
The investment-related costs are dominated by reluctant use of bipolar membrane electrodialysis
the membrane costs and are proportional to the are poor membrane stability at very high or low
required membrane area for a given capacity pH-values and insufficient permselectivity at
plant. They are a function of the current density high ion concentrations, which results in a sub-
applied in a given stack operation. A unit cell stantial product salt contamination, low current
Electrodialysis with Bipolar Membranes 3

efficiency, and short membrane life. Neverthe- simplified model to determine trends. J Membr Sci
less, there are a number of smaller-scale applica- 112:199–208
Liu KJ, Chlanda FP, Nagasubramanian KJ (1977) Use of
tions in the chemical process industry, in bipolar membranes for generation of acid and base: an
biotechnology, in food processing, and in waste- engineering and economic analysis. J Membr Sci
water treatment. 2:109–124
Simons R (1993) Preparation of high performance bipolar
membranes. J Membr Sci 78:13–23

References

Gineste JL, Pourecelly G, Lorrain Y, Presin F, Gavach

C (1996) Analysis of factors limiting the use of BPM: a
B
Blood Separation
A. Higuchi
Department of Chemical and Materials
Engineering, National Central University,
Chung-Li, Taoyuan, Taiwan
Blood separation can be performed by centrifu-
gation, magnetic cell selection system (MACS),
fluorescence-activated cell sorting (FACS), and
membrane filtration method. Blood is a living
tissue composed of several blood cells in plasma.
The cellular elements of red blood cells (RBCs),
platelets, and white blood cells make up 45 % of
the volume of whole blood. Another 55 % is
plasma, which contains 7–8 % of the plasma pro-
teins and 92–93 % of water (Higuchi 2010). Fig-
ure 1 shows typical blood after centrifugation
with and without addition of Ficoll-Paque
(Ficoll-Hypaque) solution. After centrifugation
of blood without addition of Ficoll-Paque
(Ficoll-Hypaque) solution (native blood centrifu-
gation), blood can be separated into plasma layer,
platelet and leukocyte layer, and RBC layer
(Fig. 1a). In this case, each layer contains other
contaminant cells, e.g., RBC layer contains 96 %
of RBCs, 3 % of leukocytes, and 1 % of platelets
in blood cells. Platelets and leukocytes are also
included in plasma layers. Platelet-rich plasma is
necessary to use for the evaluation of biocompat-
ibility of biomaterials (Higuchi et al. 2003).
Platelet-rich plasma is obtained by centrifugation
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_72-7
of peripheral blood or umbilical cord blood at
3,000 rpm. Platelet-poor plasma is used for
plasma protein adsorption on biomaterials for
the evaluation of biocompatibility of the bioma-
terials (Higuchi et al. 2003). Platelet-poor plasma
is obtained by centrifugation of peripheral blood
or umbilical cord blood at a relatively high speed
of 3,000 rpm. Mononuclear cells including hema-
topoietic stem cells (HSCs) cannot easily be
obtained by centrifugation of native blood.
Therefore, Ficoll-Paque (or Ficoll-Hypaque)
solution was injected into blood sample, and the
mixed solution was centrifuged at 400 g for
30–40 min at 20  C (Fig. 1b). The upper layer
contains plasma and platelets. Mononuclear cells
including lymphocytes (T cells, B cells, and NK
(natural killer) cells) and HSCs can be isolated
from the upper second layer (Fig. 1b). When
specific cells such as HSCs, T cells, N cells, or
NK cells should be isolated, MACS or FACS are
applied. Direct application of MACS and FACS
to isolate the specific blood cells is difficult due to
large quantity of RBCs in blood samples. After
the mononuclear cells were isolated by Ficoll-
Paque method, residual RBCs were removed by
the treatment of lysing solution and then HSCs
(CD34+ cells) can be isolated by MACS or FACS
treatment using antibody of CD34+ (Chen
et al. 2012).
MACS is a sophisticated cell separation
method, in which magnetic beads attaching a
monoclonal antibody as the cell-surface marker
are mixed with cells. Figure 2 shows the
2 Blood Separation

Blood Separation,
Fig. 1 Blood components a Blood contains
after centrifugation of 55% of plasma.
native blood (a) and before Plasma Concentration of plasma
and after centrifugation of protein is 7 - 8%
blood with Ficoll-Paque
solution (b) Platelets
Blood contains
Lymphocytes
45% of blood cells
(96% of red blood cell,
Red Blood cell 3% of leukocytes, and
1% of platelet)

b
Blood sample
Plasma, Platelets
Centrifugation
Lymphocytes

Ficoll-Paque
Ficoll-Paque
Red blood cells,
Granulocytes

Blood Separation, a b
Fig. 2 Schematic
mechanism of the
separation method of cells
by a magnetic cell selection
system

Magnet Magnet Magnet Magnet

schematic mechanism of the separation method
by an MACS. The magnetic beads attaching the
monoclonal antibody are separated by magnetic
force to collect the specific marked cells. The
MACS needs to use an expensive antibody con-
jugated with magnetic beads to bind to the target
cells for the detection of the cells. Both cell
separation methods using FACS and MACS are
not applicable if the antibodies to the specific
markers on the surface of the target cells have
not been established.
Blood cell separation through membrane fil-
tration was recently reported by several
researchers (Komai et al. 1998; Yasutake
Blood Separation
et al. 2001; Higuchi et al. 2004, 2008). Typical
blood cell separation membranes are leukocyte
removal filter (membrane) and HSC purification
membranes.
HSC separation from peripheral blood and
umbilical cord blood through surface-modified
polyurethane membranes by membrane filtration
method was reported (Higuchi et al. 2004, 2008,
2010). Peripheral blood or umbilical cord blood
was permeated though the surface-modified
membranes by filtration. HSCs are more adhesive
cells than RBCs, platelets, and lymphocytes.
Therefore, HSCs remained to adhere on the mem-
branes during permeation of blood. The
membrane-adhering HSCs were rinsed with
phosphate buffer saline and subsequently human
serum albumin or dextran solution as surfactant
solution was permeated through the membranes.
The HSCs can be harvested in the recovery solu-
tion of human serum albumin or dextran solution.
The membrane filtration method of blood sepa-
ration should be useful, because centrifugation
instrument is not necessary to use and antibodies
targeting specific cells are not used in the method,
which cause contamination of antibodies in the
blood cell samples.
Cross-References
▶ Blood Cell Origins
▶ Blood Filtration
▶ Blood Treatment Membranes
3
References
Chen LY, Chang Y, Shiao JS, Ling QD, Chang Y, Chen
YH, Chen DC, Hsu ST, Lee H, Higuchi A (2012)
Effect of the surface density of nanosegments
immobilized on culture dishes on ex vivo expansion
of hematopoietic stem and progenitor cells from
umbilical cord blood. Acta Biomater 8:1749–1758
Higuchi A (2010) Separation and purification of stem and
blood cells by porous polymeric membranes. In:
Driolli E, Giorno L (eds) Comprehensive membrane
science and engineering. Elsevier, Cambridge
Higuchi A, Sugiyama K, Yoon BO, Sakurai M, Hara M,
Sumita M, Sugahara S, Shirai T (2003) Serum protein
and platelet adsorption on pluronic-coated polysulfone
membranes. Biomaterials 24:3235–3245
Higuchi A, Yamamiya S, Yoon BO, Sakurai M, Hara
M (2004) Peripheral blood cell separation through
surface-modified polyurethane membranes. J Biomed
Mater Res Part A 68A:34–42
Higuchi A, Sekiya M, Gomei Y, Sakurai M, Chen WY,
Egashira S, Matsuoka Y (2008) Separation of hemato-
poietic stem cells from human peripheral blood
through modified polyurethane foaming membranes.
J Biomed Mater Res Part A 85A:853–861
Higuchi A, Yang ST, Li PT, Tamai M, Tagawa T,
Chang Y, Chang Y, Ling QD, Hsu ST (2010) Direct
ex vivo expansion of hematopoietic stem cells from
umbilical cord blood on membranes. J Membr Sci
351:104–111
Komai H, Naito Y, Fujiwara K, Takagaki Y, Noguchi Y,
Nishimura Y (1998) The protective effect of a leuko-
cyte removal filter on the lung in open-heart surgery
for ventricular septal defect. Perfusion 13:27–34
Yasutake M, Sumita M, Terashima S, Tokushima Y,
Nitadori Y, Takahashi TA (2001) Stem cell collection
filter system for human placental/umbilical cord blood
processing. Vox Sang 80:101–105
B
Blood Treatment Membrane
A. Higuchi
Department of Chemical and Materials
Engineering, National Central University,
Chung-Li, Taoyuan, Taiwan
Blood treatment membrane is categorized as
dialysis membrane, leucocyte removal filter, and
plasma separation membrane.
Dialysis Membrane
Dialysis is a process for removing waste and
excess water from the blood and is used primarily
to provide an artificial replacement for lost kid-
ney function in people with renal failure. Dialysis
was used for those with an acute disturbance in
kidney function (acute kidney injury), or progres-
sive but chronically worsening kidney function.
Dialysis works on the principles of the diffu-
sion of solutes and ultrafiltration of fluid across a
semipermeable membrane. Blood flows by one
side of a semipermeable membrane, and a special
dialysis fluid flows by the opposite side.
A semipermeable membrane (dialysis mem-
brane, dialyzer) is a thin layer of material that
contains the appropriate size of pores. Smaller
solutes (urea, NaCl) and fluid pass through the
membrane, but the membrane blocks the passage
of larger substances such as red blood cells and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_73-3
large proteins (albumin, globulin). This is the
filtering process taking place in the kidneys,
when the blood enters the kidneys and the larger
substances are separated from the smaller ones in
the glomerulus (Daugirdas et al. 2006).
In hemodialysis, the patient’s blood is pumped
through the blood compartment of a dialyzer,
exposing it to a dialysis membrane. The dialyzer
is composed of thousands of tiny synthetic hol-
low fibers. The fiber wall acts as the semiperme-
able membrane. Blood flows through the fibers,
dialysis solution flows around the outside of the
fibers, and water and wastes move between these
two solutions (Daugirdas et al. 2006). The
cleansed blood is then returned via the circuit
back to the body. Ultrafiltration occurs by
increasing the hydrostatic pressure across the
dialyzer membrane. This usually is done by
applying a negative pressure to the dialysate
compartment of the dialyzer. This pressure gra-
dient causes water and dissolved solutes to move
from blood to dialysate and allows the removal of
several liters of excess fluid during a typical 3- to
5-h treatment. Hemodialysis treatments are typi-
cally given in a dialysis center three times per
week (Daugirdas et al. 2006).
Hemodialysis membranes are typically pre-
pared from cellulose materials or polysulfone-
polyvinylpyrrolidone (PVP)-blended materials.
Cellulose is hydrophilic and can be used as a
hemocompatible material, whereas polysulfone
is one of the engineering plastics and needs to
add a hydrophilic and hemocompatible material
2 Blood Treatment Membrane
as a blending material. PVP shows relatively
good hemocompatibility and the more important
fact is that PVP can be blended well with
polysulfone. There are a lot of materials reported
excellent biocompatibility. However, these bio-
compatible materials cannot be used as blending
materials in polysulfone dialysis membranes due
to low mixing with polysulfone. PVP is also used
as a porogen in dialysis membranes of
polysulfone. There is a recent demand for hemo-
dialysis membranes that remove the
low-molecular-weight proteins such as b2-
myoglobin (MW 11,500) and endotoxin
(subunit of MW = 5,000–20,000) and useful
albumin in the plasma should be recovered by
the membranes. Polysulfone hollow fibers
blended with PVP have been widely used as
suitable hemodialysis membranes which satisfy
this requirement (Higuchi et al. 2002).
Leukocyte Removal Filter
White blood cells (leukocytes) generate many
adverse reactions during blood-transfusion ther-
apy, which are graft-versus-host disease
(GVHD), platelet refractoriness, nonhemolytic
febrile transfusion reaction, and infection of
viruses, such as human T-lymphotropic virus
(HTLV), cytomegalovirus (CMV), and human
immunodeficient virus (HIV) (Higuchi 2010). It
was found that most of the viruses infect specific
type of leukocytes, such as granulocytes, mono-
cytes, lymphocytes, lymphocytes-B, T helper cell
(CD4+ cell), and T-cell suppressor/cytotoxic cells
(CD8+ cell). HTLV-1 and HIV mainly infect
T helper cell, while CMV mainly infects
granulocytes, monocytes, and lymphocytes.
GVHD was mainly generated by T helper cell
and T-cell suppressor/cytotoxic cells (CD8+
cell) (Higuchi 2010). Therefore, removal of leu-
kocytes in RBC and platelet concentrates as well
as whole blood component are essential to pre-
vent the adverse effect of contaminated leuko-
cytes. Leukocytes can be removed using a filter
comprised of nonwoven fabric or sponge mate-
rials as a filter medium. The mechanism of leu-
kocyte removal on the filters comprised of
nonwoven fabric is based on the adsorption of
leukocytes, while that comprised of sponge mate-
rials is based on the sieving effect and adsorption.
Filtration methods have several advantages
compared to other methods of removing leuko-
cytes such as centrifugation. Virus contamination
is lower in blood components during the process
in the filtration method than in the centrifugation
method due to mild operation and the ease of
operation under sterilized conditions.
Leukocyte removal filters were typically made
of polyurethane (PU) foaming membranes where
the pore was made by salt leaching method and
nonwoven fabric. The pore structure of both fil-
ters is found to be completely different, although
the pore size of those filters was almost the same
from capillary flow porometer measurements.
The mechanism of leukocyte removal (i.e., sepa-
ration of leukocyte from plasma and other blood
cells) in leukocyte removal filters is based on
leukocyte adsorption on the filters. The adsorp-
tion of leukocytes was affected significantly by
filter materials, pore structure, and pore size.
Plasma Separation Membrane
Plasma-exchange therapy has been increasingly
applied clinically over the past few years. Mem-
brane plasma separation has been used since
1979, which is similar to hemodialysis and
hemofiltration. Plasma separation from whole
blood is now performed routinely. The materials
of plasma separation membranes are typically
made of nitrocellulose, polysulfone, and
polypropylene.
Cross-References
▶ Blood Cell Origins
▶ Blood Filtration
▶ Blood Separation
▶ Diafiltration
▶ Diffusion
Blood Treatment Membrane
References
Daugirdas JT, Van Stone JC, Boag JT (2006) Hemodialy-
sis apparatus. In: Daugirdas JT, Peter G, Blake PG,
Todd S, Ing TS (eds) Handbook of dialysis. Lippincott
Williams & Wilkins, Riverwoods
Higuchi A (2010) Separation and purification of stem and
blood cells by porous polymeric membranes. In:
3
Driolli E, Giorno L (eds) Comprehensive membrane
science and engineering. Elsevier, Cambridge
Higuchi A, Shirano K, Harashima M, Yoon BO, Hara M,
Hattori M, Imamura K (2002) Chemically modified
polysulfone hollow fibers with vinylpyrrolidone hav-
ing improved blood compatibility. Biomaterials
23:2659–2666
B
Boron Reduction
Piotr Dydo
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
Synonyms
Boron removal
Characteristics
The boron element has an average concentration
in the Earth’s crust equal to about 10 mg/kg. Due
to its strong affinity toward oxygen, it exists in
nature mainly in the form of boric acids or
borates. Boric acid and borates are mainly used
in the glass and ceramic industry to obtain boro-
silicate glass, insulation fiberglass, flame retar-
dant fiberglass, ceramic glazes, and porcelain
enamels. Boron compounds are also used as a
flame retardant in plastics and cellulosic insula-
tion, neutron absorbers, herbicides (when at high
concentrations) or fertilizers (when at low doses),
and components of washing powders and soaps.
According to the WHO (2009) and (2011),
average boron concentration in surface waters
does not exceed the value of 0.5 mg/L. However,
the amount of boron in these waters depends upon
the presence of boron-bearing minerals in the
proximity of water reservoirs. It may also be
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_74-10
affected by the discharge of municipal and indus-
trial effluents into the environment. On the other
hand, naturally occurring boron is present in
ground waters at a wide concentration range
from <0.3 to >100 mg/L. This includes strongly
mineralized, naturally carbonized geothermal
waters. Considerable amounts of boron are also
present in oceans, with an average concentration
of 4.5 mg/L as reported by the WHO in 2009.
Despite the fact that boron is an important
nutrient, it manifests toxic action against plants
and animals when found at high concentration in
irrigation or drinking water. The effects of boron
on plants and mammals were summarized by the
WHO (2009), Kabay et al. (2010), and Hilal
et al. (2011). Among the reported effects, the
adverse impact of boron on the male reproductive
system in rats, mice, and dogs was presented.
Based on analysis of toxicokintetic of boron, the
WHO proposed a guideline value for boron in
drinking water of 2.4 mg/L in 2011. In areas
with high natural boron levels, local regulatory
and health authorities are, however, advised to
consider values in excess of 2.4 mg/L by
assessing exposure from other sources
(e.g., food).
The low drinking water boron content limit
implies the necessity for a reduction of boron
content in drinking water, especially when sea-
water or boron-rich underground waters (e.g.,
geothermal waters) are to be treated. There
could also be a need for boron removal from
industrial and municipal effluents that contain
2 Boron Reduction
more than the WHO guideline value. Conven-
tional methods for water treatment do not signif-
icantly remove boron. The methods proven to be
efficient in a reduction of boron content in waters
are either adsorption or membrane based.
Adsorption-based methods for boron removal
include coagulation with metal hydroxides,
adsorption on clays, fly ashes, and activated car-
bon (WHO 2009). Also, successful boron reduc-
tion with conventional anion exchange resins or
resins functionalized with N-methyl
D-glucamine (Chillon Arias et al. 2011) was
reported. Among the membrane-based methods,
boron removal by reverse osmosis is reported
most commonly. Also some achievements in
boron removal with ion-exchange membranes as
well as boron removal by electrodialysis are
presented. In addition, some hybrid systems,
which combine membrane filtration with sorp-
tion, are proposed, e.g., the adsorption-membrane
filtration (AMF) system. In this system,
microparticulate boron selective resin suspension
is recirculated in the retentate. Boron species
remains adsorbed on the resin, while the boron-
depleted water is continuously separated by
microfiltration. According to Kabay et al. 2008,
the main advantage of the AMF over other
methods of boron separation lies in the fast
removal of boron, ease of sorbent separation,
and low operating pressure.
According to the WHO (2009), the
abovementioned methods for boron removal are
likely to be prohibitively expensive, and blending
with waters of low boron content may be the only
economically feasible option to reduce high con-
centrations of boron in water.
Cross-References
▶ Boron Removal by Electrodialysis
▶ Boron Removal by Reverse Osmosis
▶ Boron Removal with Ion-Exchange
Membranes
References
Chillon Arias MF, Valero i Bru L, Prats Rico D, Varo
Galvan P (2011) Comparison of ion exchange resins
used in reduction of boron in desalinated water for
human consumption. Desalination 278:244–249
Hilal N, Kim GJ, Somerfield C (2011) Boron removal
from saline water: a comprehensive review. Desalina-
tion 273:23–35
Kabay N, Bryjak M, Schlosser S, Kits M, Avlonitis S,
Matejka Z, Al-Mutaz I, Yuksel M (2008) Adsorption-
membrane filtration (AMF) hybrid process for boron
removal from sweater: an overview. Desalination
223:38–48
Kabay N, Guler E, Bryjak M (2010) Boron in seawater and
methods for its separation – a review. Desalination
261:212–217
WHO (2009) Boron in drinking-water. Background docu-
ment for development of WHO guidelines for drinking-
water quality. World Health Organization. http://
whqlibdoc.who.int/hq/2009/WHO_HSE_WSH_09.01_
2_eng.pdf. Accessed 17 June 2012
WHO (2011) Guidelines for drinking-water quality,
4th edn. World Health Organization. http://whqlibdoc.
who.int/publications/2011/9789241548151_eng.pdf.
Accessed 17 June 2012
B
Boron Removal by Electrodialysis
Piotr Dydo
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
As in the case of boron removal by reverse osmo-
sis, the effectiveness of boron removal by elec-
trodialysis (ED) is strongly affected by the
aqueous chemistry of the boron species. In aque-
ous solutions, boric acid may exist in the form of
boric acid, metaborate, and polyborates. Boric
acid as a weak electrolyte (pKa = 9.2) dominates
in diluted aqueous solutions of a pH equal to or
less than 9, while at higher pH borate ions dom-
inate. Therefore, the effectiveness of boron trans-
port across ion-exchange membranes (IEM) in
the electrodialysis process needs to be discussed
with regard to the type of the species that domi-
nates in the dilute.
The Effectiveness of Boric Acid
Transport in ED
Boric acid, H3BO3, is a small and electrically
neutral species. The reported boric acid removal
efficiencies and electric current efficiencies in
ED are poor when compared to ionic species
(Melnik et al. 1999; Turek et al. 2005, 2007,
2008a; Kabay et al. 2008; Banasiak and Schafer
2009; WHO 2009). In fact, boric acid fluxes
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_75-4
across IEMs are so low that the possibility of
boric acid separation from ionic species, strong
acids (Melnik et al. 2005, 2007) and salts (Turek
et al. 2005, 2007; Bandura-Zalska et al. 2009;
Dydo 2012a), by the use of electrodialysis is
considered. Employing this method, ionic species
are effectively transported across IEMs while
boric acid remains in the ion-depleted dilute
solution.
The type of the membrane, the dilute boron
concentration, the presence of ions in the dilute,
and the electric current density were shown to
affect the rate of boric acid transport across IEM
to a great extent (Melnik et al. 1999; Yazicigil
and Oztekin 2006; Kabay et al. 2008; Dydo
2012a). The reported mechanism for boric acid
transport across IEMs is diffusion (Dydo 2012b);
however, the flux of boric acid was found to
increase with an increase in the flux of ionic
species. This was suggested to be the result of a
kind of ion-coupled transport of boric acid across
IEMs. The effectiveness of such a transport was
found to decrease in the following ion series:
sulfate  nitrate  chloride. It was also reported
that most of the boric acid was transported across
anion-exchange membrane (AEM).
Turek et al. 2008b reported high boron fluxes
and exceptionally high electric current efficien-
cies of up to 220 % when boric acid was
transported from ion-depleted, neutral or acidic,
dilute into the alkaline concentrate of pH >11.
Such a behavior was identified to be the result of
Donnan dialysis, in which hydroxyl acts as a
2 Boron Removal by Electrodialysis
carrier for boric acid. However, in the light of
recent reports, simple boric acid diffusion should
explain the results as well.
Tentative results on boron removal by electro-
dialysis units equipped with ion-exchange
spacers were also presented by Oren et al. in
2006. The possibility of up to an 80 % reduction
of boron from water containing 4.5 mg/L was
reported.
The Effectiveness of Borate Transport
in ED
Melnik et al. (1999), Yazicigil et al. (2006), and
Kabay et al. (2008) reported that as the pH of
boron-containing water was brought up to just
above the value of 9, a significant increase in
the rate of boron transport across IEMs is
observed. Moreover, Melnik et al. 1999 reported
that in the case of heterogeneous membranes, an
increase in the boron transport rate across anion-
exchange membrane at pH >9 is accompanied by
a decrease in the rate of boron transport across
cation-exchange membrane (CEM). It is clear
that under these conditions (pH >9), borates are
the boron species that dominates and their trans-
port across AEMs rather than CEMs should be
discussed. The effectiveness of borate transport
across AEMs in ED systems was found to depend
upon the pH of the dilute, the type of the mem-
brane, dilute boron concentration, and the kind of
the ion cotransported across the membrane.
Yazicigil et al. in 2006 reported that at a dilute
pH of approx. 9, there is a maximum boron trans-
port rate, and at higher pH the rate of boron
transport decreases. These results are contradic-
tory to those presented by Melnik et al. (1999)
(heterogeneous membranes), Turek et al. (2007),
and Kabay et al. (2008), according to which there
is a continuous increase in the rate of boron
transport with dilute pH even when above 9.0.
However, the Yazicigil et al. (2006) results seem
to be justified by high boron concentration
(0.1 mol/L) in their experiments. Similar behav-
ior was observed by Ayyildiz and Kara in 2005. It
is agreed that an increase in dilute boron concen-
tration causes an increase in boron (borate) flux
(Yazicigil et al. 2006; Kabay et. al 2008; Turek
et al. 2008a). It is also agreed that boron (borate)
is transported faster in the presence of chloride
ions than in the presence of sulfates (Yazicigil
et al. 2006; Kabay et al. 2008) or nitrates.
In 2005 and 2008a, Turek et al. analyzed the
effect of salinity on the electric current efficiency
of boron (borate) transport. They found that the
observed electric current efficiencies are low as
long as dilute salinity remains high. During the
initial part of the experiments, no, or almost no,
boron was transported from the dilute. Then, i.e.,
when more than 90 % of the Cl was removed
from the dilute, a dramatic increase in boron
(borate) electric current efficiency was observed.
This increase was accompanied by an increase in
boron flux. Such an effect can be identified as the
result of low borate mobility (diffusivity) when
compared to other ions present in the waters, i.e.,
Cl . As long as there are ions of higher mobility
than borates in the dilute, boron (borate) flux
remains low. However, even in an ion-depleted
dilute, the electric current efficiency of boron
(borate) transport has not exceeded the value of
30 %. The remaining percentage of the electric
current was probably utilized for hydroxyl ion
transport. A considerable drop in the pH of the
dilute was reported afterwards. This resulted in a
drop in dilute pH and in a consequent reduction in
the flux of boron since all the borate present was
converted into boric acid. So the low electric
current efficiency of borate transport in an ED
system and the necessity for deep dilute demin-
eralization make the economic feasibility of
borate removal by ED questionable.
Cross-References
▶ Boron Reduction
▶ Boron Removal by Electrodialysis
▶ Boron Removal by Reverse Osmosis
References
Ayyildiz HF, Kara H (2005) Boron removal by ion
exchange membranes. Desalination 180:99–108
Boron Removal by Electrodialysis
Banasiak LJ, Schafer AI (2009) Removal of boron, fluo-
ride and nitrate by electrodialysis in the presence of
organic matter. J Membr Sci 334:101–109
Bandura-Zalska B, Dydo P, Turek M (2009) Desalination
of boron-containing wastewater at no boron transport.
Desalination 241:133–137
Dydo P (2012a) The effect of process parameters on boric
acid transport during the electrodialytic desalination of
aqueous solutions containing selected salts. Desalina-
tion. In press. doi:10.1016/j.bbr.2011.03.031
Dydo P (2012b) The mechanism of boric acid transport
during an electrodialytic desalination process.
J Membr Sci 407–408:202–210
Kabay N, Arar O, Acara F, Ghazal A, Yuksel U, Yuksel
M (2008) Removal of boron from water by electrodi-
alysis: effect of feed characteristics and interfering
ions. Desalination 223:63–72
Melnik L, Vysotskaja O, Kornilovich B (1999) Boron
behavior during desalination of sea and underground
water by electrodialysis. Desalination 124:125–130
Melnik L, Goncharuk V, Butnyk I, Tsapiuk E (2005)
Boron removal from natural and wastewaters using
combined sorption/membrane proces. Desalination
185:147–157
Melnik L, Goncharuk V, Butnyk I, Tsapiuk E (2007)
Development of the sorption-membrane “green”
3
technology for boron removal from natural and waste-
waters. Desalination 205:206–213
Oren Y, Linder C, Daltrophe N, Mirsky Y, Skorka J,
Kedem O (2006) Boron removal from desalinated
seawater and brackish water by improved electrodial-
ysis. Desalination 199:52–54
Turek M, Dydo P, Ciba J, Trojanowska J, Kluczka J,
Palka-Kupczak B (2005) Electrodialytic treatment of
boron-containing wastewater with univalent
permselective membranes. Desalination 185:139–145
Turek M, Dydo P, Trojanowska J, Bandura B (2007) Elec-
trodialytic treatment of boron-containing wastewater.
Desalination 205:185–191
Turek M, Bandura B, Dydo P (2008a) Electrodialytic
boron removal from SWRO permeate. Desalination
223:17–22
Turek M, Bandura B, Dydo P (2008b) The influence of
concentrate alkalinity on electrodialytic boron trans-
port. Desalination 223:119–125
WHO (2009) Boron in drinking-water. Background
document for development of WHO guidelines for
drinking-water quality. World Health Organization.
http://whqlibdoc.who.int/hq/2009/WHO_HSE_WSH
_09.01_2_eng.pdf. Accessed 17 Jun 2012
Yazicigil Z, Oztekin Y (2006) Boron removal by electro-
dialysis with anion-exchange membranes. Desalina-
tion 190:71–78
B
Boron Removal by Reverse Osmosis
Piotr Dydo
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
Reverse osmosis (RO) is a commonly applied
membrane technique of desalination capable of
producing permeates of drinking-water quality.
In most cases, the boron content in the product
should not exceed the WHO 2009 and 2011
guideline value of 2.4 mg/L. The effectiveness
of boron rejection by reverse osmosis membranes
is, however, strongly affected by its concentra-
tion in the feedwater and the aqueous chemistry
of boron specie (Kabay et al. 2010; Hilal
et al. 2011). In aqueous solutions, boric acid
may exist in the form of boric acid, metaborates,
and polyborates. Boric acid as a weak electrolyte
(pKa = 9.2) dominates in diluted aqueous solu-
tions of a pH less than 9. Since the pH of most
naturally occurring waters is lower than 9, the
rate of boric acid transport determines the effec-
tiveness of boron removal by RO.
According to Kabay et al. 2010, the rejection
of boric acid by RO membranes is, however, low
due to its small size and lack of electric charge.
The reported boron rejection coefficients range
from around 20 % in the case of old RO mem-
branes to approx. 90 % in the case of modern RO
membranes (WHO 2009; Kabay et al. 2010; Hilal
et al. 2011).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_76-11
The effectiveness of boron removal from sea-
water by RO can be enhanced by adjusting the
feedwater pH to above the value of 9.25. The
monoborate anion, which dominates in diluted
solutions at pH > 9.5, was found to be rejected
more effectively than boric acid due to its larger
size and discrete charge (Kabay et al. 2010; Hilal
et al. 2011). The reported boron rejection coeffi-
cients at pH = 11 exceeds 99 % in the case of
dense seawater reverse osmosis membranes.
Also, in the case of boron-rich geothermal waters
and industrial wastewaters, high boron rejection
is observed only at pH > 10.5 (Koseoglu
et al. 2010; Dydo et al. 2005). Furthermore, it
was shown that the effectiveness of boron
removal can be further enhanced by creating
borate complexes (esters) with polyhydroxyl
alcohols (Geffen et al. 2006; Dydo et al. 2012),
although again, under alkaline conditions only.
The results of mechanistic studies on boron
rejection by reverse osmosis membranes
conducted by Sagiv and Semiat (2004), Hyung
and Kim (2006), Hun et al. (2009), and Tu
et al. (2010) showed that permeabilities of boric
acid are at least one order of magnitude larger
than those of monoborate ion. It proves more
intensive diffusion of boric acid than of borate
across RO membranes. Also, the reflection coef-
ficients for boric acid (<0.985) are considerably
lower than those specific for monoborate
(>0.995) as reported by Hyung and Kim (2006).
This, in turn, indicates strong boric acid–water
interaction.
2 Boron Removal by Reverse Osmosis
Feedwater pH is said to have a dominant
impact on boron rejection by RO membranes
(Hilal et al. 2011). Among other RO parameters
that affect boron rejection are: operating pressure
(increase), feed temperature (decrease),
feedwater salinity (decrease), and recovery
(decrease).
However, RO systems cannot be directly oper-
ated at high feedwater pH due to the possibility of
membrane scaling with insoluble calcium and
magnesium basic compounds. Therefore, several
modifications to the operation of RO and its
design have been proposed. In general, a cascade
design for RO systems in which a fraction of the
first stage permeate is treated in the following RO
stages (if possible at elevated pH’s) and a blend-
ing of all the permeates produces water of the
desired quality (Hilal et al. 2011; Faigon and
Hefer 2008). This design was successfully
applied, e.g., in the full-scale seawater treatment
plant in Eliat.
Cross-References
▶ Boron Reduction
▶ Boron Removal by Electrodialysis
▶ Boron Removal with Ion-Exchange
Membranes
References
Dydo P, Turek M, Ciba J, Trojanowska J, Kluczka
J (2005) Boron removal from landfill leachate by
means of nanofiltration and reverse osmosis. Desali-
nation 185:131–137
Dydo P, Nemś I, Turek M (2012) Boron removal and its
concentration by reverse osmosis in the presence of
polyol compounds. Sep Purif Technol 89:171–180
Faigon M, Hefer D (2008) Boron rejection in SWRO at
high pH conditions versus cascade design. Desalina-
tion 223:10–16
Geffen N, Semiat R, Eisen MS, Balazs Y, Katz I, Dosoretz
CG (2006) Boron removal from water by complexa-
tion with polyol compounds. J Membr Sci 286:45–51
Hilal N, Kim GJ, Somerfield C (2011) Boron removal
from saline water: a comprehensive review. Desalina-
tion 273:23–35
Hun PVX, Cho S-H, Moon S-H (2009) Prediction of boron
transport through seawater reverse osmosis mem-
branes using solution-diffusion model. Desalination
247:33–44
Hyung H, Kim J-H (2006) A mechanistic study on boron
rejection by sea water reverse osmosis membranes.
J Membr Sci 286:269–278
Kabay N, Guler E, Bryjak M (2010) Boron in seawater and
methods for its separation – a review. Desalination
261:212–217
Koseoglu H, Harman BI, Yigit NO, Guler E, Kabay N,
Kitis M (2010) The effects of operating conditions on
boron removal from geotermal waters by membranes
processes. Desalination 258:72–78
Sagiv A, Semiat R (2004) Analysis of parameters affect-
ing boron permeation through reverse osmosis mem-
branes. J Membr Sci 243:79–87
Tu KL, Nghiem LD, Chivas AR (2010) Boron removal by
reverse osmosis membranes in seawater desalination
applications. Sep Purif Technol 75:87–101
WHO (2009) Boron in drinking-water. Background docu-
ment for development of WHO guidelines for drinking-
water quality. World Health Organization. http://
whqlibdoc.who.int/hq/2009/WHO_HSE_WSH_09.01_2_
eng.pdf. Accessed 17 June 2012
WHO (2011) Guidelines for drinking-water quality,
4th edn. World Health Organization. http://whqlibdoc.
who.int/publications/2011/9789241548151_eng.pdf.
Accessed 17 June 2012
B
Boron Removal with Ion-Exchange
Membranes
Piotr Dydo
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
Apart from boron removal by electrodialysis,
ion-exchange membranes are able to transport
boron in the so-called Donnan dialysis (DD) or
diffusion dialysis processes (Fig. 1).
Ayyildiz and Kara (2005) examined the effec-
tiveness of boron transport across anion-
exchange membranes in a DD process. They
found that boron flux depends upon the mem-
brane, concentration of boron in the feed solution,
pH of the feed and receiving solution, presence of
the accompanying ions in the feed solution, and
the type of the carrier anion in the receiving
solutions. The effect of pH of the feed solution
was found to be complex. At high boron concen-
tration (0.1 mol/L), maximum boron flux was
observed at around the pH of 9.5, while in the
case of a diluted solution (0.001 mol/L), maxi-
mum boron flux was observed at the maximum
examined feedwater pH of 11.5. Such behavior
was explained by the formation of polyborate
ions at high boron concentrations and their
absence in diluted solutions. The maximum rate
of boron transport at the pH of around 9.5 in the
case of concentrated boron solution was later
confirmed by Yazicigil et al. in 2006. Ayyildiz
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_77-5
and Kara in 2005 reported also that the pH of the
receiving phase affects boron flux with its maxi-
mum at around a pH of 9.5. Moreover, the boron-
accompanying anions, chlorides, bicarbonates,
and sulfates, were found to affect the rate of
boron transport in DD with a maximum observed
in the presence of bicarbonate. On the other hand,
the highest boron transport rates were observed
with sodium chloride in the receiving solution.
Neosepta AHA and AMH membranes produced
similar fluxes of boron, while the superiority of
AFN was clearly seen. In 2011, Kir et al. showed
that plasma modification of the existing anion-
exchange membranes may result in a significant
enhancement of the rate of boron transport in a
DD process.
The mechanistic study on boric acid transport
across cation-exchange membranes (CEMs) in a
DD process was presented by Goli et al. in 2010.
It was reported that the membrane diffusion coef-
ficients for boric acid depend not only upon the
manufacturer of the CEM but also upon the type
of the cation present in the membrane. The same
behavior is reported for arsenite. In general, in the
presence of monovalent cations in the membrane,
higher fluxes of boron were observed than in the
presence of divalent cations. Such a behavior was
later confirmed by Dydo in 2012. The existing
differences in boric acid membrane diffusion
coefficients were rationalized by Goli
et al. (2010) as being the result of the change in
the mean viscosity of the solution confined in
membrane pores.
2 Boron Removal with Ion-Exchange Membranes

Boron Removal with Ion-Exchange Membranes, Fig. 1 Boron Removal with Ion-Exchange Membranes

In 2007, Bryjak et al. proposed a Donnan
dialysis-based method for the regeneration of
finely divided boron selective resin (BSR)
DOWEX XUS 43594.00. In this process, BSR
slurry with boron adsorbed on it is fed into the
DD feed compartment. It was assumed that there
are always some minute amounts of borate in the
feedwater at equilibrium with the BSR. These
amounts were subject to transport into the receiv-
ing solution as a result of Donnan dialysis, which
should ultimately result in complete boron
removal from the BSR. The net effect of the
process would be a regenerated resin in the chlo-
ride form and boron (borate)-rich receiving solu-
tion. As reported by Bryjak et al. (2007),
considerably high boron fluxes were observed
during the course of a DD regeneration of boron
containing BSR. Boron desorption was found to
be the phenomena that governs kinetics of the
boron transport in the process.
Unfortunately the tentative, mostly mechanis-
tic report on DD boron removal presented in this
chapter does not provide much information about
the effectiveness of boron removal from water
nor its final concentration. It seems that a lot of
work needs to be done to enhance the kinetics of
the diffusive transport of borate during DD.
Cross-References
▶ Boron Reduction
▶ Boron Removal by Electrodialysis
▶ Boron Removal by Reverse Osmosis
References
Ayyildiz HF, Kara H (2005) Boron removal by ion
exchange membranes. Desalination 180:99–108
Bryjak M, Pozniak G, Kabay N (2007) Donnan dialysis of
borate anions through anion exchange membranes: a
new method for regeneration of boron selective resins.
React Funct Polym 67:1635–1642
Dydo P (2012) The mechanism of boric acid transport
during an electrodialytic desalination process.
J Membr Sci 407–408:202–210
Boron Removal with Ion-Exchange Membranes
Goli E, Hiemstra T, Van Riemsdijk WH, Rahnemaie R,
Malakouti MJ (2010) Diffusion of neutral and ionic
species in charged membranes: boric acid, arsenite,
and water. Anal Chem 82:8438–8445
Kir E, Gurler B, Gulec A (n.d.) Boron removal from
aqueous solution by using plasma-modified and
3
unmodified anion-exchange membranes. Desalination
267: 114–177
Yazicigil Z, Oztekin Y (2006) Boron removal by electro-
dialysis with anion-exchange membranes. Desalina-
tion 190:71–78
B
Bulk Biotech Industry
Frank Lipnizki
Alfa Laval Copenhagen, Søborg, Copenhagen,
Denmark
The term “bulk biotech industry” is referring to
the use of biological processes on industrial scale
to produce bulk products. Examples of products
from the bulk biotech industry are antibiotics,
enzymes, organic and amino acids, vitamins,
bioalcohols, and biopolymers. One of the earliest
biotechnological processes adopted by humans is
the production of alcohol by fermenting fruits
around 5000–6000 years ago. The production of
lactic acid by Pasteur in 1857 is often considered
to be the beginning of modern biotechnology
followed by the industrial scale production of
citric acid by Pfizer in 1923 (Chotani
et al. 2007). The first wave of biotechnology
started with the discovery of penicillin by Flem-
ing in 1928 paving the way for the industrial scale
production of antibiotics and amino acids. The
discovery and increased understanding of the
DNA created the foundation to use molecular
engineering to recombine DNA leading to the
second wave of biotechnology processes in the
1980s. The current third and so far final wave of
biotechnology – the white biotechnology – aims
to replace the C2/C3 chemistry based on fossil
fuels such as oil and gas by biotechnological
processes. It is foreseen that in the near future,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_82-1
up to 20 % of all chemical products with a market
value of approx 250 € billion will be produced by
biotechnology. Approximately 60 % of the prod-
ucts produced by white biotechnology will be
intermediated chemicals used in the pharmaceu-
tical industry, and the remaining 40 % will be
biopolymers and special chemicals for various
industries (Festel et al. 2004).
Since the 1970s, cross-flow membrane pro-
cesses have established themselves in the down-
stream processing of the biotechnology industry
for the recovery and purification of the products.
It is foreseen that membrane processes will also
play an important role in white biotechnology
and the related concept of biorefineries. Similar
to petroleum refineries, biorefineries are aiming
for the full utilization of biomass for the simulta-
neous production of biofuels, biochemicals, heat,
and power (Axegård 2005). The integrated pro-
duction of biomaterials can be based on, e.g.,
sugar, starch, and cellulose-based feedstock and
as such extend current sugar, starch, and pulp
factories. Membrane processes as highly selec-
tive and energy-saving processes are well suited
to play an important part in biorefineries and thus
the white biotechnology.
The key membrane technologies for the bulk
biotech industry are microfiltration (MF), ultra-
filtration (UF), nanofiltration (NF), and reverse
osmosis (RO). Other membrane technologies
such as membrane contactors (MC), electrodial-
ysis (ED), pervaporation (PV), and vapor perme-
ation (VP) plus membrane bioreactors for
2 Bulk Biotech Industry
continuous fermentation are less established but
have, nevertheless, the potential to become
increasingly important.
References
Axegård P (2005) The future pulp mill – a biorefinery?
Presentation at the 1st international biorefinery work-
shop, Washington, DC
Chotani GK, Dodge TC, Gaertner AL, Arbige MV
(2007) Industrial biotechnology: discovery to delivery.
In: Kent JA (ed) Kent and Riegel’s handbook of indus-
trial chemistry and biotechnology, 11th edn. Springer,
Berlin
Festel G, Knöll J, Götz H, Zinke H (2004) Der einfluss der
biotechnologie auf produktionsverfahren in der
chemieindustrie. Chem Ing Technol 76:307–312
B
Bulk Liquid Membrane
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Bulk liquid membrane (BLM) consists of a bulk
aqueous feed and receiving phases separated by a
bulk organic, water-immiscible liquid phase. The
feed and receiving phases may be separating from
the LM by microporous supports or may be with-
out supports (layered BLM).
Many technologies that were developed and
tested in the last two decades have to be included
in the BLM group. These are hybrid liquid mem-
brane (HLM), hollow-fiber liquid membrane
(HFLM), hollow-fiber-contained liquid membrane
(HFCLM), pertraction, flowing liquid membranes
(FLM), membrane-based extraction and stripping,
multimembrane hybrid system (MHS), and mem-
brane contactor systems (see entry “▶ Liquid
Membranes”). All these systems are based on
membrane-based nondispersive (as the means for
blocking the organic reagent from mixing with the
aqueous feed and strip solutions) selective extrac-
tion coupled to permselective diffusion of solute-
extractant complexes and selective stripping of the
solute in one continuous dynamic process (see
Fig. 1). A great number of terms for similar bulk
LM processes confuse the readers. The terms vary
by membrane type used (hollow fiber, flat neutral,
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_83-1
ion-exchange sheets) or by module design. All
abovementioned bulk LM processes with water-
immiscible organic liquid membrane solutions
may be unified under the term bulk organic hybrid
liquid membrane (BOHLM) systems (for more
details, see Kislik 2010a).
Bulk LM processes with water-soluble carriers
are defined as bulk aqueous hybrid liquid mem-
brane (BAHLM) systems (for more details, see
Kislik 2010b). Regenerable water-soluble
polyionic complexants are used as suitable aqueous
liquid membrane carriers. These polyelectrolytes
typically have a very high effective concentration
of charged groups and could constitute highly
selective complexants. The BAHLM technology
is based on a combination of liquid membrane
(LM) process and dialysis (D) in the case of neutral
hydrophilic membranes or Donnan dialysis
(DD) in the case of ion-exchange membranes used.
BOHLM and BAHLM technologies achieve
the necessary transport and selectivity character-
istics to have potential for commercial applica-
tions. Applications of the BOHLM processes are
mainly in metal separation, wastewater treat-
ment, biotechnologies, drugs recovery-
separation, organic compounds, and gas separa-
tion. Selective separations of alkali, alkali earth,
rare earth, heavy metal ions, precious metals, etc.,
are studied by many authors using all above-
described techniques. Recovery and separation
of carboxylic and amino acids from fermentation
broth have been tested using layered BLM, rotat-
ing, creeping, spiral-type FLM, HFLM, HLM,
2 Bulk Liquid Membrane
Bulk Liquid Membrane, Fig. 1 Schematic transport models of a bulk organic hybrid liquid membrane (BOHLM)
system with a, d hydrophobic membranes and b, e hydrophilic or ion-exchange membranes
and MHS-PV techniques of the BOHLM pro-
cesses. Separation of ethylene, benzene,
propanol, olefin, and aromatic amines from
organic liquid mixtures and of volatile organic
compounds (VOC) and phenol from wastewater
was investigated using a rotating film module,
spiral-type FLM, and hollow-fiber and layered
LM techniques. High separation factors
(>1,000) in pilot- and industrial-scale experi-
ments were found. In the last two decades,
BOHLM techniques were intensively used in
analytical chemistry for separation and
preconcentration of metals, organic acids,
organic, and pharmaceutical compounds.
BAHLM is a new technology and few studies
are known up to date. In metal separations copper-
cadmium recovery from chloride aqueous solu-
tions and cadmium, copper, and zinc separation
from wet-process phosphoric acid are studied.
BAHLM systems were tested for the separation
of carboxylic acids such as lactic, citric, and acetic
or their anions. Continuous separation of different
isomeric mixtures of organic compounds has been
studied by means of a hollow-fiber-contained liq-
uid membrane, HFCLM.
In recent years, integrated hybrid systems
incorporating two or more functions in one mod-
ule, for example, biotransformation and separa-
tion, become of great interest to researchers. The
BOHLM systems, integrating reaction, separa-
tion, and concentration functions in one appara-
tus (bioreactor) attracted great interest in the last
few years. Bioreactors combine the use of spe-
cific biocatalyst for the desired chemical reac-
tions, with repeated or continuous application of
it under very specific conditions. Such techniques
were termed hybrid membrane reactors.
References
Kislik V (2010a) Bulk hybrid liquid membrane with organic
water-immiscible carriers: application to chemical, bio-
chemical, pharmaceutical, and gas separations. In:
Kislik V (ed) Liquid membranes principles and applica-
tions in chemical separations & wastewater treatment,
1st edn. Elsevier, Amsterdam, pp 201–276, Ch. 5
Kislik V (2010b) Bulk Aqueous Hybrid Liquid Membrane
(BAHLM) processes with water-soluble carriers:
application in chemical and biochemical separations.
In: Kislik V (ed) Liquid membranes principles and
applications in chemical separations, 1st edn, Elsevier,
Ch. 6, pp 277–326
C
Capillary
Andras Koris
Corvinus University of Budapest, Budapest,
Hungary
The word capillary originated from the Latin
adjective capillaris, which means “pertaining to
the hair.” Possibly, the scientific phenomenon
was first observed between contiguous hairs, for
example, within a paintbrush.
In medicine and biology, capillary is the
smallest of a body’s blood vessel and is part of
the microcirculation. The word capillary, in the
nonmedical sense, means narrow tube.
In membrane science the noun capillary is
both used to name the inner spaces of a porous
media and to specify a typical membrane (see
▶ Capillary Membrane). The classification of
porous membrane filter types is mainly based on
the nominal diameter of the capillaries in the
membrane. Artificial capillaries in porous media
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_98-1
are produced by interfacial polymerization, or the
natural porosity in solid materials is adjusted to
the desirable nominal diameter. The shape and
size of the pores in the membrane are very
diverse.
The pore theory of membrane transport
through the capillaries considers that both con-
vection and diffusion contribute to solute trans-
port across the porous membrane, the two
processes being impeded by steric hindrance at
the entrance of the pores and by frictional forces
within the pores; the same steric hindrance and
frictional resistance terms were used in the con-
vection and diffusion terms of the solute transport
equation (Pappenheimer et al. 1951).
Reference
Pappenheimer JR, Renkin EM, Borrero LM (1951) Filtra-
tion, diffusion and molecular sieving through periph-
eral capillary membranes. Am J Physiol 167:13
C

Capillary Flow r 2 DP
u¼
8m L
Andras Koris
Corvinus University of Budapest, Budapest, where DP is the total pressure drop along the
Hungary channel and m is the fluid viscosity.
In the general case of two immiscible fluids:

Capillary flow means the movement of the fluid r 2 DP  Pc

in the internal gaps and on the surface of the solid
material, where the driving force is the molecular
interaction between the solid and fluid material
(see “▶ Capillary Force”). If the fluid is incom-
pressible and Newtonian, the flow is laminar
through a pipe of constant circular cross section
that is substantially longer than its diameter, and
since there is no acceleration of fluid in the pipe,
the total flow rate (Q) could be estimated
according to Poiseuille’s law (Briant et al. 1989):
d4 p  DP
Q¼
128  m  L
where d represents capillary diameter, DP is the
total pressure drop along the channel, m is the
fluid viscosity, and L represents the capillary
length.
For velocity calculation, let us consider a lam-
inar horizontal flow through a straight circular
channel of length L and a radius r. The mean
flow velocity u through the channel is given by
(Landau and Lifshitz 1987):
u¼
8meff L
where
x Lx
meff ¼ mw þ ma
L L
is the effective viscosity; mw and ma are viscosities
for phase w and phase a fluids, respectively; x is
the location of the interface measured from the
inlet; Pc is the capillary pressure across the inter-
face; and a0 is a constant associated with the
channel cross-sectional shape.
Assuming that the fluid system is in static
equilibrium, the capillary pressure at an interface
in a circular channel is (Young-Laplace eq.):
4g  cos y
Pc ¼
dc
where g represents the interfacial tension, y is the
contact angle, and dm represents the capillary
diameter.
Since the determination of the number of
active capillaries during membrane filtration is

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_99-3
2 Capillary Flow
very difficult, statistical approach from Darcy can
be applied basically. Darcy’s law is a simple
proportional relationship between the instanta-
neous discharge rate through a porous medium,
the viscosity of the fluid, and the pressure drop
over a given distance:
k  A  DP
Q¼
mL
where Q is overall flow rate, k represents perme-
ability of the medium, A is the cross-sectional
area to flow, DP is the pressure drop, m represents
viscosity, and L is the length over which the
pressure drop is taking place.
Due to the concentration polarization phe-
nomenon, gel layer forming, membrane fouling,
and pore blocking, the global model was further
developed for different membrane techniques,
see, e.g., resistances-in-series model or solution-
diffusion model.
The diffusion of gasses, liquids, and solids in
solids is quite important in mass transfer opera-
tions. The diffusion is greatly affected by the size
and shape of pores and capillaries. For example,
in porous solids, the effective diffusion of salts
(A) in water (B) is described as:
ϵ
D_f_A, eff g ¼ DAB
k2
where DAB represents the diffusivity of salt in
water, e is the porosity, and k is a correction
factor for the distance (when it is nonlinear; gen-
eral value = 1.2–2.5).
The diffusion of a liquid in capillaries has
three types: Knudsen diffusion, molecular
(Fick’s) diffusion, and transition region diffusion
(Geankoplis 1972).
The power-law is an improvement to the
Poiseuille’s equation by generalizing the flow to
include non-Newtonian effect. The beauty of this
model is its simplycity. However there are other
aspects of the flow properties of fluids which this
model fails to examine, one of them being the
presence of yield stress (Mazumdar 1992)
References
Briant J, Guy Parc JD (1989) Rheological properties of
Lubricants, ch. 3., p. 69-71
Geankoplis CJ (1972) Mass transport phenomena.
Rinehart and Winston, Holt
Landau LD, Lifshitz EM (1987) Fluid mechanics,
2nd edn. Pergamon Press, Oxford
Mazumdar J (1992) Biofluid Mechanics, p. 86-87, World
Scientific
C
Capillary Force
Andras Koris
Corvinus University of Budapest, Budapest,
Hungary
Capillary force is the force which generates
movement of a liquid along the surface of a
solid caused by the attraction of molecules of
the liquid to the molecules of the solid. For exam-
ple, molecules of water are naturally attracted to
each other and form temporary hydrogen bonds
with each other; their attraction for each other on
the surface of a liquid, for example, gives rise to
surface tension. But they are also attracted in a
similar way to other molecules, called hydro-
philic molecules, such as those in the sides of a
narrow glass tube inserted into water. These
attractive forces can draw water up against the
force of gravity to a certain degree.
Where three different fluid interfaces are
contacting each other along one line, equilibrium
exists only when the vector polygon of the
stresses is closed. This requirement determines
the angle between the edges of disjunctive sur-
faces (Pattantyús 1961) (Fig. 1).
Sometimes |C1–3| > |C1–2| + |C2–3| occurs.
Because vector C1–3 is always larger, equilib-
rium is not possible; therefore, fluid no. 2 is per-
manently moving on the no. 1 and 3 fluid
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_100-2
interface. For example, mineral oil unfolds the
water surface even to molecule thick layer when
the available area is sufficient.
One angle of the vector triangle is given in
cases where instead one of the liquids a solid
material presents. In Fig. 2 this angle is 180 .
The requirement of equilibrium: C1–3 = C2–3
+ C1–2*cosa.
In case of solid particle or material, |C1–3| >
|C1–2| + |C2–3| can also exist sometimes, and
no. 2 liquid could totally cover the solid surface
(1). This movement is usually limited by impuri-
ties on the solid surface. For mercury–air–glass
system, |C1–3| < |C2–3| and a > 90 .
The Young–Laplace equation is a nonlinear
partial differential equation that describes the
capillary pressure difference or capillary force
sustained across the interface between two static
fluids, due to the phenomenon of surface tension
or wall tension, although usage on the latter is
only applicable if assuming that the wall is very
thin. The Young–Laplace equation relates the
pressure difference to the shape of the surface or
wall, and it is fundamentally important in the
study of static capillary surfaces. It is a statement
of normal stress balance for static fluids meeting
at an interface, where the interface is treated as a
surface (scpacp).
2 Capillary Force

References

Sályi I (ed) (1961) Pattantyús gépész és villamos-

mérnökök kézikönyve, 2. Alaptudományok –
Anyagismeret. Műszaki Könyvkiadó

Capillary Force, Fig. 1 Contact of three fluids

Capillary Force, Fig. 2 Contact when one solid phase is

present next to two fluids
C
Capillary Membranes
Andras Koris
Corvinus University of Budapest, Budapest,
Hungary
Artificial capillary membranes are one type of the
tubular-shaped membrane filters. With capillary
membranes, the membrane serves as a selective
barrier, which is sufficiently strong to resist fil-
tration pressure. Because of this, the flow through
capillary membranes can be both inside out and
outside in.
The diameter of capillary membranes is much
smaller than that of tubular membranes, namely,
0.5–5 mm. Because of the smaller diameter, the
chances of plugging are much higher with a cap-
illary membrane. A benefit is that the packing
density is much greater. The first capillary mem-
brane was fabricated from polymers, but nowa-
days the technology development enables the
production of inorganic capillary modules
(Fig. 1).
Description of a Capillary Membrane
Module
A complete description of a membrane module
requires the simultaneous solution of local trans-
port equations that describe the flow and transport
conditions. In a capillary membrane module with
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_101-2
a permeable membrane wall, three regions of
flow should be considered: flow in the lumen,
flow within the membrane matrix, and flow in
the extracapillary space. The pressure distribu-
tion in the membrane is determined by applica-
tion of the overall balance of linear momentum.
The utilization of this conservation principle is
complicated by the fact that an external force
must be applied to keep the polymer membrane
stationary. In order to describe the behavior of a
membrane module, three submodels are required:
two that describe the transport on either side of
the membrane and a third model that character-
izes the separation properties of the membrane
and any porous support material (Nagy 2012).
Membrane Development
Besides polymeric and ceramic capillary mem-
branes, other types are also developing due to its
benefits. For example, supported zeolite mem-
branes have been synthesized under microwave
heating in order to reduce synthesis time in the
work of Sebastian et al. (2010) to prevent support
dissolution and to reproducibly obtain a thin
defect-free zeolite layer. The MFI-type zeolite
membranes were synthesized on ceramic capil-
laries, with a high membrane surface area-to-
volume ratio (>1,000 m2 m 3), which is by far
higher than that of classical tubular supports
(<500 m2 m 3).
2 Capillary Membranes
Capillary Membranes, Fig. 1 Ceramic capillary mem-
brane (Source: www.kerafol.com)
In a study of Zhu et al. (2010), alumina
microfiltration membranes were prepared on the
inner surface of alumina capillary support (outer
diameter, 4 mm; inner diameter, 2.5 mm) by a
dip-coating method. Scanning electron micros-
copy (SEM) observation, gas bubble pressure
(GBP) method, and membrane permeation test
were carried out to evaluate membrane perfor-
mance. Two major effects in preparation of
crack-free membrane, capillary filtration, and
film coating upon the thin support were studied.
Bonyadi and Mackley (2012) reported the
experimental results for the processing of
micro-capillary film (MCF) membranes. MCFs
are films with embedded multiple hollow capil-
laries and can be considered as a hybrid geometry
between flat sheet and hollow fibers. Compared
to the conventional membrane geometries, MCFs
potentially provide a higher surface area per unit
volume, better mechanical strength, ease of han-
dling, and more efficient module fabrication.
MCF membranes were fabricated out of ethylene
vinyl alcohol (EVOH) copolymer through a solu-
tion extrusion followed by a nonsolvent induced
phase separation (NIPS) process.
Solvent resistant nanofiltration (SRNF) is a
membrane separation process allowing for an
efficient separation of small molecules of
200–1,000 g mol 1 from organic solvents. The
application of SRNF in industry applications is
currently hindered by a limited choice of SRNF
membranes and configurations. In the work of
Dutczak et al. (2011), SRNF composite capillary
membranes made of an a-alumina support and a
selective poly(dimethylsiloxane) (PDMS) top
layer were prepared and studied. We combine
the advantages of a ceramic support such as
high mechanical, thermal, and chemical stability
with very good separation properties of the
PDMS coating.
Possible Applications
The number of practical applications of capillary
membranes is also expanding. A new combined
method is reported to localize the sites of enzyme
immobilization and to determine its catalytic
activity on a polymeric capillary membrane
reactor activity (Mazzuca et al. (2006)).
b-Glucosidase from olive fruit was selected as
enzyme model because of its suitable relevance
in the industrial processing of foods, in biotech-
nology, and in pharmaceuticals and for its
activity against the synthetic substrate 5-bromo-
4-chloro-3-indolyl-b-d-glucopyranoside which
develops an insoluble dyed product. The enzyme
was physically immobilized within 30 kDa cutoff
capillary polysulfone membranes, and results
obtained by means of a polyclonal antibody
against b-glucosidase and the synthetic substrate
clearly showed a coherent localization of the
immobilization enzyme sites and its activity.
Commercial flat sheet membranes were com-
pared to capillary one’s (Van der Bruggen
et al. 2003). For the capillary membrane, the
water flux could, however, easily be increased
and maintained at a stable level by a combination
of forward flushing and airflushing, which is not
possible with the flat sheet membranes. Further-
more, the water permeability for the capillary
membrane was 3–15 times higher than for the
commercial flat sheet membranes, which leads
to lower operating pressure and a correspond-
ingly lower energy consumption. For the capil-
lary membrane, rejections of organic and
inorganic compounds were satisfactory to reach
for COD and conductivity standards in one step
starting from the surface water. Rejections for
most flat sheet membranes were comparable to
the rejections obtained with the capillary mem-
brane, but the rejection of ions was usually
higher, except for the N30F and NF PES 10 mem-
branes. Low ion rejections are advantageous for
Capillary Membranes
drinking water production because demineraliza-
tion is avoided.
Suitability of capillary modules to the decol-
orization of both synthetic and actual dye solu-
tions by ultrafiltration was investigated as well.
The process involved capillary membranes made
of polysulfone and modified polysulfone. Mem-
brane modules (UFTA PS10, UFTA PS30, and
UFTA PSA50) of various molecular cutoffs were
applied (Majewska-Nowak et al. 1996).
Investigations concerning the application of
ceramic and capillary microfiltration and ultrafil-
tration membranes for the purpose of treatment of
natural water were carried out by Bodzek and
Konieczny 1998. The effectiveness of ultra- and
microfiltration was assessed by volumetric mea-
surements of the permeate flux as well as by
microbiological and physicochemical analyses.
Analysis of oxygen permeation fluxes through
Ba0.5Sr0.5Co0.8Fe0.2O3 d (BSCF) capillary
membranes, fabricated via a phase inversion
spinning technique using polysulfone as binder,
showed a significant limiting role of the surface
oxygen exchange kinetics. Within the studied
temperature and oxygen partial pressure ranges,
the activation of core and shell sides of the BSCF
capillary with praseodymium oxide (PrOx)
resulted in an increase in permeation rate of
about 300 % (Kovalevsky et al. 2011).
Capillary membrane diffusion scrubber
(CMDS) was scaled down to match with capillary
electrophoresis (CE), a quick separation technique
that requires nothing more than some nanoliters of
sample and, when combined with capacitively
coupled contactless conductometric detection
(C4D), is particularly favorable for ionic species
that do not absorb in the UV–vis region, like the
target analytes formaldehyde, formic acid, acetic
acid, and ammonium (Coelho et al. 2010).
Ceramic tube and ceramic capillary mem-
branes and their effect on permeate flux, oil reten-
tion, and specific energy consumption were
compared in the work of Gáspár et al. (2011).
The results, obtained with a stable oil-in-water
microemulsion as feed, demonstrated that the use
of novel ceramic capillary membranes at optimal
operating cross-flow velocity and transmembrane
pressure is reasonable.
3
References
Bodzek M, Konieczny K (1998) Comparison of ceramic
and capillary membranes in the treatment of natural
water by means of ultrafiltration and microfiltration.
Desalination 119(1–3):191–198
Bonyadi S, Mackley M (2012) The development of novel
micro-capillary film membranes. J Membr Sci
389:137–147
Coelho LHG, Melchert WR, Rocha FR, Rocha FRP, Gutz
IGR (2010) Versatile microanalytical system with
porous polypropylene capillary membrane for calibra-
tion gas generation and trace gaseous pollutants sam-
pling applied to the analysis of formaldehyde, formic
acid, acetic acid and ammonia in outdoor air. Talanta
83(1):84–92
Dutczak SM, Luiten-Olieman MWJ, Zwijnenberg HJ,
Bolhuis-Versteeg LAM, Winnubst L, Hempenius
MA, Benes NE, (. . .), Stamatialis D (2011) Composite
capillary membrane for solvent resistant
nanofiltration. J Membr Sci 372(1–2):182–190
Endre N (2012) 7 – Transport of fluid phase in a capillary
membrane. Basic equations of the mass transport
through a membrane layer. p 177–192
Gaspar I, Koris A, Bertalan Z, Vatai G (2011) Comparison
of ceramic capillary membrane and ceramic tube
membrane with static mixer inside. Chem Pap
65(5):596–602
Kovalevsky A, Buysse C, Snijkers F, Buekenhoudt A,
Luyten J, Kretzschmar J, Lenaerts S (2011) Oxygen
exchange-limited transport and surface activation of
Ba0.5Sr0.5Co0.8Fe0.2O3-d capillary membranes.
J Membr Sci 368(1–2):223–232
Majewska-Nowak K, Kabsch-Korbutowicz M, Winnicki
T (1996) Capillary membranes for separation of dye
particles. Desalination 105(1–2):91–103
Mazzuca S, Giorno L, Spadafora A, Mazzei R, Drioli
E (2006) Immunolocalization of b-glucosidase
immobilized within polysulphone capillary membrane
and evaluation of its activity in situ. J Membr Sci
285(1–2):152–158
Sebastian V, Mallada R, Coronas J, Julbe A, Terpstra RA,
Dirrix RWJ (2010) Microwave-assisted hydrothermal
rapid synthesis of capillary MFI-type zeolite-ceramic
membranes for pervaporation application. J Membr
Sci 355(1–2):28–35
Van der Bruggen B, Hawrijk I, Cornelissen E,
Vandecasteele C (2003) Direct nanofiltration of sur-
face water using capillary membranes: comparison
with flat sheet membranes. Sep Purif Technol
31(2):193–201
Zhu J, Fan Y, Xu N (2010) Preparation and characteriza-
tion of alumina membranes on capillary supports:
effect of film-coating on crack-free membrane prepa-
ration. Chin J Chem Eng 18(3):377–383
C
Capillary Tubes
Andras Koris
Corvinus University of Budapest, Budapest,
Hungary
Def. (Engineering) A tube sufficiently fine so that
capillary attraction of a liquid into the tube is
significant. (General Physics) A glass tube with
a fine bore and thick walls, used in thermometers,
etc. (Medical) Glass capillary tubes are used for
the collection of blood in a variety of healthcare
settings, including hospitals, ambulatory care
facilities, physicians’ offices, blood donation
facilities, and blood testing centers.
Basic Description
A capillary tube works by its being tension
pulling between the circumference and the inner
wall of the tube. The restriction and metering of
the liquid will maintain pressure differential. See
more at ▶ Capillary Force.
Capillary tubes can be made of different mate-
rials like plastic, glass, stainless steel, and
ceramics.
Wall thickness of microhematocrit capillary
tubes is 0.01 mm.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_102-2
Applications
It can be a device used to measure kinematic
viscosity. Kinematic viscosity is the time it
takes for a fixed amount of fluid to move through
a measured length of the capillary tube with grav-
ity alone.
In Membrane Science once capillary tubes
present in the filter media, they are called pores.
Symmetric pore structure is usually formed by
pressing and sintering, extruding and stretching,
irradiation and etching, template leaching, or
phase inversion. On the other hand, capillaries
can be found in capillary membranes as well.
Capillary tubes are used in analytical applica-
tions, such as chromatography, gas and liquid
lines, and measurement components in remote
thermometer systems (with or without
compensation).
An indispensible capillary tube is used for
calculating blood clotting time or determining
melting points.
Also a capillary tube is used in refrigeration
and air-conditioning systems. It is a copper tube
that has a small internal diameter. A capillary
tube functions by dropping pressure due to its
small internal diameter. The refrigerant leaves
the condenser and enters the capillary tube and
when it reaches the capillary tube falls in pressure
and keeps the pressure constant. It limits the
maximum amount of the refrigerant that can be
charged in the refrigeration system.
C
Carbon Membrane
May-Britt Hägg
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Norway
Carbon membranes are usually characterized as
carbon molecular sieves (CMS membranes) as
they basically separate based on molecular size.
This means that the pores can be tailored for a
specific gas mixture, permeating the smallest
molecule and retaining the larger ones.
There are two main ways of preparing the
CMS membranes: pyrolysis of polymeric hollow
fibers or performing pyrolysis of a polymer
sprayed onto a ceramic support tube. In both
cases a pyrolysis protocol needs to be developed
for the specific polymer and pores to be obtained.
Important variables to be controlled during the
pyrolysis is heating rate, soak time, final carbon-
ization temperature, and which gas to use as
purge (typically an inert gas or CO2) vacuum
may also be used. Each of these variables will
influence the final pore size and separation prop-
erties of the membrane. The final carbonization
temperature is usually in the range of 500–900  C.
Carbon membranes are fairly easy to produce
on lab scale as much is known on how carboni-
zation conditions affect separation properties
(Geiszler and Koros 1996; He and Hägg 2012).
However, the scaling up to commercial-size
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_106-1
modules may be more of a challenge as
commented on further down.
The first carbon membranes were prepared
from carbonization of cellulose hollow fibers by
Koresh and Soffer (1983). Since then various
polymers have been used such as polyimides,
polyacrylonitrile (PAN), poly(phenylene oxide)
(PPO), cellulose derivates, and others. The sepa-
ration properties of CMS membranes are very
attractive as their sieving properties easily exceed
the upper Robeson boundary of permeability ver-
sus selectivity trade-off relationship (Robeson
2008) – this makes it also attractive for industrial
applications. The making of the membranes may
thus involve six steps: material selection, mate-
rial functionalization, precursor preparation,
pretreatment, carbonization, and possibly
posttreatment (Fig. 1). Functionalization usually
means adding a porogen or a metal salt to the
precursor. The porogen will degrade during the
carbonization and thereby increase the pore vol-
ume. When the additive is a metal salt (doping the
precursor), the final CMS membrane will contain
the metal which may functionalize the membrane
by showing high affinity to one of the permeating
gases (Lie and Hägg 2005). Then if using
posttreatment, surface modifiers may adjust the
pore size. A big advantage of carbon membranes
is that they may be used for high-temperature gas
separations. This advantage may, however, be
compromised if the surface modifier is a degrad-
able polymer at process operation temperature.
The different ways of tailoring microporous
2 Carbon Membrane

Carbon Membrane,
Fig. 1 Comparing the
CO2/CH4 Robeson upper
bound for dense and
thermally rearranged
(TR) polymer membranes
to the carbon membranes
and the region for industrial
applicability – data for
CMS membranes and
industrial applicability
region added to the original
Robeson plot (see Hägg and
He 2011)

a b c

Porogens Doping/spacers Surface modifiers

Carbon Membrane, Fig. 2 Schematic model of different ways of tailoring microporous carbon. The dashed line
shows the limit of an original slit-shaped pore (Lie and Hägg 2005)

carbon membranes are illustrated in Fig. 2 (Lie
and Hägg 2005).
Although showing excellent separation per-
formance, the self-supported hollow fiber mem-
branes may be quite brittle, thus the scaling up
and module making are challenging. The Norwe-
gian company MemfoACT did successfully dem-
onstrate on pilot scale the use of carbonized self-
supported cellulose hollow fibers for upgrading
of biogas (CO2/CH4 separation) (Fig. 3). The
scaling up to full-size commercial module has
however not yet been reported (in 2015).
The supported carbon membranes will provide
better mechanical strength than self-supported
fibers but will naturally have lower packing den-
sity. These types of carbon membranes have been
especially studied for high-temperature applica-
tions (e.g., H2/CO2 separation and as carbon
membrane reactors). The special challenge of
making these membranes is to obtain a defect-
free carbon layer on the top of the
support – compatibility between support and car-
bon layer may also be a problem. Supported CMS
membranes have been studied by several.
A method by using spin-coat technique was
Carbon Membrane
Carbon Membrane,
Fig. 3 Left: SEM picture
of a CMS fiber; wall
thickness is 16 mm. Right:
A bundle of CMS hollow
fibers ready for mounting in
a pilot module as illustrated
by the company
MemfoACT in 2013 on
their homepage
developed already in 1996 by Rao and Sirkar
(1996). Stainless steel disks (Acharya and Foley
1999) as well as porous a-alumina tubes (Zhou
et al. 2003) have been reported as suitable support
for pyrolized carbon membranes. Acharaya and
Foley studied the separation of O2/N2 and
obtained a separation factor of 12. A challenge
of concern with respect to any CMS membrane is
the possibility of aging, whereby separation per-
formance may decline over time; hence, the
membranes need to be regenerated. Several
ways are proposed, such as using heat, purging
with air or propane, or using low-voltage direct
current at intervals (Lie and Hägg 2006). The
research on CMS membranes is however contin-
uously moving forward, and is well documented,
and example is Fu et al. (2015). The main chal-
lenge still seems to be scaling up to commercial-
size modules.
Potential of Applications
Due to the possibility of tailoring the pores, the
CMS membranes have a very nice potential of
separating gas pairs which are difficult to separate
using other type of membranes and gases which
are much alike in structure and physical proper-
ties, typically O2/N2 and C3H8/C3H6 (olefin/par-
affins in general) (Yoshino et al. 2003). Other
type of gas separations can typically be CO2/
CH4 (both as biogas and as natural gas) and
recovery of hydrogen from gas streams such as
H2/CO2 (precombustion) and H2 from refinery
gasses.
3
References
Acharya H, Foley H (1999) Spray-coating of nanoporous
carbón membranes for air separation. J Membr Sci
161:1–5
Fu S, Sanders E, Kulkarni SS, Koros WJ (2015) Carbon
molecular sieve membrane structure–property rela-
tionships for four novel 6FDA based polyimide pre-
cursors. J Membr Sci 487:60–73
Geiszler VC, Koros WJ (1996) Effects of polyimide pyrol-
ysis conditions on carbon molecular sieve membrane
properties. Ind Eng Chem Res 35:2999–3003
Hägg MB, He X (2011) Carbon molecular sieve mem-
branes for gas separation, chapter 15. In: Drioli E,
Barbieri G (eds) Membrane engineering for the treat-
ment of gases, membrane engineering handbook. RCS
Publishing, Cambridge CB4 0WF, UK. ISBN:978-1-
84973-239
He X, Hägg MB (2012) Structural, kinetic and perfor-
mance characterization of hollow fiber carbon mem-
branes. J Membr Sci 390–391:23–31
Koresh J, Soffer A (1983) Molecular sieve carbon mem-
brane. Part I. Presenting a new device for gas mixture
separation. Sep Sci Technol 18:723–734
Lie JA, Hägg MB (2005) Carbon membranes from cellu-
lose and metal loaded cellulose. Carbon 43:2600–2607
Lie JA, Hägg MB (2006) Carbon membranes from cellu-
lose: synthesis, performance and regeneration.
J Membr Sci 284:79–86
Rao MB, Sirkar S (1996) Performance and pore charac-
terization of nanoporous carbon membranes for gas
separation. J Membr Sci 110:109
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320:390–400
Yoshino M, Nakamura S, Kita H, Okamoto K, Tanihara N,
Kusuki Y (2003) Olefin/parafin separation perfor-
mance of carbonized membranes derived from asym-
metric hollow fiber membranes of 6FDA/BPDA-
DDBT copolyimide. J Membr Sci 215:169–183
Zhou W, Yoshino M, Kita H, Okamoto K (2003) Prepa-
ration of gas permeation properties of carbón molecu-
lar sieve membranes based on sulfonated phenolic
resin. J Membr Sci 217:55–67
C
Carbon Nanotube Membranes (CNT
Membranes)
Enrica Fontananova and Enrico Drioli
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, University
of Calabria, Rende(CS), Calabria, Italy
Carbon nanotubes (CNTs) are allotropic forms of
carbon that can be conceptually visualized as a
cylindrical nanostructure formed by rolling a
graphene sheet along a lattice vectors (m,n) in
the graphene plane (Fig. 1).
Depending from the number of concentric cyl-
inders, it is possible to have: single-, double-, or
multiwalled carbon nanotubes (SWCNTs,
DWCNTs, MWCNTs). The indices (m,n) deter-
mine the diameter and chirality (i.e., the chiral
angle between hexagons and the tube axis) of the
CNTs (Dai 2002). The CNTs can be in the zigzag,
armchair, or chiral form with metallic or semicon-
ducting properties (Table 1).
CNTs, thanks to their diameter in the nanome-
ter range and their atomically smooth surfaces,
offer unique systems for fast molecular transport
(Hummer et al. 2001; Kalra et al. 2003). Molecu-
lar dynamics (MD) simulations showed spontane-
ous and continuous filling of a CNT with a
one-dimensionally ordered chain of water
molecules.
Membranes made of ordered arrays of carbon
nanotubes well aligned along the direction
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_109-1
perpendicular to the substrate surface have been
already synthesized in which the transport occur
through the inner core of the CNTs (Majumder
et al. 2011). High permeability enhancement than
predictions (>10 for gases and >1000 for liquids)
have been obtained with these membranes. How-
ever, the small area (typically in the order of few
mm2), the long and complex fabrication process,
and the poor mechanical stability of these type of
CNT membranes, limit the practical applicability
of these interesting nanostructured systems. On
the contrary, more easy is the scale up of CNT
membranes in which the CNTs are mixed with a
polymer in the form of mixed matrix membranes.
The main limitations of these membranes are
related to the poor dispersion of the CNTs in the
polymeric matrix and the moderate increase of the
membrane performance.
It is interesting to note that graphitic carbon
nanomaterials like CNTs are usually introduced at
lower content (
2 wt%) in mixed matrix mem-
branes in comparison with three-dimensional
inorganic nanofillers like TiO2 and ZrO2 (usually
blended at loading 5 wt%, up to 60 wt%), thank
to their high specific surface, elevated aspect ratio,
and the intrinsic properties of graphitized struc-
ture. In addition, the relatively easy functiona-
lization of the surface of carbon nanomaterials
render them ideal candidate to tailor the poly-
mer/nanofiller interface.
CNTs were succesfully entrapped in mixed
matrix membranes made of various polymeric
materials by several techniques including:
2 Carbon Nanotube Membranes (CNT Membranes)
Carbon Nanotube a
Membranes (CNT
Membranes),
Fig. 1 Schematic
honeycomb structure of a
graphene sheet (sp2
hybridized carbon network)
(a) and image of single-,
double-, and multiwalled
carbon nanotubes
(SWCNTs, DWCNTs,
MWCNTs), (b)
SWCNT
dispersion in the casting solution and successive
phase separation, entrapping in the membrane
pores using a polymer binder, in situ crosslinking
of a polymer matrix around oriented CNTs (Ismail
et al. 2009). The resulting mixed matrix CNT
membranes offer, in many cases, relevant advan-
tages in comparison with the polymeric samples.
Poly(vinyl alcohol) (PVA)/MWCNTs membranes
were realized for pervaporation application,
obtaining significant improvement in Young’s
modulus and thermal stability, as compared to
pure PVA membranes (Peng et al. 2007). The
entrapment of MWCNTs in polyethersulfone
(PES) membranes reduced fouling problems in
water treatment (Celik et al. 2011). Mixed matrix
membranes consisting of sulfonated carbon
nanotubes (sCNTs) and sulfonated poly
(ethersulfone ether ketone ketone) (SPESEKK)
were also fabricated via the solution casting
method (Zhou et al. 2011). The proton conductiv-
ity of the SPESEKK membrane increased while
the methanol permeability decreased as the sCNTs
content increased. MWCNTs were covalently
linked to aromatic polyamide (PA) membranes
by a polymer grafting process (Shawky
et al. 2011). Measurements of mechanical proper-
ties of this composite showed an increased
n
m
DWCNT MWCNT
membrane mechanical strength relative to the PA
polymeric membranes.
Mixed matrix polyimide membranes were also
prepared using functionalized MWCNTs
(aminated or oxidized). The MWCNTs functiona-
lization improved their dispersion in the casting
solution in comparison to pristine MWCNTs and,
as a consequence, in the formed membranes. The
membranes containing functionalized MWCNTs
showed better performance in the rejection of
dyes (enhanced flux and reduced fouling, with
similar or higher rejection), with respect to refer-
ence polymeric membranes (without MWCNTs).
These results were attributed to the formation of
low-resistance pathways for solvent transport at
the interface between the MWCNTs and the poly-
meric chains. Moreover, the MWCNTs reduced
the severe membrane fouling caused by the
absorption of the positively charged dye Safranine
(used as a model of organic pollutant) with respect
the polymeric membrane, by a screening effect of
the attractive electrical interactions between the
Safranine and the membrane surface character-
ized by a negative value of zeta potential
(Grosso et al. 2014).
The presence of oxygen-containing polar
groups on oxidized MWCNTs, resulted also in a
Carbon Nanotube Membranes (CNT Membranes) 3

Carbon Nanotube Membranes (CNT Membranes), Table 1 Different forms of a SWCNT and its electrical
properties
(n, m) Form Electrical conductivity
(n, 0) Zigzag Metallic when n is multiple of 3, otherwise, semiconducting

(n, m) Armchair Metallic

with n = m

(n, m) Chiral Metallic when (n-m)/3 is an integer, otherwise, semiconducting

with m 6¼ 0 and n

good dispersion in polyvinylidene difluoride References

(PVDF) membranes, allowing the formation of
mixed matrix membranes with a lower fouling
tendency in comparison with the bare polymeric
samples (Fontananova et al. 2014).
MWCNTs were also immobilized in the pores
of a hydrophobic membrane improving the water-
membrane interactions to promote vapor perme-
ability in membrane distillation process (Gethard
et al. 2011). In this case, the CNTs dispersion was
forced under vacuum into the pores of a polypro-
pylene (PP) membrane, using PVDF as binder.
Celik E, Park H, Choi H, Choi H (2011) Carbon nanotube
blended polyethersulfone membranes for fouling con-
trol in water treatment. Water Res 45:274–282
Dai H (2002) Carbon nanotubes: synthesis, integration,
and properties. Acc Chem Res 35:1035–1044
Fontananova E, Bahattab MA, Aljlil SA, Alowairdy M,
Rinaldi G, Vuono D, Nagy BJ, Drioli E, Di Profio
G (2014) From hydrophobic to hydrophilic polyvinyli-
denefluoride (PVDF) membranes by gaining new
insight into material’s properties. RSC Adv
5:56219–56231
Gethard K, Sea-Know O, Mitra S (2011) Water desalina-
tion using carbon-nanotube-enhanced membrane distil-
lation. Appl Mater Interfaces 3:110–114
Grosso V, Vuono D, Bahattab MA, Di Profio G, Curcio E,
Al-Jilil SA, Alsubaie F, Alfife M, Nagy BJ, Drioli E,
Fontananova E (2014) Polymeric and mixed matrix
polyimide membranes. Sep Purif Technol 132:684–696
4 Carbon Nanotube Membranes (CNT Membranes)
Hummer G, Rasaiah JC, Noworyta JP (2001) Water con-
duction through the hydrophobic channel of a carbon
nanotube. Nature 414:188–190
Ismail AF, Goh PS, Sanip SM, Aziz M (2009) Transport
and separation properties of carbon nanotube-mixed
matrix membrane. Sep Purif Technol 70:12–26
Kalra A, Garde S, Hummer G (2003) Osmotic water trans-
port through carbon nanotube membranes. Proc Natl
Acad Sci U S A 100:10175–10180
Majumder M, Chopra N, Bruce JH (2011) Mass transport
through carbon nanotube membranes in three different
regimes: ionic diffusion and gas and liquid flow. ACS
Nano 5:3867–3877
Peng F, Hu C, Jiang Z (2007) Novel ploy(vinyl alcohol)/
carbon nanotube hybrid membranes for pervaporation
separation of benzene/cyclohexane mixtures. J Membr
Sci 297:236–242
Shawky HA, Chae S-R, Lin S, Wiesner MR (2011) Syn-
thesis and characterization of a carbon nanotube/poly-
mer nanocomposite membrane for water treatment.
Desalination 272:46–50
Zhou W, Xiao J, Chen Y, Zeng R, Xiao S, Nie H, Li F, Song
C (2011) Sulfonated carbon nanotubes/sulfonated poly
(ether sulfone ether ketone ketone) composites for
polymer electrolyte membranes. Polym Adv Technol
22:1747–1752
C
Carbon Porous Membranes Modified electropolymerization at +0.9 V vs. Ag/AgCl.
with Enzymes The oxidation of pyrrole allowed the entrapment
Christophe Innocent
cc 407, UMR 5635 CNRS - ENSCM - UM II,
Institut Européen des Membranes, Montpellier
Cedex 5, France
The carbon porous tubes (from Novasep-Orelis-
France) have been characterized by average pore
diameter of 3 mm and an inner diameter of 0.6 cm
(Fig. 1).
The immobilization of enzyme on the carbon
tube surface has been carried out by dipping in
enzyme solution and then addition of pyrrole
monomer just before starting the anodic
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_112-5
of enzyme in polypyrrole coated on the electrode
surface.
A glucose/O2 biofuel cell is based on tubular
cathode (coated with laccase/ABTS on the exter-
nal surface for dioxygen reduction) and the tubu-
lar anode (coated with glucose oxidase enzyme
(GOD) and hydroxyquinoline sulfonic acid as
mediator) on the internal surface for glucose
oxidation.
The two electrodes were soaked in an
unstirred 10 mM glucose solution. Glucose dif-
fused through the polypyrrole film to be oxidized
by the GOD at the anode. In order to prevent the
presence of dioxygen in the vicinity of GOD,
dissolved oxygen was supplied to the system by
2 Carbon Porous Membranes Modified with Enzymes

Carbon Porous
Membranes Modified
with Enzymes,
Fig. 1 Photography of
carbon tube (photo IEM)

circulating through the inner cavity of the

biocathode, then before being reduced at the
external surface by the BOD.
Cylindrical and porous carbon tubes were used
as original conducting support for the compart-
ment of the bioelectrodes, for enzyme immobili-
zation and transport of dissolved oxygen via
diffusive flow through the porosity (Fig. 2). The
resulting glucose/oxygen biofuel cell is operated
at a maximum power density of 42 mWcm 2at
0.3 V and 37  C in phosphate buffer pH 7.4.

Carbon Porous Membranes Modified with Enzymes,

Fig. 2 Scheme of concentric biofuel cell (thesis of G.
MERLE, University Montpellier 2, 2008)
C
Catalytic Membranes
Jose M. Sousa
Chemistry Department, School of Life and
Environment Sciences, University of Tras-os-
Montes e Alto Douro, Vila Real, Portugal
LEPABE - Laboratory for Process Engineering,
Environment, Biotechnology and Energy,
Chemical Engineering Department, Faculty of
Engineering, University of Porto, Rua Roberto
Frias, Porto, Portugal
A catalytic membrane is a membrane with cata-
lytic properties. The catalytic activity can be
intrinsic to the material itself, as in the case of
membranes made of Pd, TiO2, and H-ZSM-5
zeolite, which are catalytic for specific reactions,
or can be obtained by coating the external or the
internal (porous) surfaces of the membrane with
the catalyst (metal or oxides) or even by occlud-
ing the catalyst (metal nanoclusters, zeolites,
activated carbon, metal complexes) inside a
dense polymer matrix (Gryaznov 1986, 1992;
Irusta et al. 1998; Gobina and Hughes 1994;
Saracco and Specchia 2000; Itoh 2000; Dittmeyer
et al. 2001; Piera et al. 2001; Julbe 2005; van Dyk
et al. 2003; Marcano and Tsotsis 2002; Basile
2012; Fritsch and Peinemann 1995).
Catalytic membranes can be inorganic
(metallic, ceramic, or carbon made) or polymeric
in their nature. Examples of dense inorganic cat-
alytic membranes are the ones made of
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_116-6
palladium, which are catalytically active for
hydrogenation reactions (though presenting low
activity), while porous catalytic inorganic mem-
branes can be made of a variety of materials,
namely, alumina, silica, titania, and zeolites
among others. Porous polymeric membranes are
usually made, for example, of polysulfone, poly-
acrylonitrile, or polypropylene, while dense poly-
meric membranes are prepared from PDMS
(polydimethylsiloxane) and other silicones,
PVA (polyvinyl alcohol), perfluoropolymers,
polyimides, or polyamides among other polymers
(Basile and Gallucci 2011; Basile 2012).
Membranes in general can be permselective or
nonpermselective. Catalytic permselective mem-
branes are characterized by two important param-
eters concerning their separation ability:
Permselectivity, which describes the ability of
the membrane to transport the different compo-
nents of a mixture at different rates, and the
permeability, which quantifies the total amount
permeated by the membrane when subjected to
specific operation conditions. Nonpermselective
membranes can be described by their permeabil-
ity, but they are not able to discriminate between
the different components of a mixture (Marcano
and Tsotsis 2002).
The mass transport mechanism suitable to
describe the permeation rate through a
(catalytic) membrane is primarily a function of
the type of membrane. For dense membranes, the
accepted model is the sorption (solution) diffu-
sion (the permeant species in gas or liquid phase
2 Catalytic Membranes
Catalytic Membranes,
Fig. 1 Porous catalytic
membrane for wastewater
treatment (Reprinted with
permission from Raeder
2010)
sorbs into the membrane at the higher chemical
potential side, diffuses through the membrane
subjected to the driving force gradient, and
desorbs on the opposite side). These membranes
are usually permselective. Concerning porous
membranes, the total mass transport results from
different contributions, namely, a diffusive com-
ponent (activated, surface, Knudsen and bulk)
and a viscous component (Poiseuille flow). The
contribution of each one depends on the operating
conditions and on the pore’s size. For pore radius
between 1 and 50 nm, Knudsen diffusion is nor-
mally the predominant mass transfer mechanism
(Knudsen diffusion is characterized by the mean-
free path of the traveling species being much
larger than the pore radius and is independent of
any pressure gradient along the pore), and the
membranes present some permselectivity, related
with the ratio of the species molar mass. For
membranes with larger pores, namely,
macroporous, the mass transfer mechanism is a
viscous flow if a total pressure gradient across the
porous membrane is present or bulk diffusion if
not. Neither of these situations allows any
permselectivity. When the membrane has micro-
pores and the species adsorb significantly, as in
the case of zeolites, surface diffusion has a rele-
vant contribution. Also in these cases the mem-
branes are permselective (Basile and Nunes
2011).
A catalytic membrane is used to carry out
different types of reactions, namely, chemical,
biochemical, electrochemical, or photocatalytic,
in a so-called membrane reactor. The type of
membrane to be used, porous or dense, polymeric
or inorganic, etc., depends on several factors,
namely, the type of reaction. For example,
dense polymeric catalytic membranes are used
for low-temperature reactions where the
permselectivity is important for shifting the con-
version beyond the thermodynamic equilibrium
value based on feed conditions (e.g., selective
removal of water in esterification reactions) or
to enhance the reaction selectivity (e.g., hydra-
tion, epoxidation, isomerization, and hydrogena-
tion reactions). Dense polymeric catalytic
membranes can also be used as contactors for
promoting reactions between two immiscible
phases with segregated feed (e.g., oxyfunctiona-
lization of hydrocarbons with hydrogen peroxide
reactions) (Basile and Gallucci 2009).
Another type of reaction that has been studied
is the photocatalytic removal of contaminants
from water, either using porous or dense poly-
meric catalytic membranes. The catalyst typi-
cally used is TiO2, occluded or coated, but also
occluded Fe in an H2O2 oxidant medium (photo-
Fenton process) has been considered (Basile and
Nunes 2011).
Catalytic nonpermselective porous mem-
branes, polymeric or inorganic, can be used to
improve the contact between the reactants and the
catalyst, in order to obtain higher reaction con-
versions. Particularly in the case of triphasic
(gas/liquid/solid) reactions, usually limited by
the diffusion of the gaseous reactant, porous
membrane reactors show conversion advantages.
By controlling the pressure of the gas and liquid
Catalytic Membranes
flows, it is possible to shift the reactants to meet
the catalyst zone (Fig. 1).
The same segregated feeding strategy can also
be used in cases of reactions where a strict control
of the reactants is important, namely, in the case
of very fast or highly exothermic reactions.
In the case of reactions where a complete
conversion of some components, like VOCs, is
of high importance, porous catalytic membranes,
permselective or not, are usually used in a “flow-
through” mode, that is, all the reactants are fed
conjointly. In these cases, it is critical controlling
the residence time of the reactants to guarantee a
complete conversion (Westermann and Melin
2009).
References
Basile A (ed) (2012) Handbook of membrane reactors.
Woodhead, Cambridge, UK (in press)
Basile A, Gallucci F (eds) (2009) Modeling and simula-
tion of membrane reactors. Nova, New York
Basile A, Gallucci F (eds) (2011) Membranes for mem-
brane reactors: preparation, optimization and selec-
tion. Wiley, New York
Basile A, Nunes S (eds) (2011) Advanced membrane
science and technology for sustainable energy and
environmental applications. Woodhead, Cambridge,
UK
Dittmeyer R, Hollein V, Daub K (2001) Membrane reac-
tors for hydrogenation and dehydrogenation processes
based on supported palladium. J Mol Catal A Chem
173:135–184
Fritsch D, Peinemann K-V (1995) Catalysis with homo-
geneous membranes loaded with nanoscale metallic
clusters and their preparation. Catal Today
25:277–283
Gobina E, Hughes R (1994) Ethane dehydrogenation
using a high-temperature catalytic membrane reactor.
J Membr Sci 90:11
3
Gryaznov VM (1986) Hydrogen permeable palladium
membrane catalysts. Platinum Met Rev 30:68
Gryaznov VM (1992) Platinum metals as components of
catalyst-membrane systems. Platinum Met Rev 36:70
Irusta S, Pina MP, Menendez M, Santamaria J (1998)
Development and application of perovskite-based cat-
alytic membrane reactors. Catal Lett 54:69
Itoh N, Haraya K (2000) A carbon membrane reactor.
Catal Today 56:103
Julbe A (2005) Zeolite membranes – a short overview. In:
Cejka J, van Bekkum H (eds) Zeolites and ordered
mesoporous materials: progress and prospects. Studies
in surface science and catalysis, Elsevier science &
technology, vol 157. p 135
Marcano JS, Tsotsis TT (2002) Catalytic membranes and
membrane reactors. Wiley, Weinheim
Piera E, Tellez C, Coronas J, Menendez M, Santamaria
J (2001) Use of zeolite membrane reactors for selec-
tivity enhancement: application to the liquid-phase
oligomerization of i-butene. Catal Today 67:127
Raeder H (2010) Wastewater oxidation using catalytic
contactor – a revolutionary catalytic membrane reactor
for wastewater treatment. SINTEF Materials and
Chemistry. https://www.sintef.no/globalassets/
upload/materialer_kjemi/energikonvertering-og-
materialer/dokumenter/watercatox-screen.pdf
Saracco G, Specchia V (2000) Catalytic combustion of
propane in a membrane reactor with separate feed of
reactants. IV. Transition from the kinetics- to the trans-
port-controlled regime. Chem Eng Sci 55:3979
van Dyk L, Miachon S, Lorenzen L, Torres M, Fiaty K,
Dalmon JA (2003) Comparison of microporous MFI
and dense Pd membrane performances in an extractor-
type CMR. Catal Today 82:167–177
Westermann T, Melin T (2009) Flow-through catalytic
membrane reactors – principles and applications.
Chem Eng Process 48:17–28
Further Reading
Seidel-Morgenstern A (ed) (2010) Membrane reactors:
distributing reactants to improve selectivity and
yield. Wiley, New York
C
Catalytic Reactions, Membrane
Operations of
Adelio Mendes
Faculty of Engineering, University of Porto,
Porto, Portugal
Catalytic reactions (chemical, biochemical, pho-
tochemical, electrochemical, and photoelectro-
chemical) are promoted or enhanced in their
rate by a catalyst. Most of the chemical catalytic
reactions are heterogeneous; the catalyst is nor-
mally a solid, while reactants are in fluid phase. In
the petrochemical industry, for example, the cat-
alyst is usually composed of micro- or
nanoclusters of a noble metal in a support, usually
a metal oxide. In the fine chemical and organic
synthesis, on the other hand, it is common that the
reactions be homogeneous.
Membrane is a permselective medium or inter-
face between two fluid phases. Membrane pro-
cesses can be synergistically combined with
catalytic reactors targeting conversion, selectivity,
or safety enhancements. These effects may be
obtained by selective product extraction and puri-
fication, normally originating conversion and
selectivity enhancements, or by segregated or dis-
tributed feed of reactants, aiming selectivity
and/or safety enhancements. When a reactor is
synergistically combined with a membrane pro-
cess, the unit is called membrane reactor. Usually,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_118-3
membrane and reactor are integrated in the same
housing (Marcano and Tsotsis 2002).
Membranes can be inorganic (metallic,
ceramic, carbon) or polymeric in their nature.
Membranes can be permselective or
non-permselective. Permselective membranes
are characterized by two important parameters:
permselectivity, which describes the ability of the
membrane to transport the different components
of a mixture at different rates, and permeability,
which quantifies the total amount permeated by
the membrane when subjected to specific opera-
tion conditions, normalized by the membrane
thickness. The mass transport mechanism is
described by the sorption – diffusion models for
dense and microporous membranes. For porous,
different contributions should be considered: dif-
fusive (activated, surface, Knudsen, and bulk)
and viscous (Poiseuille flow). The contribution
of each one depends on the operating conditions,
pore size, penetrant mass and size and the sur-
face, and penetrant nature (Basile and Gallucci
2011).
There are various potential industrial applica-
tions that take advantage of combining a catalytic
reactor with a membrane process, integrated or
not in the same device, operating either in liquid
and/or gas phases. One of the main membrane
studied functions has been the selective removal
of components from the reaction medium.
Biorefining and biofuel production, for example,
take advantage of process integration of a biore-
actor and a permselective membrane, as is the
2 Catalytic Reactions, Membrane Operations of
case of bioethanol and acetic acid production: the
continuous removal of the main product from the
reaction medium decreases or even eliminates the
potential reaction inhibition (Ma et al. 2009; He
et al. 2012). Also the removal of fermentation
inhibitors generated during the pretreatment pro-
cess of lignocellulosic material for the second-
generation bioethanol production is important,
because of the negative impact in the ethanol
yield and productivity and in the cell growth
inhibition (He et al. 2012). Still in the selective
removal of a reaction product from the reaction
medium, it can be referred to as the selective
removal of water in esterification reactions and
the selective removal of hydrogen in dehydroge-
nation and water-gas shift reactions for a conver-
sion shifting beyond the thermodynamic
equilibrium based on feed conditions. In case of
using palladium-silver membranes in the dehy-
drogenation and water-gas shift reactions, high-
purity hydrogen can be obtained (Marcano and
Tsotsis 2002; Basile and Nunes 2011).
The membrane can also play a role of a selec-
tive distributor, dosing a reactant along the reac-
tion medium. This approach has been extensively
used in consecutive-parallel reaction schemes,
especially in partial oxy-dehydrogenation or oxi-
dation of alkanes and oxidative coupling of meth-
ane, using dense ceramic or metallic membranes
permselective to oxygen (silver, yttrium-
stabilized zirconia, perovskites and related
oxides, or composite membranes involving a
mixture of ionic and electronic conducting mate-
rials, usually oxides and metals). Separating the
hydrocarbon and oxygen feed, the reaction is
carried on in much safer conditions, and the pos-
sibility of thermal optimization and oxygen con-
centration control along the reaction medium can
be used to improve the selectivity for the inter-
mediate desired oxygenated product. Though in
less extension, also proton-conducting mem-
branes have been considered as distributors for
hydrogenation reactions (Marcano and Tsotsis
2002; Seidel-Morgenstern 2010).
References
Basile A, Gallucci F (eds) (2011) Membranes for mem-
brane reactors: preparation, optimization and selec-
tion. Wiley, New York
Basile A, Nunes S (eds) (2011) Advanced membrane
science and technology for sustainable energy and
environmental applications. Woodhead Publishing
Limited, Cambridge
He Y, Bagley DM, Leung KT, Liss SN, Liao BQ
(2012) Recent advances in membrane technologies
for biorefining and bioenergy production. Biotechnol
Adv 30:817–858
Ma Y, Wang J, Tsuru T (2009) Pervaporation of water/
ethanol mixtures through microporous silica mem-
branes. Sep Purif Technol 66:479–485
Marcano JS, Tsotsis TT (2002) Catalytic membranes and
membrane reactors. Wiley-VCH Verlag GmbH,
Weinheim
Seidel-Morgenstern A (ed) (2010) Membrane reactors:
distributing reactants to improve selectivity and
yield. Wiley, New York
Further Reading
Basile A (ed) (in press) Handbook of membrane reactors.
Woodhead Publishing Limited, Cambridge
I
Ion-Exchange Membranes
Heiner Strathmann
Institute for Chemical Technology, Stuttgart
University, Stuttgart, Germany
Ion-exchange membranes. Most of today’s
ion-exchange membranes used in commercially
relevant processes are 0.2–1 mm thin sheet of
hydrocarbon or fluorinated hydrocarbon poly-
mers which carry positively or negatively
charged ions fixed to the polymer structure
(Xu 2005; Bergsma and Kruissink 1961; Molau
1981). The type and the concentration of the fixed
ions in a membrane structure determine
permselectivity and the electrical resistance of a
membrane, while the chemical stability and the
mechanical properties of the membrane are deter-
mined mainly by the matrix polymer. There are
three types of ion-exchange membranes:
• Cation-exchange membranes which contain
fixed negatively charged ions and which have
a selective permeability for cations
• Anion-exchange membranes which contain
fixed positively charged ions and which have
a selective permeability for anions
• Bipolar membranes which consist of a cation-
and an anion-exchange membrane laminated
together
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_119-1
The ions often used as fixed charges in cation-
exchange membranes are
SO
3 and
COO .


Fixed charges used in anion-exchange mem-
branes are
Nþ HR2 and
Nþ R3 .
The structure of a cation-exchange membrane
is illustrated in Fig. 1 which shows the polymer
matrix with the fixed negative ions and the
mobile counterions as well as their pathway
through the membrane.
The most desired properties for ion-exchange
membranes are:
• High permselectivity – an ion-exchange mem-
brane should be highly permeable for counter-
ions, but should be impermeable to co-ions.
• Low electrical resistance – the permeability of
an ion-exchange membrane for the counter-
ions under the driving force of an electrical
potential gradient should be as high as
possible.
• Good mechanical and form stability – the
membrane should be mechanically strong
and should have a low degree of swelling or
shrinking in transition from dilute to concen-
trated ion solutions.
• High chemical stability – the membrane
should be stable over the entire pH range
from 1 to 14 and in the presence of oxidizing
agents.
For the practical preparation of ion-exchange
membranes, two rather different procedures are
2 Ion-Exchange Membranes

Ion-Exchange
Membranes,
Fig. 1 Schematic drawing
illustrating the structure of
a cation-exchange
membrane showing fixed
negative ions and mobile
positive counterions in the
polymer matrix

used. The first procedure results in a homoge-
neous ion-exchange membrane structure and is
closely related to the preparation of ion-exchange
resins. Homogeneous ion-exchange membranes
are produced by either a polymerization of mono-
mers that carry anionic or cationic moieties or by
introducing these moieties into a polymer which
may be in an appropriate solution or a solid
preformed film. The second widely used
ion-exchange membrane preparation technique
which leads to a rather heterogeneous structure
is based on mixing an ion-exchange resin powder
with a binder polymer, such as polyvinylchloride
or polyethylene, and extruding the mixture as a
film at a temperature close to the melting point of
the polymer.
A cation-exchange membrane with excep-
tional good chemical and thermal stability
which is widely used in the electrolytic
chlorine-alkaline production and as polymer
electrolyte in low-temperature fuel cell consists
of a polyfluorocarbon material. This membrane is
often referred to as “Nafion ® membrane” which
is the trade name of DuPont. There are several
more ion-exchange membranes with special
properties commercially available such as the
bipolar membrane which is composed of an
anion- and a cation-exchange layer laminated
together (Simons 1993).
References
Bergsma F, Kruissink CH (1961) Ion-exchange mem-
branes. Fortschr Hochpolym Forsch 21:307–362
Molau GE (1981) Heterogeneous ion-exchange mem-
branes. J Membr Sci 8:309–330
Simons R (1993) Preparation of high performance bipolar
membranes. J Membr Sci 78:13–23
Xu TW (2005) Ion-exchange membranes: state of their
development and perspective. J Membr Sci 263:1–29
C
Cell Adhesion
Loredana De Bartolo
National Research Council of Italy, Institute on
Membrane Technology, CNR-ITM, Rende,
CS, Italy
Cell adhesion is the binding of a cell to a surface,
extracellular matrix (ECM), or another cell using
cell adhesion molecules, which are integral mem-
brane proteins that have cytoplasmic, transmem-
brane, and extracellular domains. The
extracellular domains of adhesion molecules
extend from the cell and bind to other cells or
matrix by binding to other adhesion molecules of
the same type (homophilic binding), binding to
other adhesion molecules of a different type
(heterophilic binding), or binding to an interme-
diary “linker” which itself binds to other adhesion
molecules. Adhesion molecules belong to four
major families: cadherins, immunoglobulin-like
adhesion molecules, integrins, and selectins.
Cadherins cause adhesion via homophilic bind-
ing to other cadherins in a calcium-dependent
manner. As is the case for their role in desmo-
somes and adherens junctions, cadherins ulti-
mately anchor cells through cytoplasmic actin
and intermediate filaments. Immunoglobulin-
like adhesion molecules are involved in both
homophilic and heterophilic binding.
The well-studied members of this group are
the neural cell adhesion molecules (N-CAMs),
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_120-6
which are expressed predominantly in nervous
tissue, and the intercellular cell adhesion mole-
cules (ICAMs). Integrins are a diverse and large
group of heterodimeric glycoproteins. The two
subunits, designated as alpha and beta, both par-
ticipate in binding. Integrins participate in
cell–cell adhesion and are of great importance
in binding and interactions of cells with compo-
nents of the extracellular matrix such as fibronec-
tin. Importantly, integrins facilitate
“communication” between the cytoskeleton and
extracellular matrix, allow each to influence the
orientation and structure of the other. Selectins
are expressed primarily on leukocytes and endo-
thelial cells and, like integrins, are important in
many host defense mechanisms involving those
cells. In contrast to other cell adhesion molecules,
selectins bind to carbohydrate ligands on cells,
and the resulting binding forces are relatively
weak. Cell adhesion is believed to be the first
and dominant step for cell growth.
Cells adhere strongly to some materials, but
not to others (Hynes 2002). This is determined by
the special structure of individual cell mem-
branes and material surface properties. The initial
cellular events that take place at the biomaterials
interface mimic to a certain extent the natural
adhesive interaction of cells with the extracellu-
lar matrix (Griffin and Naughton 2002).
Cell adhesion on a substrate such as a mem-
brane is a multistep process that involves, in
sequence, adsorption of ECM proteins onto the
surface, recognition of ECM components by cell
2 Cell Adhesion
receptors, cytoskeletal rearrangements, and cell
spreading. In particular, immediately after the
biomaterial comes into contact with cell environ-
ment, protein adsorption to its surface occurs.
This happens within seconds, long before the
first cells reach the surface. Consequently, cells
almost never come into direct contact with the
material surface; they rather interact with the
layer of adsorbed proteins. This layer mediates
the cell adhesion and also provides signals to the
cell through the cell adhesion receptors. The
membrane properties (roughness, physicochemi-
cal, mechanical, and transport) especially the sur-
face characteristics play an important role in the
adhesion process (De Bartolo et al. 2004, 2008).
Surface free energy, electric charge, and mor-
phology might all affect cell attachment and its
behavior either indirectly, e.g., by controlling
adsorption of the proteins present in the culture
medium (or secreted by the cells), or directly,
e.g., by guiding cell spreading with suitable sur-
face topography (De Bartolo et al. 2002). Such
properties resulted in being critical to
cell–substratum interaction and have to be
considered in the choice of material suitable for
biomedical device.
References
De Bartolo L, Morelli S, Bader A, Drioli E (2002)
Evaluation of cell behaviour related to physico-
chemical properties of polymeric membranes to be
used in bioartificial organs. Biomaterials
23(12):2485–2497
De Bartolo L, Gugliuzza A, Morelli S, Cirillo B,
Gordano A, Drioli E (2004) Novel PEEK-WC mem-
branes with low plasma protein affinity related to sur-
face free energy parameters. J Mater Sci Mater Med
15:877–883
De Bartolo L, Rende M, Morelli S, Giusi G, Salerno S,
Piscioneri A, Gordano A, Di Vito A, Canonaco M,
Drioli E (2008) Influence of membrane surface prop-
erties on the growth of neuronal cells isolated form
hippocampus. J Membr Sci 325:139–149
Griffin L, Naughton G (2002) Tissue engineering – current
challenges and expanding opportunities. Science
259:1009–1014
Hynes RO (2002) Integrins: bidirectional, allosteric sig-
naling machines. Cell 10:673–687
C
Cell Adhesion in Bio Artificial Organs receptors recognize and interact with either
Loredana De Bartolo
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
Binding of cells to a surface, extracellular matrix,
or other cells in an artificial device is used to
replace a nonfunctioning organ. Correct cellular
adhesion is essential in maintaining multicellular
structure and allows cells to interact dynamically
with adjacent cells and the extracellular matrix.
In bio artificial organs the cell adhesion process
involves cell–cell and cell–natural or artificial
matrix/material that plays essential roles in over-
all tissue architecture and proper physiological
functions of the device.
The functional units of cell adhesion are typ-
ically multiprotein complexes made up of three
general classes of proteins: the cell adhesion mol-
ecules/adhesion receptors, the extracellular
matrix (ECM) proteins, and the cytoplasmic
plaque/peripheral membrane proteins. The cell
adhesion receptors are usually transmembrane
glycoproteins that mediate binding interactions
at the extracellular surface and determine the
specificity of cell–cell and cell–ECM recogni-
tion. They include members of the integrin,
cadherin, immunoglobulin, selectin, and proteo-
glycan (for example, syndecans) superfamilies.
At the extracellular surface, the cell adhesion
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_121-5
other cell adhesion receptors on neighboring
cells or with proteins of the ECM. ECM proteins
are typically large glycoproteins, including the
collagens, fibronectins, laminins, and proteogly-
cans that assemble into fibrils or other complex
macromolecular arrays. Owing to their binding to
adhesion receptors, they can also be tightly asso-
ciated with the cell surface. At the intracellular
surface of the plasma membrane, cell adhesion
receptors associate with cytoplasmic plaque or
peripheral membrane proteins. Cytoplasmic
plaque proteins serve to link the adhesion systems
to the cytoskeleton, to regulate the functions of
the adhesion molecules, and to transmit signals
initiated at the cell surface by the adhesion recep-
tors. Several substrates different for the shape and
physico-chemical properties are used for cell
adhesion in artificial devices. Natural substrates
such as ECM proteins (collagen, fibronectin,
vitronectin, laminin) or polymers (chitosan,
polylactic acid, polylysine, etc.) and synthetic
substrates such as polystyrene, polycarbonate in
the shape of scaffolds, gels, sponge, and mem-
branes can be used in devices. Semipermeable
membranes made from polyethersulfone,
polysulfone, polycarbonate, polytetrafluor-
oethylene, modified polyetheretherketone,
chitosan, polycaprolactone, polylactic acid,
polyglycolic acid, and copolymers in flat and
hollow fiber configurations are used for adhesion
of different type of anchorage-dependent cells
(hepatocytes, endothelial cells, neuronal cells,
2 Cell Adhesion in Bio Artificial Organs
keratinocytes, progenitor cells, osteoblasts). In
the case of bioartificial organs, isolated cells are
compartmentalized in a polymeric membrane
which provides a number of important functions
for the success of these devices. Membranes
should act as barriers to immunocompetent
species present in the patient’s blood and should
permit the rapid passage of key metabolites such
as nutrients and oxygen from the surrounding to
the cell compartment (Curcio et al. 2005). In such
devices cells are contacting with membranes, the
surface properties of membrane could affect the
various bioresponses. Thus, one major approach
of the materials scientists has been to try to influ-
ence the extent and the character of the cell
response by modifying the surface composition
and properties of the polymer. The response of
cells to different material properties is a complex
process and even minute changes in composition
of the substrate produce amplified differences in
cell responses. Although surface properties are
often derived from the bulk properties of the
materials, the bulk materials do not entirely
define them, because the used substrates are
coated with proteins almost immediately after
implantation in the body or immersion in culture
media. Surface chemistry and topography deter-
mine the identity, quantity, and conformational
change of these adsorbed proteins. In particular,
the roughness and pore size of polymeric mem-
branes seem to play an important role since they
have been shown to influence the viability and
metabolic rates of cells (De Bartolo et al. 2008).
Modification of surface chemistry including
grafting of functional groups, peptides, and pro-
teins represents a strategy to control cell
responses in in vitro and in vivo systems. The
most common peptide immobilized onto surfaces
is RGD amino acid (arginine-glycine-aspartic
acid) sequence that stimulates cell adhesion and
growth since this peptide represents the minimal
adhesion domains of the most ECM proteins
(De Bartolo et al. 2005). The immobilization of
specific moieties that interact with specific recep-
tors of cell membrane is a challenge to enhance
the selectivity of the membrane with respect to a
cell type in order to employ it in tissue engineer-
ing for the reconstruction of a specific tissue. For
example the immobilization of galactose motifs
on the surface could enhance the specific interac-
tion with hepatocytes owing to the specific bind-
ing between the galactose moiety and the
asialoglycoprotein receptor present on hepato-
cyte cytoplasmatic membrane (De Bartolo
et al. 2006).
References
Curcio E, De Bartolo L, Barbieri G, Rende M, Giorno L,
Morelli S, Drioli E (2005) Diffusive and convective
transport through hollow fiber membranes for liver cell
culture. J Biotechnol 117:309–321
De Bartolo L, Morelli S, Lopez L, Giorno L, Campana C,
Salerno S, Rende M, Favia P, Detomaso L, Gristina R,
d’Agostino R, Drioli E (2005) Biotransformation and
liver specific functions of human hepatocytes in cul-
ture on RGD-immobilised plasma-processed mem-
branes. Biomaterials 26(21):4432–4441
De Bartolo L, Morelli S, Rende M, Salerno S, Giorno L,
Lopez LC, Favia P, d’Agostino R, Drioli E (2006)
Galactose derivative immobilized glow discharge
processed PES membranes maintain the metabolic
activity of human and pig liver cells. J Nanosci
Nanotechnol 6:2344–2353
De Bartolo L, Rende M, Morelli S, Giusi G, Salerno S,
Piscioneri A, Gordano A, Di Vito A, Canonaco M,
Drioli E (2008) Influence of membrane surface prop-
erties on the growth of neuronal cells isolated form
hippocampus. J Membr Sci 325:139–149
C
Cell Separation
Loredana De Bartolo
National Research Council of Italy, Institute on
Membrane Technology, CNR-ITM, Rende(CS),
Italy
Cell separation is the process aimed at separating
cells. Cells can be separated on the basis of dif-
ferent size, shape, physicochemical characteris-
tics, specific molecules, or receptors present over
their plasmatic membrane (Orfao and Ruiz-
Arguelles 1996). Traditionally cells are separated
through centrifugation technique for the different
density and size. This technique only requires the
resuspension of the cells in an appropriate buffer
and the knowledge of their approximate compo-
sition and density or size. Cells of different
masses and densities are pelleted accordingly,
with the densest cells pelleting first and at com-
paratively low centrifugation speeds, while the
smallest, lightest cells require much faster
speeds. The pellets can then be collected and
resuspended in the desired buffer. Another
method consists to use antibody which are able
to recognize cell membrane proteins. All cells
have an array of proteins on their surface mem-
brane, some of which are found only on particular
cells. The antibodies are often tagged with a
fluorescent compound (fluorophore) so that the
whole cell suspension can then undergo flow
cytometry, which will identify and then isolate
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_122-4
each cell individually. The antibodies can be also
combined with a tiny magnet. The cells are then
applied to a magnetic column that is capable of
retaining these tagged cells when a magnetic field
is generated within it. Cells can be separated
through a biochemical method, which involves
perturbing a biochemical process that is required
by the cell for its growth and/or survival, and it
should only be performed if a drastic manipula-
tion will not detrimentally affect other steps in the
experiment. Biochemical separations include
blocking DNA synthesis, e.g., with hydroxyurea,
and serum deprivation, i.e., growing cells in
serum-free media for a specific amount of time.
Membrane processes are used for separation of
blood cells from other blood components through
filtration. Cells are isolated by using membranes
with suitable molecular weight cutoff that permit
the passage of all components excluding only
cells. Membrane filtration has also been used for
the industrial separation of blood cells. Blood for
transplantation is typically passed through mem-
brane filters to eliminate leukocytes, which can
help prevent infection by viruses such as human
immunodeficiency virus and hepatitis C virus.
Compared with other cell separation methods,
membrane filtration is simple and inexpensive,
and it is easy to maintain sterility during the
process. Various porous polymeric membranes
have been used for separation by filtration of
different types of marrow stromal cells (KUSA-
A1 osteoblasts and H-1/A preadipocytes), due to
the different cell size (Higuchi et al. 2005).
2 Cell Separation

Separation of hepatocytes and fibroblasts has polyurethane membranes. J Biomed Mater Res
been realized through surface-modified polyure- A 71A(3):470–479
Higuchi A, Shindo Y, Gomei Y, Mori T, Uyama T,
thane membranes combining the filtration pro- Umezawa A (2005) Cell separation between mesen-
cess with the use of negatively charged chymal progenitor cells through porous polymeric
membranes (Higuchi and Tsukamoto 2004). membranes. J Biomed Mater Res B Appl Biomater
74(1):511–519
Orfao A, Ruiz-Arguelles A (1996) General concepts about
cell sorting techniques. Clin Biochem 29(1):5–9
References

Higuchi A, Tsukamoto Y (2004) Cell separation of hepa-

tocytes and fibroblasts through surface-modified
C
CH4/N2 Separation
A. Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
The US pipeline specification requires an inert
content lower than 4 % in natural gas. It is esti-
mated that 14 % of US present proven gas
reserves contain more than 4 % nitrogen (Baker
and Lokhandwala 2008; Lokhandwala
et al. 2010). The most trivial solution consists in
diluting small flow rates of nitrogen-concentrated
natural gas with main streams of natural gas
containing a low concentration in inert gases.
However, if this is not feasible (for instance,
when all the surrounding gas fields contain high
concentrations in nitrogen), it is necessary to
install a nitrogen removal plant to comply with
the regulatory natural gas composition specifica-
tions. Cryogenic distillation is the dedicated tech-
nology for large-scale nitrogen removal
operations (60,000–600,000 Nm3/h capacity for
operation life higher than 10 years). At the very
end of the 1990s, 26 such plants were in operation
on US ground (Lokhandwala et al. 2010). Two
technologies have been recently introduced in
order to solve this challenge at small and medium
scale: pressure-swing adsorption (PSA) with
molecular sieves (Molecular Gates ® by the
Engelhard company (Mitariten 2001, 2004) and
gas permeation, which has been promoted by
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_127-2
MTR Inc. since the end of the 1990s
(Lokhandwala et al. 2010).
In the mid-1990s, MTR Inc. evaluated at lab
scale (on 1–2 m2 membrane modules) a wide
array of composite membranes which selective
membranes were made of various glassy or rub-
bery polymers (Lokhandwala et al. 2010). Intui-
tively, rubbery polymers proved to be more
selective toward methane (due to its higher sorp-
tion, induced by its more condensable behavior
than nitrogen), while glassy polymers, especially
fluorinated ones, proved to be more selective
toward nitrogen (due to diffusive selectivity).
MTR Inc. evaluated the economic feasibility
of a membrane-based nitrogen removal operation
on a 12,000 Nm3/h natural gas stream entering
the process at 32 bar and containing 10 % nitro-
gen. The target of the membrane operation was to
reach the 4 % nitrogen specification in the prod-
uct gas while the waste gas was containing at
least 50 % nitrogen and the overall methane
recovery yield was to be higher than 93 %.
Based on the performances of the various tested
membrane materials, the study led to the conclu-
sion that a single-stage membrane operation was
not viable, whether the membrane material was
nitrogen-selective or methane-selective. There-
fore, two-stage recycle schemes were studied
involving only nitrogen-selective membranes or
only methane-selective membranes or a combi-
nation of both. Only the use of methane-selective
membranes proved to offer interesting perfor-
mances (Lokhandwala et al. 2010), though the
2 CH4/N2 Separation

Nitrogen removal (4 to 8% N2) 1 2 3 4 5

2
(NitrosepTM, MTR Inc.)
Flow rate (103 Nm3/h) 12 9.7 2.3 1.5 0,8
Pressure (bar) 70 14 ? ? 5.6 1 3 5
N2 8 4 26 50 12.6
Composition (% mol.)
CH4 92 96 92.5 50 87.4

CH4 recovery = 86 %
550 m² membrane area 4
690 kW (theoretical compression power)
stream 5 used as compressor fuel
stream 4 to flare
2
3
Nitrogen removal (8 to 15% N2 ) 1 2 3 4 5 6
(NitrosepTM, MTR Inc.)
Flow rate (103 Nm3/h) 12 9 ? ? 1,9 1,1
Pressure (bar) 70 14 ? ? ? 3.5 1 6
N2 15 4 8.7 50 65 26
Composition (% mol.)
CH4 85 96 81.3 50 35 74

CH4 recovery = 86 %
1,800 m² membrane area 4 5
1,860 kW (theoretical compression power)
stream 6 used as compressor fuel
stream 5 to flare
4
3

Nitrogen removal (15 to 30% N2 ) 1 2 3 4

(NitrosepTM, MTR Inc.)
Flow rate (103 Nm3/h) 12 9 ? ? 1
Pressure (bar) 70 14 ? ?
N2 15 80 11 4
Composition (% mol.)
CH4 85 20 89 96

CH4 recovery = 96 %
3,500 m² membrane area
2,680 kW (theoretical compression power)
part of stream 1 used as compressor fuel
stream 2 to flare
2

CH4/N2 Separation, Fig. 1 Permeation-based nitrogen removal from natural gas (After Lokhandwala et al. 2010)

resulting process schemes were leading to signif-
icant extra cost due to the presence of two com-
pressors: the first compression unit was used to
pressurize the methane-enriched permeate pro-
duced by the first membrane stage to the pipeline
pressure, while the second one was aiming at
boosting the pressure of the permeate stream
issued from the second-stage in order to recycle
it at the input of the first membrane stage. With
this scenario, the total equipment investment cost
was in a 4–8 million US dollar range (in 2009),
while the required membrane area was approxi-
mately equal to 4,000 m2. This appears to be
acceptable by gas processors as the payback
time of this type of installation was estimated to
be 1 year.
The first field test of these membranes was
therefore conducted with a 40 in-long module
equipped with few m2 of methane-selective
membranes for more than 1 year on a shut-in
gas well containing 15 % nitrogen operated by
Butcher Energy in Southern Ohio. The perfor-
mances of the spiral-wound module were very
similar to those observed at lab scale, and its
permeation properties remained unchanged for
the first 6-month period. After this proof of prin-
ciple, MTR Inc. designed different membrane-
based nitrogen removal process schemes, trade-
CH4/N2 Separation
named Nitrosep™, with various module/compres-
sor configurations depending on the nitrogen con-
centration to be addressed (Fig. 1).
Up till now, 12 Nitrosep™ units have been
installed in the industry. Few examples depicting
the applications addressed by this membranes
process are listed hereafter:
– A very small unit was installed in Southern
Kentucky in order to upgrade 200 Nm3/h of
natural gas containing 7 % nitrogen. This
two-membrane module unit was able to
recover 80 % of the natural gas with a nitrogen
content of 3.8 %. Part of the residue gas was
used as compressor engine fuel, while the rest
was vented.
– A much larger unit was installed in Rio Vista,
California (14,000 Nm3/h treatment capacity).
The membrane operation was aiming at
upgrading a 16 % nitrogen containing natural
3
gas to a gas stream offering 10 % more heating
value (lowering thus the nitrogen content to
9 %). The membrane system involved three
stages in series and allowed a methane recov-
ery yield of 95 % for pipeline delivery.
References
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47:2109–2121
Lokhandwala KA, Pinnau I, He ZJ, Amo KD, DaCosta
AR, Wijmans JG, Baker RW (2010) Membrane sepa-
ration of nitrogen from natural gas: a case study from
membrane synthesis to commercial deployment.
J Membr Sci 346:270–279
Mitariten M (2001) New technology improves nitrogen-
removal economics. Oil Gas J 99:42–44
Mitariten M (2004) Economic nitrogen removal.
Hydrocarb Eng 9:53–57
C
Charged Ultrafiltration Membrane
Andrew Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
Electrically charged ultrafiltration membranes
can be used to reduce the fouling and increase
the retention of like-charged species. Most poly-
meric membranes have a net negative charge in
solution due to the presence of trace anionic
groups (e.g., carboxylic acids) and/or the prefer-
ential adsorption of negatively charged ions from
the aqueous solution. It is also possible to cast
membranes from polymers containing fixed
charge groups, e.g., a positively charged mem-
brane can be developed using polymers
containing fixed amine groups. However, the
most common method for generating charged
ultrafiltration membranes is by surface modifica-
tion of a base polymer through the attachment of
appropriate anionic (e.g., carboxylic or sulfonic
acid) or cationic (e.g., quaternary amine) groups.
The overall performance of these membranes is
determined by the density of the charge groups,
the chemistry of the ligand and the covalent link-
age, and the properties of the spacer arm used to
attach the ligand to the membrane (Zydney
2011).
One of the first applications of charged ultra-
filtration membranes was in the recovery of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_129-4
electropaint. Electrodeposition of a charged
paint resin is used extensively in the industrial
painting of metallic surfaces in automobiles and
large household appliances. The paint resins are
organic polymers with attached anionic or cat-
ionic groups. Ultrafiltration has been used to
recover the charged electropaint from the dilute
solution produced by washing the excess paint off
of the metal part. Ultrafiltration can also be
applied directly to the paint in the electrodeposi-
tion bath, with the permeate (essentially water)
used for subsequent rinsing steps (Zeman and
Zydney 1996). The use of charged membranes
(having the same polarity as the electropaint)
provides significantly greater filtrate flux with
less fouling than neutral or oppositely charged
membranes.
Charged ultrafiltration membranes can be
used to significantly improve the inherent
tradeoff between the permeability and selectivity
of an ultrafiltration membrane (Mehta and
Zydney 2005). The rate of solute transport
through a charged ultrafiltration membrane is
determined by a combination of steric (size
based) and electrostatic interactions (Mehta and
Zydney 2006). Electrostatic interactions strongly
effect the partitioning of charged solutes into the
membrane pores. For example, the presence of
positively charged groups on the pore surface
causes a strong electrostatic exclusion of posi-
tively charged species from the membrane pores
significantly increasing the selectivity of the
membrane. This makes it possible to employ
2 Charged Ultrafiltration Membrane
Charged Ultrafiltration Membrane, Fig. 1 Positively charged membrane provides high retention of positively
charged protein while allowing transmission of neutral proteins
charged ultrafiltration membranes with relatively
large pore size and thus with very high perme-
ability, with the required selectivity achieved by
electrostatic exclusion of the protein.
There is also considerable interest in
performing protein separations by charged UF
membranes. In this case, the charged ultrafiltra-
tion membrane provides very high retention of
like-charged proteins, enabling uncharged pro-
teins and smaller impurities to be washed into
the permeate by a diafiltration process (see
Fig. 1). The solution pH and ionic strength can
be adjusted to obtain high-resolution protein sep-
arations (van Reis et al. 1999). Van Reis and
Zydney (2007) have discussed a number of sep-
aration processes using charged ultrafiltration
membranes, including a nonaffinity process for
purifying a monoclonal antibody from harvested
cell culture fluid.
References
Mehta A, Zydney AL (2005) Permeability and selectivity
analysis for ultrafiltration membranes. J Membr Sci
249:245–249
Mehta A, Zydney AL (2006) Effect of membrane charge
on flow and protein transport during ultrafiltration.
Biotechnol Prog 22:484–492
van Reis R, Zydney AL (2007) Bioprocess membrane
technology. J Membr Sci 297:16–50
van Reis R, Brake JM, Charkoudian J, Burns DB, Zydney
AL (1999) High performance tangential flow filtration
using charged membranes. J Membr Sci 159:133–142
Zeman LJ, Zydney AL (1996) Microfiltration and ultrafil-
tration: principles and applications. Marcel Dekker,
New York
Zydney AL (2011) High performance ultrafiltration mem-
branes: pore geometry and charge effects. In: Oyama
ST, Stagg-Williams SM (eds) Inorganic, polymeric,
and composite membranes: structure, function, and
other correlations. Elsevier, Amsterdam, pp 333–352
C
Chemical Binding of Biomolecules
to Membranes
Christophe Innocent
Institut Européen des Membranes, University of
Montpellier, Montpellier Cedex 5, France
The immobilization in electropolymerized poly-
mers such as polypyrrole has been developed for
a variety of biomolecules and provides very sta-
ble environment for the biocatalyst. The advan-
tages of the polypyrrole are the control of film
thickness and its contribution in electron transfer
between the biocatalysts and the conductive
support.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_130-5
Amino pyrrole is synthetized according the
following scheme (Fig. 1).
Electropolymerization of 1-(2-cyanoethyl)
pyrrole monomer (1) in acetonitrile 0.1 M
NBu4PF6 was performed by controlled-potential
oxidation of the pyrrole at +1.01 V vs. SC-
E. Reduction of the nitrile to amine function
was carried out using a large excess of LiAlH4
in dried ether at room temperature.
Enzyme is grafted on the modified tube (with
amino polypyrrole) by using glutaraldehyde as
coupling agent (Fig. 2).
Fixation of laccase (enzyme which catalyzed
the oxygen reduction) on the modified electrode
has been investigated and applied to the fabrica-
tion of biocathode for enzymatic biofuel cell
(Servat et al. 2007).
2 Chemical Binding of Biomolecules to Membranes

Et2O, AlLiH4
N N

NH2
N
1 2

Chemical Binding of Biomolecules to Membranes, Fig. 1 Scheme of synthesis of amino propyl pyrrole

Chemical Binding
of Biomolecules
a
to Membranes, O O
Fig. 2 Laccase
immobilization on NH2
modified electrode with H2N laccase
polyaminopyrrole; (a)
nucleophilic attack on the
glutaraldehyde, (b)
reduction of imine function
(IEM picture)
b

N N laccase

N N laccase
H H

References of porous carbon tubes with enzymes: application for

biofuel cells. J Appl Electrochem 37:121–127
Servat K, Tingry S, Brunel L, Querelle S, Cretin M,
Innocent C, Jolivalt C, Rolland M (2007) Modification
C
Chlorine-Resistant Polymeric
Membranes
Pejman Ahmadiannamini
Biomedical Engineering, University of Arkansas,
Fayetteville, AR, USA
A chlorine-resistant polymeric membrane is
mainly referred to a polymeric reverse osmosis
(RO) desalination membrane that can withstand
exposure to chlorine and preserve its separation
characteristics under such a harsh condition.
Currently, commercially available RO mem-
branes are derived from two classes of polymers:
cellulose acetate (CA) and aromatic polyamide
(PA) (Li and Wang 2010). CA membranes are
relatively low cost and tolerant to limited free
chlorine. However, CA membranes suffer from
some disadvantages such as a narrow operating
pH range (4.5–7.5), susceptibility to biological
attack, structural compaction under high pres-
sure, and low upper temperature limit. On the
other hand, PA thin film composite (TFC) mem-
branes feature thin highly selective interfacially
polymerized layers, which exhibit superior flux
and salt rejections, wider operating temperature
and pH range, and higher stability to biological
attack, as compared with CA membranes (Park
et al. 2008). Thus, PA TFC membranes used in
RO are most preferred by the desalination indus-
try. However, PA membranes encounter signifi-
cant drawbacks in desalination processes,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_131-14
namely, membrane degradation under continuous
exposure to trace amount of chlorine and deteri-
oration of their performances.
Chlorine is the most common industrial oxi-
dizing biocide in water treatment that is used for
disinfection of domestic water and for the
removal of tastes and odors from water. It is
also typically used in RO treatment processes in
order to control microorganisms that biofoul and
clog the membrane. Consequently, water to be
purified is often chlorinated, to disinfect it and
ultimately inhibit biofouling of the membranes,
and then dechlorinated before being fed to mem-
brane desalination units. After passing through
the membranes, the water is then rechlorinated
before being sent to the distribution network.
However, this requires additional equipments
and chemicals and increased operating cost for
the plant, accordingly.
When chlorine gas is added into water, it is
hydrolyzed to form hydrogen ion, chloride, and
hydrochlorous acids. The hydrochlorous can be
further ionized to produce hypochlorite ions
according to the following reactions (Geise
et al. 2010):
Cl2 + H2O HCIO + H+ + Cl-
HCIO H+ + CIO-
Cl2, HOCl, and OCl are in equilibrium, and
depending on the pH, different distributions of
aqueous chlorine species are observed (Deborde
2 Chlorine-Resistant Polymeric Membranes

and von Gunten 2008). The established oxidative chlorine. The Orton rearrangement
chlorinating strength of these species is takes place only when amide linkage is directly
Cl2 ~ HOCl > OCl (Soice et al. 2003). connected with benzene ring. Generally, the chlo-
The amide nitrogen of the membrane is highly rine resistance increases in the order of PA syn-
vulnerable to chlorine attack because of electron- thesized from aromatic, cycloaliphatic, and
withdrawing effect of carbonyl group. Upon aliphatic diamines, respectively.
exposure to free chlorine, N-H group is chlori- Thus, the following modifications can be con-
nated to N-Cl group which can reversibly form sidered as potential strategies to enhance the
the initial amid by treatment with reducing chlorine resistance of PA membranes (Geise
agents. The aromatic rings are also susceptible et al. 2010):
to attack by chlorine because it is an electron-rich
region. Two possible chlorination mechanisms 1. Replacing chlorine-sensitive amidic hydrogen
are proposed for aromatic rings, i.e., direct chlo- on the amide linkages with other moieties,
rination of the aromatic ring and Orton e.g., methyl ( CH3) or phenyl ( C6H5)
rearrangement, which involves initial chlorina- 2. Replacing the aromatic ring bonded to the
tion of amid nitrogen followed by an amide nitrogen with aliphatic chain or cyclics
intermolecular rearrangement, forming various 3. Prevention of Orton rearrangement by adding
aromatic substitution products (Fig. 1) (Raval protective groups at the possible chlorination
et al. 2010). sites on the aromatic rings
According to the chlorination mechanisms,
chlorine resistance of PA membranes largely Other than PA, polysulfone has much better
depends on the chemical structures of the chlorine resistance as it has stronger chemical
diamine components used. Aliphatic PA revers- bonds. However, due to hydrophobic nature of
ibly reacts with chlorine to yield N-chlorinated polysulfone, introduction of controlled levels of
amide. Tertiary PAs are inactive towards hydrophilic groups, e.g., SO3H, while retaining

O O H H O O H H
Cl2
C C N N C C N N
Irreversible direct aromatic chlorination

n Cl n

Cl
Re 2,
HC e t
ve IO ibl en
rs
ibl an ers em
e d ev ng
ch Cl Irr ra
lor O- ar
ina re
tio ton
n Or

O O Cl H

C C N N

Chlorine-Resistant Polymeric Membranes, film composite RO membrane by controlled chlorine

Fig. 1 Proposed mechanism of chlorination of aromatic treatment, 945–949, Copyright (2010) with permission
PA (Reprinted from Desalination, 250, Raval HD, Trivedi from Elsevier)
JJ, Joshi SV, Devmurari CV, Flux enhancement of thin
Chlorine-Resistant Polymeric Membranes
its physical properties is necessary for
polysulfone RO membranes. The polymer chain
cleavage and side reactions, which can make it
difficult to control the degree of sulfonation and
molecular weight and consequently drop the
mechanical and the thermal properties of poly-
mer, can occur in the post-sulfonation method.
The direct synthesis of the functionalized
polysulfone from a sulfonated monomer is
found to be more advantageous since the associ-
ated challenges can be avoided (Park et al. 2008).
References
Deborde M, von Gunten U (2008) Reactions of chlorine
with inorganic and organic compounds during water
3
treatment—kinetics and mechanisms: a critical
review. Water Res 42(1–2):13–51
Geise GM, Lee H, Miller DJ, Freeman BD, McGrath JE,
Paul DR (2010) Water purification by membranes: the
role of polymer science. J Polym Sci B: Polym Phys
48(15):1685–1718
Li D, Wang H (2010) Recent developments in reverse
osmosis desalination membranes. J Mater Chem
20:4551–4566
Park HB, Freeman BD, Zhang Z, Sankir M, McGrath JE
(2008) Highly chlorine-tolerant polymers for desalina-
tion. Angew Chem Int Ed 47(32):6019–6024
Raval HD, Trivedi JJ, Joshi SV, Devmurari CV
(2010) Flux enhancement of thin film composite RO
membrane by controlled chlorine treatment. Desalina-
tion 250(3):945–949
Soice NP, Maladono AC, Takigawa DY, Norman AD,
Krantz WB, Greenberg AR (2003) Oxidative degrada-
tion of polyamide reverse osmosis membranes: studies
of molecular model compounds and selected mem-
branes. J Appl Polym Sci 90(5):1173–1184
C
Citric Acid Recovery by
Electrodialysis
Gerald Pourcelly
Institut Europeen des Membranes, CC 047,
Universite Montpellier II, Place Eugene
Bataillon, Montpellier Cedex 5, France
Citric Acid Recovery by Electrodialysis
[G. Pourcelly]
Carboxylic acids such as lactic, succinic,
gluconic, citric, and tartaric are widely used in
food processing, detergent manufacture, and bio-
degradable plastic production (Bailly et al. 2001).
Their production at the industrial scale is mainly
achieved by mean of fermentation from molas-
ses, starch hydrolysates, or sugars. Traditional
processes to obtain these carboxylic acids consist
on the precipitation of both the acids and their
salts, so they can be isolated from the rest of the
components of the raw material. Then, they are
placed in an acid medium (sulfuric acid) to gen-
erate the acid form. A latter concentration step is
carried out by evaporation followed by a crystal-
lization. This generates large volumes of efflu-
ents with high salt contents. For example, typical
yields of 1 kg of citric acid are obtained per 2 kg
of gypsum which is very difficult to dispose
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_133-1
(Bialey and Ollis 1986). In order to reduce this
environmental impact, the design of alternative
production scheme was investigated. Extraction,
adsorption, and membrane technologies, like
electrodialysis (ED), were proposed to replace
precipitation (Novalic et al. 1995). A complete
scheme for carboxylic acid recovery is depicted
in Fig. 1.
For EDC step of citric acid salts to the three
dissociation constants of citric acid, the conduc-
tivity is mainly influenced by the pH value and
the concentration. More ion dissociation leads to
formation of further citric-acid-charged com-
plexes in the solution which in turn causes elec-
trical resistance reduction of the solution. The
maximum ion density and consequently the min-
imum electrical resistance of the solution is
obtained at pH 8 (Novalic et al. 1995). The
EDBM step, which is water splitting by mem-
brane electrodialysis, provides an attractive com-
plement to the fermentation technology by
removing the product acid while simultaneously
providing an equivalent amount of base for use in
adjusting the pH in the fermentor (Fig.1). More-
over, the produced citric acid is usually at a
relatively high concentration (0.5 M) so that the
subsequent purification via crystallization or
other techniques is relatively inexpensive
(Xu and Yang 2002).
2 Citric Acid Recovery by Electrodialysis

Citric Acid Recovery by

Electrodialysis,
Fig. 1 Scheme of a
process of carboxylic acid
production from
fermentation. (EDC)
concentration ED step,
(EDBM) ED with bipolar
membranes

References Bialey JE, Ollis DF (1986) Biochemical engineering fun-

Bailly M, Roux-de-Balman H, Aimar P, Lutin F, Cheyran
M (2001) Production processes of fermented organic
acids targeted around membrane operations: design of
the concentration step by conventional electrodialysis.
J Membr Sci 191:129–142
damentals. MacGraw-Hill, Singapore
Novalic S, Jagschits F, Okwor J, Kulbe KD (1995) Behav-
iour of citric acid during electrodialysis. J Membr Sci
108:201–205
Xu T, Yang W (2002) Citric acid production by electro-
dialysis with bipolar membranes. Chem Eng Process
41:519–524
C
Composite Membrane
with Inorganic Fillers: Electrolyser
Application
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
Composite Membrane with Inorganic
Fillers: Electrolyzer Application
Composite recast Nafion ® membranes containing
inorganic fillers have been primarily employed in
fuel cells for high-temperature operation (Aricò
et al. 1998) and self-humidification purposes
(Watanabe et al. 1996). Composite membrane
with inorganic fillers for electrolyzer application
has been developed in order to extend the oper-
ating temperature range of polymer electrolyte
membrane (PEM) electrolyzer and to reduce gas
crossover effects (Antonucci et al. 2008). Gener-
ally, Nafion® membrane is used as conducting
polymer electrolyte in PEM electrolyzer systems.
An increase of the operation temperature of an
electrolyzer should enhance the oxygen evolution
reaction rate that is the rate-determining step of
this process allowing to obtain high current and
high conversion efficiency. However, commer-
cial Nafion membranes loose conductivity at tem-
perature above 100  C due to membrane
dehydration. Perfluorosulfonic acid (PFSA) com-
posite membranes containing hygroscopic
ceramic oxide fillers that require water for proton
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_140-2
conduction appear suitable for this application
especially in the light of the high operating pres-
sure of PEM electrolyzers (up to 100 bars) that
allows to maintain a good fraction of liquid water
even at temperatures above 100  C. The inor-
ganic fillers enhance the water retention inside
the composite membrane allowing to operate
properly at high temperatures. A composite
Nafion–SiO2 membrane for SPE electrolyzers
has shown promising properties for high-
temperature operation allowing to achieve signif-
icantly higher performances with respect to a
bare commercial Nafion. This effect is mainly
due to a significantly better water retention than
the bare perfluorosulfonic membrane and lower
gas crossover as a result by the increased tortu-
osity effect produced by the inorganic filler inside
the membrane. The performance of the
electrolyzer based on Nafion–SiO2 membrane
increased as a function of the temperature up to
120  C and pressure. A maximum current density
of about 2.1 A cm 2 versus 0.7 A cm 2 at 1.9 V,
120  C, and 3 bar abs was recorded for the com-
posite membrane compared to Nafion
115 (Fig. 1). An increase of electrical efficiency
was recorded at low current densities for the high-
temperature SPE electrolyzer compared to con-
ventional membrane-based devices (Antonucci
et al. 2008).
2 Composite Membrane with Inorganic Fillers: Electrolyser Application

Composite Membrane a 2
with Inorganic Fillers:
Electrolyser Application,
Fig. 1 Polarization
1.8
measurements for a PEM

Terminal voltage / V
water electrolysis cell 80°C
based on conventional 90°C
Nafion 115 and composite 1.6 100°C
PFSA–SiO2 membrane at 110°C
Nafion 115 120°C
various temperature and
3.0 bar abs pressure 1.4

1.2

1
−0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4
Current density / A cm-2

b 2

1.8
Terminal voltage / V

80°C
90°C
1.6
100°C
110°C
1.4 Composite Membrane 120°C

1.2

1
−0.2 0.2 0.6 1 1.4 1.8 2.2
-2
Current density / A cm

References Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998)

Antonucci V, Di Blasi A, Baglio V, Ornelas R,
Matteucci F, Ledesma-Garcia J, Arriaga LG, Aricò
AS (2008) High temperature operation of a composite
membrane-based solid polymer electrolyte water
electrolyser. Electrochim Acta 53:7350
Comparison of ethanol and methanol oxidation in a
liquid-feed solid polymer electrolyte fuel cell at high
temperature. Electrochem Solid-State Lett 1:66–68
Watanabe M, Uchida H, Seki Y, Emori M, Stonehart
P (1996) Self-Humidifying Polymer Electrolyte Mem-
branes for Fuel Cells. J Electrochem Soc 143:3847
C
Composite Membrane
with Inorganic Fillers: Fuel Cell
Application
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
Composite recast Nafion ® membranes containing
inorganic fillers have been employed in high-
temperature (~150  C) direct alcohol (Aricò
et al. 1998) and H2-air fuel cells (Watanabe
et al.1996). These composite membranes were
originally developed for reduced humidification
operation in polymer electrolyte fuel cells
(Watanabe et al.1996) due to the enhanced
water retention inside the membrane by the effect
of the inorganic filler (Aricò et al. 1998).
A further advantage of composite membranes
relies in the barrier effect given by the inorganic
filler for methanol cross over (Ren et al. 1996)
which is of particular relevance at high tempera-
ture. It is well known that the physical adsorption
of water by materials such as silica (one of the
most used inorganic fillers) is mainly determined
by their surface properties; similar considerations
can be made for other hygroscopic inorganic
oxides such as alumina. Functional groups on
the surface of these oxides are believed to act as
water coordination centers (Aricò et al. 2003).
FTIR analysis of various silica materials suggests
that oxygen surface functionalities play a
prevailing role in the adsorption of water. The
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_141-2
surface characteristics of an inorganic oxide can
be modified by thermal treatments in inert or
oxidizing atmosphere through reactions with
strong inorganic acids (Aricò et al. 2003). Most
of the works on composite membranes have
addressed the technical aspects related to the
use of these materials as electrolytes in high-
temperature fuel cells. Accordingly, perfor-
mance, conductivity, and stability characteristics
have been investigated in-depth. Parallel work
has been concerned with the investigation of rel-
evant filler properties for application in compos-
ite membranes such as surface area analysis,
surface chemistry studies, and surface acid-base
investigations of the fillers. The conductivity of
perfluorosulfonic acid (PFSA) composite mem-
branes and fuel cell power density at high tem-
perature have been found to be related to the
characteristics of the water adsorbed on the filler
particles. Inorganic fillers characterized by acidic
properties undergo a strong interaction with
water and enhance the DMFC performance at
high temperature. Appropriate selection of the
surface properties for the inorganic fillers thus
allows to enhance proton conductivity and fuel
cell performance and extends the operating tem-
perature range of composite membranes (Aricò
et al. 2003; Fig. 1).
2 Composite Membrane with Inorganic Fillers: Fuel Cell Application

a
3300 3550
surface OH groups stretching/ cm-1

H2O stretching vibration / cm-1

3200 3500

3100 3450

3000 3400
2 3 4 5 6 7 8 9
pH filler slurry
b 1650

400
H2O bending vibration / cm-1

Power Density / mW cm-2

1640
300

200

1630

100

1620 0
0 2 4 6 8 10
pH filler slurry

Composite Membrane with Inorganic Fillers: Fuel corresponding performance of a composite membrane-
Cell Application, Fig. 1 Relationships between water based direct methanol fuel cell at 145  C
adsorption characteristics of inorganic fillers and

References performance of composite membranes in direct meth-

Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998)
Comparison of ethanol and methanol oxidation in a
liquid-feed solid polymer electrolyte fuel cell at high
temperature. Electrochem Solid-State Lett 1:66–68
Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
Antonucci V (2003) Influence of the acid-base charac-
teristics of inorganic fillers on the high temperature
anol fuel cells. Solid State Ion 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells. J
Electrochem Soc 143:L12
Watanabe M, Uchida H, Seki Y, Emori M, Stonehart
P (1996) Self-Humidifying Polymer Electrolyte Mem-
branes for Fuel Cells. J Electrochem Soc 143:3847
C
Computational Fluid Dynamics (CFD) about the wall shear stress distribution at the
and Membranes surface of the membrane. The study of hydrody-
Philippe Moulin
Laboratoire de Mécanique, Modélisation et
Procédés Propres (M2P2-UMR 7340), Equipe
Procédés Membranaires (EPM), Aix Marseille
Université, AIX en PROVENCE, France
The increasing number of CFD membrane stud-
ies is clearly related to the recent developments in
computer power and to the use of finer grid
meshes in the vicinity of the membrane. Two
approaches have been particularly considered:
the comprehension of the hydrodynamics and of
the mass transfer.
The hydrodynamics allows the increase of the
shear stress near the wall or the transmembrane
pressure thus allowing the enhancement of per-
meate flux and the membrane processes. CFD
allows determining the hydrodynamics, i.e., the
pressure and velocity fields, taking into account
the geometry of the module and the membranes,
the membrane permeability and compactness, as
well as the operating entry values such as filtra-
tion or backwash pressures, filtration mode, and
gravity. For example, it is possible to determine
the pressure and velocity fields in (i) a hollow
fiber module containing more than 40,000 fibers
(small diameter (di = 0.93 mm) and large flow
rate (50 m3.h 1) or in (ii) ceramic multichannel
membranes or module to obtain information
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_142-1
namics reveals the optimum operating conditions
and the most suitable geometry characteristics to
determine a compromise between membrane
area, channel (geometry and number), and energy
consumption to optimize membrane processes.
A large number of studies relate to the diphasic
flows, to the turbulence promoters, and to the
geometries of membranes capable of generating
secondary flows. Usually a good agreement is
obtained between CFD and experimental data
obtained for the transfer of solvent. Some recent
studies consider turbulent flows and the signifi-
cant number of turbulence models in numerical
simulations, and their comparison with experi-
mental results in the case of membrane processes
is not excellent, which limits the use of CFD in
turbulent regime.
Fouling remains a major problem in mem-
brane processes: this phenomenon limits the pro-
cess efficiency and is difficult to predict and
anticipate. These difficulties are linked to the
complexity of this phenomenon which implies
different interdependent mechanisms occurring
at pore scale. The relative importance of each
fouling mechanism has been determined
according to the particle size, the pore size, and
the surface density of pores. By CFD progress it
is now possible (a) to pursue the description of
the different fouling mechanisms by integrating
the complexity of the real membrane structure in
the numerical simulation and (b) to simulate
2 Computational Fluid Dynamics (CFD) and Membranes

different kinds of experimental deposit structure.
The limitation is the membrane reconstruction
technique limiting this description at the MF
and UF membranes. The filtration in a cylindrical
pore (i.e., microchannels) can be simulated for
different sizes of particles or pores, tortuosities,
and hydrodynamic conditions. For these CFD
studies, the difficulties are to well describe parti-
cle/particle colloidal interactions and
resuspension of particles after capture.
Thus, CFD is without any doubt an important
tool for understanding mass transfer in membrane
processes, and opportunities for the development
of new membrane geometries are numerous.
C
Computer-Aided Methods and Tools
Giorgio De Luca
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rende (CS), Italy
Computational methods can be divided into
approaches using adjustable or empirical param-
eters and those which do not use them.
Concerning the first methods, several procedures
have been developed for the optimization of the
adjustable parameters. For example, design of
experiments is an approach defining the mini-
mum number of experiments required to obtain
the fitting parameters. Instead, in the ab initio
methods, these quantities are obtained by direct
experimental measurements or from other simu-
lations carried out in smaller time-space scale
(Steinhauser 2008), until the sub-nanometer
scale is reached.
The choice of the computational approaches
strictly depend on the proprieties to be studied.
Figure 1 shows the various computational
methods and properties that can be obtained.
Binding energies, molecular electrostatic
properties must be evaluated by quantum
mechanics (QM) approaches (Veszprémi and
Fehér 1999). These generally require significant
computational resources, although the develop-
ment of parallel supercomputers and efficient
algorithms have allowed to carry out QM calcu-
lations unthinkable few years ago. The quantities,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_143-2
obtained at QM level, can be used in subsequent
molecular dynamics (MD), Monte Carlo (MC),
or semiempirical calculations to describe proper-
ties related to a huge number of molecules and
atoms, like polymers. MD methodologies are
based on the simultaneous solution of Newton’s
equation of motion referred to the atoms of the
physical system (Allen and Tildesley 2003). The
potential energy surface (interaction potential),
also called force field (FF), used in the MD sim-
ulations is defined by QM or parameterized over
measurements. The temperature, volume, pres-
sure, and number of particles define the statistical
ensemble in which the MD can be performed.
The classic MC method is generally based on
the von Neumann, Metropolis, and Ulam algo-
rithm (Metropolis and Ulam 1949; Wood 1986).
Later, the method has grown to the point where it
leads to several methods all belonging to the MC
family. In the grand canonical MC ensemble, the
simulations are performed at chemical potential,
volume, and temperature constant, whereas the
number of molecules varies. The potential sur-
face energy is always defined by means of a
specific FF. Interesting MC approaches are
based on the quantum MC methodology. The
semiempirical methods use Hamiltonians to
describe the system, but some contributions of
these operators are obtained empirically
(Clementi and Corongiu 1995). These
approaches allow to evaluate the target properties
more quickly than the QM methods. In Table 1,
2 Computer-Aided Methods and Tools

Time, s D,α, J,θ, Κeq. FEM, Lattice Bolztmanm

Macro

10–3
Phase distri.,
Morphologies,
Micro fluids. Micro
Lattice Bolztmanm

10–9
FFV,FAV, d-spa,Tg, Conformationa analysis,
Molecular and sorption diffusion in large
Nano system Semiempirical, Monte Carlo

10–15 Bond energies ,Dipoles, Electr. Charges,

Sub Accurate geometries, Spectroscopic analysis.
Nano Quantum Mechanics
10–9 10–7 10–4 100
Space, m

Computer-Aided Methods and Tools, Fig. 1 Computational methods and achievable properties

Computer-Aided Methods and Tools, Table 1 Advantages and disadvantages of some computational methods
Method Advantages Disadvantages
Molecular Systems of thousands of atoms, low Experimental data or values from quantum
mechanics and computational costs mechanics, absence of bond breaking/
Monte Carlo forming. Noncovalent bonds are not well
dynamics described, less general
Semiempirical Less computational demand than quantum Experimental data or values from quantum
mechanics approaches, systems of hundreds mechanics, less general
of atoms
Ab initio, density Do not depend on experimental data, useful Computationally very expensive
functional theory for a broad range of molecules without Small systems
quantum mechanics available experimental data, general

the illustrated computational methods are sum-
marized with their advantages and disadvantages.
The information provided by smaller scales
can be utilized in mesoscale calculations: coarse
grain MD or Lattice Boltzmann (LB) (Swift
et al. 1996). In particular, LB is a powerful
method for simulating fluid confined in
microsystems, as may be precisely a membrane.
This method allows to solve the Navier-Stokes
equations in a simple way and with a notable
reduction of computational time. LB allows an
easy description of the interfaces and especially
without the use of adjustable parameters as made
by the conventional finite elements methods
(FEM). Finally, the description of the properties
of macrosystems can be carried out using
methods based on classic mechanics or dynam-
ics. The differential equations describing these
physical systems are evaluated numerically by
means of FEM or finite volume procedures (De
Luca et al. 2014). There is a notable number of
codes implemented for each method just
described. These are divided into programs in
which a single methodology is implemented or
those in which several methods, radically differ-
ent, can be found. Therefore, it is possible to find
codes in which only QM (based on different
theories) or MD are implemented separately and
others in which both the methodologies are pre-
sent. Particular attention should be given to
Computer-Aided Methods and Tools
parallel algorithms since parallel supercomputers
allow the use of huge number of processors (or
computers interconnected by the net). These pos-
sibilities allow to perform complex calculations
in short computational time.
References
Allen MP, Tildesley DJ (2003) Computer simulation of
liquids. Oxford University Press, New York
Clementi E, Corongiu G (eds) (1995) Methods and tech-
niques in computational chemistry METECC-95.
STEF, Cagliari. ISBN 88-86327-02-1, Club Europeen
MOTECC
3
De Luca G, Bisignano F, Paone F, Curcio S (2014) Multi-
scale modeling of protein fouling in ultrafiltration pro-
cess. J Membr Sci 452:400–414
Metropolis N, Ulam S (1949) The Monte Carlo method.
J Am Stat Assoc 44:335–341
Steinhauser MO (2008) Computational multiscale model-
ing of fluids and solids. Springer, Heidelberg
Swift MR, Orlandini E, Osborn WR, Yeomans JM
(1996) Lattice Boltzmann simulations of liquid-gas
and binary fluid systems. Phys Rev E 54(5):5041–5052
Veszprémi T, Fehér M (1999) Quantum chemistry.
Kluwer Academic/Plenum Publishing, New York
Wood WW (1986) Early history of computer simulations
in statistical mechanics molecular dynamics simula-
tion of statistical systems. Proceedings of the Enrico
Fermi Summer School. Varenna, pp 3–13
C
Computer-Aided Models
Giorgio De Luca
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rende (CS), Italy
Models can be divided into mathematical and
structural (chemical models), both connected to
each other. Mathematical models and procedures
can be numerical algorithms, in which each sin-
gle step is simple arithmetic and logical relations,
or they can be defined by analytical relationships,
regardless of how they are evaluated. In either
case, mathematical models and procedures are
the result of some assumptions or approximations
based on structural or chemical models (Allen
and Tildesley 2003; De Luca et al. 2006, 2008).
For example, the description of a droplet forma-
tion during membrane emulsification by means of
analytical force-balance relationships requires
some approximations about the droplet shape
and its evolution along the membrane membrane
pore. Moreover, the shape of the membrane pores
should be also modeled. Therefore, any mathe-
matical model can be correlated with structural or
chemical models. By using computational pro-
cedures, starting from quantum mechanical cal-
culations, molecular dynamics (MD) or Monte
Carlo (MC), in fact particular attention should
be paid to the molecular (chemical) models.
Molecular models are closely dependent on the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_144-2
target properties to be assessed as well as on the
computational time required to get these proper-
ties. Computational time, in turn, depends on the
level of theory used, that is, the mathematical
approaches.
For example, at the moment, quantum
mechanical methods are not applicable to opti-
mize the geometry of macromolecules as poly-
mers or systems containing thousands of atoms
like biological systems. Molecular dynamics
methodologies or coarse grain Monte Carlo can
be used in these cases. However, molecular
dynamics approaches cannot be used to study
systems in which the breaking and formation of
bonds or noncovalent bonds are decisive. Thus, in
the latter case, the choice of a chemical model of
macromolecules is crucial. These structural
models, also called analogues, inevitably lead to
neglect some aspects; nevertheless in some cases
these may be irrelevant if the choice of the ana-
logues is done correctly. In fact, albeit molecular
models certainly introduce approximations in the
evaluation of the macromolecular or biological
proprieties, some functions of these only depend
on a limited part of the whole structures. Thus,
chemical models can mimic very well the func-
tion of complex systems (Gademann et al. 2007;
Z€urcher et al. 2006; Saxer et al. 2010). Some
examples, concerning models of carbon
nanotubes (CNT), have been presented in Fig. 1.
In summary, mathematical models, computa-
tional methods, and structural (chemical) models
2 Computer-Aided Models
Computer-Aided Models, Fig. 1 CNT structural models
carefully tune as a function of the type of calcu-
lation which is required to be done. Huge litera-
ture exists about studies on any kind of chemical
models (periodic surfaces, slabs, or clusters) and
correlated computational procedures (periodic
calculations, embedded clusters, and quantum
mechanics/molecular mechanics methods, etc.).
References
Allen MP, Tildesley DJ (2003) Computer simulation of
liquids. Oxford University Press, New York
Gademann K, Bethuel Y, Locher HH, Hubschwerlen
C (2007) Biomimetic total synthesis and antimicrobial
evaluation of anachelin H. J Org Chem 72:8361–8370
De Luca G, Drioli E (2006) Force balance conditions for
droplet formation in cross-flow membrane emulsifica-
tions. Journal of Colloid and Interface Science
294:436–448
De Luca G, Di Maio FP, Di Renzo A, Drioli E (2008)
Droplet detachment in cross-flow membrane emulsifi-
cation: Comparison among torque- and force-based
models. Chemical Engineering and Processing
47:1150–1158
Saxer S, Portmann C, Tosatti S, Gademann K, Zurcher S,
Textor M (2010) Surface assembly of catechol-
functionalized poly(L-lysine)-graft poly(ethylene
glycol) copolymer on titanium exploiting combined
electrostatically driven self-organization and biomi-
metic strong adhesion. Macromolecules 43:1050–1060
Z€
urcher S, Wackerlin D, Bethuel Y, Malisova B,
Textor M, Tosatti S, Gademann K (2006) Biomimetic
surface modifications based on the cyanobacterial iron
chelator anachelin. J Am Chem Soc 128:1064–1065
C
Constant-Volume Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Constant-volume diafiltration (also called
constant-volume dilution mode) is a batch
diafiltration process for separating microsolutes
from macrosolutes, in which the volume of the
process liquor is kept constant during filtration by
continuously adding a diluant into the feed tank at
a rate equal to the permeation rate. The schematic
representation of its configuration is shown in
Fig. 1. The constant tank volume can be
maintained by the use of a ball float valve or by
means of liquid level controller (Beaton and
Klinkowski 1983). As filtration progresses, the
concentration of membrane-permeating
microsolutes in the feed tank continuously
decreases, while that of the macrosolutes remains
ideally unchanged (or close to constant in case of
incomplete rejection).
Note that some literature sources misleadingly
refer to “constant-volume diafiltration” as “con-
tinuous diafiltration.” Although the addition of
diluant is performed in a continuous manner,
constant-volume diafiltration should not be
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_149-3
considered as a continuous process. It is a true
batch process. It is advised, however, to use the
term “constant-volume dilution mode” which is
less common in the literature. The term “dilution
mode” reveals that this technique is actually an
operational mode of a membrane filtration pro-
cess in which the process liquor is diluted with
pure solvent.
Depending on the technological goal, either
the permeate or the retentate represents the
phase of primary economic importance. Thus,
the product of the operation is either formed in
the feed tank as a purified mixture of
macrosolutes or collected in the permeate tank
where the microsolutes are accumulated. Both
treatments pose a dynamic modeling problem.
A mass balance on component i in the feed tank
gives the following initial value problem for its
concentration cf,i(t):
8
< dcf , i ðtÞ ¼ cf , i ðtÞqðtÞ½Ri ðtÞ  1
dt Vf
:
½3 mmcf , i ð0Þ ¼ c0f , i
where q(t) and Ri(t) are the permeate flow and the
solute rejection that are subject to change during
operation. The constants Vf and cf,i denote the
volume of the feed tank and the initial feed con-
centration of component i. The equation
describes the evolution in time of the feed
2 Constant-Volume Diafiltration

Constant-Volume Retentate
Diafiltration, Diluant u(t)
Fig. 1 Schematic
representation of constant- Permeate q(t)
Membrane
volume diafiltration module
settings
Feed
diafiltration level

Feed tank

Constant-Volume 0
Diafiltration,
Fig. 2 Dependence of
Microsolute reduction in percentage [%]

R = 0.9
microsolute removal on
applied diavolumes in
constant-volume R = 0.8
diafiltration
R = 0.7
90
R = 0.6

R = 0.5
R = 0.4
R = 0.3
R = 0.2
R = 0 R = 0.1
99
0 1 2 3 4 5 6 7 8 9 10
Diavolumes [-]

concentration cf,i(t) assuming that the diluant however, the problem can be reduced to the fol-
consists of no component i and the feed tank is lowing algebraic expression:
well mixed.
 
In many applications, the flux and the rejec- cf , i ðtÞ
ln ¼ DðRi  1Þ% for i ¼ 1, 2, N
tions are concentration-(inter)dependent quanti- cf , i ð0Þ
ties (Kovács et al. 2009) and may vary with
operating conditions such as temperature, applied where D is the diafiltration factor (also called
pressure, and hydrodynamics. In such cases, no diavolume) that is defined as the ratio of applied
closed form solution of the set of resulting com- volume of diluant to feed volume. For applica-
plex differential algebraic equations exists; thus, tions where the objective is to reduce the
numerical techniques are required to solve the microsolute concentration by a fixed amount,
model equations. Under the simple assumptions the necessary diavolumes can be determined
of constant permeate flow and rejections, based on Eq.2 as illustrated in Fig. 2.
Constant-Volume Diafiltration
In practice, constant-volume dilution mode is
frequently preceded and/or followed by batch
concentration operational steps in order to reduce
the initial feed volume to a desired level and,
thus, to concentrate the macrosolutes (for further
details, see entry on “traditional diafiltration”).
3
References
Beaton NC, Klinkowski PR (1983) Industrial ultrafiltra-
tion design and application of diafiltration processes.
J Sep Process Technol 4(2):1–10
Kovács Z, Discacciati M, Samhaber W (2009) Modeling
of batch and semi-batch membrane filtration pro-
cesses. J Membr Sci 327(1–2):164–173
C
Contactor-Type Catalytic Membrane
Reactor
Juergen Caro
Institute of Physical Chemistry and
Electrochemistry, Leibniz University, Hannover,
Germany
Synonyms
Catalytic diffuser; Pore-through-flow catalytic
membrane
The term “catalytic membrane contactor” refers
to a device in which a membrane containing a
catalytically active phase is used to provide the
reaction zone for conversion of one or more reac-
tants from one or more fluid phases (Dittmeyer
and Caro 2008). The membrane not always has a
separation function, it provides the surface-rich
reaction zone for a gas-liquid, but also for a
gas-gas and a liquid-liquid reaction. Applications
of membranes with built-in catalysts for
gas-liquid reactions have been also reviewed in
Dittmeyer et al. (2004).
The catalytic diffuser concept can be utilized
for solid-catalyzed gas/liquid reactions in various
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_151-3
ways. If the membrane is not wetted, the opera-
tion principle is similar to that of a membrane
contactor. The gas is on the support side, and the
liquid is pumped through the shell side. The gas-
eous reactants enter the liquid phase at the
gas/liquid contact plane which is established at
the pore mouth towards the external membrane
surface. The catalyst is deposited on this surface
and gets in contact with the reactants. On the
contrary, if the membrane is wetted the gas and
not the liquid is at overpressure as described in
Dittmeyer and Caro (2008).
Gas–liquid contactors without catalytic func-
tion can be used in gas adsorption. Examples are
carbon dioxide removal from gas mixtures using
monoethanolamine (Simons et al. 2009) or ionic
liquids (Albo et al. 2010) as carbon dioxide
absorbing solutions.
For liquid-liquid and gas-gas catalytic mem-
brane contactors, see Dittmeyer and Caro (2008)
(Fig. 1).
Catalytic diffuser with wettable membrane:
The active material is placed solely into the sur-
face layer of an asymmetric membrane. By
applying overpressure on the gas side, above the
bubble point pressure of the intermediate layer
but below that of the surface layer, the gas/liquid
contacting plane is established inside the
2 Contactor-Type Catalytic Membrane Reactor

membrane close to the surface layer. In this way,

a short diffusion path for the liquid and for the gas
reactant is achieved (after Dittmeyer and Caro
(2008)).

References

Albo J, Luis P, Irabien A (2010) Ind Eng Chem Res

49:11045–11051
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
In: Ertl G, Knözinger H, Sch€
uth F, Weitkamp J (eds)
Handbook of heterogeneous catalysis. Wiley-VCH,
Weinheim, pp 2198–2248
Dittmeyer R, Svajda K, Reif M (2004) A review of cata-
lytic membrane layers for gas/liquid reactions. Top
Catal 29:3–27
Simons K, Nijmeijer K, Wessling M (2009) J Membr Sci
Contactor-Type Catalytic Membrane Reactor, 340:214–220
Fig. 1 Catalytic diffuser with wettable membrane as an
example for a Contactor-Type Catalytic Membrane Reac-
tor for a solid-catalyzed gas-liquid reaction. By applying
overpressure on the gas side, the gas-liquid contacting
plane is established inside the membrane close to the
surface. In this way, a hort diffusion path for the liquid
and for the gas is achieved. Reproduced from Roland
Dittmeyer, Karel Svajda, Martin ReifA review of catalytic
membrane layers for gas/liquid reactionsTopics in Catal-
ysis, 29 (2004), 3-27 reprinted with permission from
Elsevier)
C

Continuous Stirred Tank Membrane Inlet
Outlet þ Generation

Reactor (CST-MR) ¼ Accumulation (1)

Giuseppe Barbieri The mass balance for the component i-th consid-
Institute on Membrane Technology, Italian ering a single reaction will be:
National Research Council, Rende (CS), Italy
NX
reactions
dN i
FInlet
i
FOutlet
i þ ni, j r j V Reaction
CSTR ¼ (2)
j¼1
dt
Before introducing the continuous stirred tank
membrane reactor (CST-MR), it is useful/helpful Mass balances provide a set of ordinary differen-
to report about the continuous stirred tank reactor tial equations (ODEs), in which the number of
(CSTR). moles of component i-th is time dependent. In
The continuous stirred tank reactor (CSTR) is Eq. 2, FiInlet and FiOutlet are, respectively, the inlet
an ideal reactor model assuming perfect mixing, and outlet molar flow of the component i-th, ri is
with no spatial gradients of any variable such as the reaction rate, Ni is the number of moles, and
species concentration, temperature, pressure, V is the reactor/reaction volume.
etc. The effect of the perfect mixing is the same In steady-state condition, the mass balance
value for, e.g., concentration, temperature, etc., equations fall into algebraic equations:
in any point of the whole reactor volume; and
their values are equal to those of the stream NX
reactions

exiting the reactor. In addition, the reaction rate FInlet
FOutlet þ ni, j r j V Reaction ¼0 (3)
i i CSTR
has the same value in any point of the reactor. j¼1
Therefore, this reactor model operating at the
lowest reactant concentration and the highest Equation 3 provides the design equation Eq. 4 for
product concentration results in the lowest reac- a CSTR in steady-state conditions:
tion rate. However, an important effect of perfect
mixing is an easy temperature and reaction rate FInlet
FOutlet
control, which results quite simply. Figure 1 V Reaction
CSTR ¼ i i
(4)
NX
reactions

shows a CSTR scheme.
ni, j r j

The generic balance equation on the reactor j¼1
volume will be:
An increase in reaction rate ri causes a reduction
of reactor volume (Eq. 4). The design equation
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_152-1
2 Continuous Stirred Tank Membrane Reactor (CST-MR)

Continuous Stirred Tank

Membrane Reactor
(CST-MR),
Fig. 1 Continuous stirred
tank reactor (CSTR)
scheme

transfer coefficient, A is the heat exchange area,

and DH is the enthalpy of the chemical reaction.
This equipment is very commonly used in
continuous industrial processes as well as in the
plug flow reactor. For reactions of greater than
zero order, CSTR always requires a volume
larger than that of a plug flow reactor to achieve
the same conversion; this is owing to the lower
reactant concentrations, as said, at which it
operates. Therefore, the use of CSTR is
recommended when the desired reaction rate is
smaller than that of the side reaction one in order
to limit by-product formation.

Continuous Stirred Tank Membrane Reactor

(CST-MR), Fig. 2 Continuous stirred tank membrane
reactor (CST-MR)
also provides the reactor volume necessary for
obtaining the exit flow rate FiOutlet, from the feed
conditions FiInlet, and the reaction rate
knowledge.
The energy balance, coupled to mass balance,
is given by Eq. 5:
Conversion ¼
   
Cp T Outlet
T Inlet
UA T Outlet
T External

DH Reaction
(5)
where Cp is the mean heat capacity, TExternal is the
external temperature, U is the overall heat
CST Membrane Reactor
A membrane reactor is a device that combines in
one unit a chemical reaction with selective prod-
uct separation by means of a permselective mem-
brane. The selective removal of products from the
reaction side to the permeate side also provides
an increase, e.g., of the reaction rate and equilib-
rium conversion (Fig. 2).
A continuous stirred tank membrane reactor
[1, 2] (CST-MR) is a device characterized (1) in
addition to the same properties described above
for the CSTR (perfect mixing that has no spatial
gradients of species concentration, temperature,
pressure, etc.) on both reaction and separation
sides (2) by the selective removal of reaction
product by the membrane allowing improved
performance (see later on) with respect to
a CSTR.
Continuous Stirred Tank Membrane Reactor (CST-MR) 3

The generic mass balance (Eq. 1) is still valid FSweep
FPermeate þ AMembrane J i Permeating
i i
and has to be written down for both reaction and
permeation even though another term has to be dN Permeate
¼ i
(7)
included: the one taking into account the perme- dt
ation through the membrane. Therefore, Eqs. 6
The mass balance equations for steady state have
and 7 include the permeating flow rate (AMembrane
an algebraic form:
JPermeating, the product of the membrane area and
Reaction side:
permeating flux). This term is negative (being
mass leaving the reaction volume) on the
retentate side and positive (entering the perme-
ation volume) on the permeate one.
Reaction side:

FFeed
i
FRetentate
i
AMembrane J i Permeating
NX
reactions

þ ni, j r j V Reaction
CST
MR
j¼1

dN Retentate
¼ i
(6)
dt

Permeation side:

NX
reactions

FFeed
i
FRetentate
i
A Membrane
Ji Permeating
þ ni, j r j V Reaction
CST
MR ¼ 0
j¼1

 
FFeed
FRetentate
AMembrane J i Permeating
V Reaction
CST
MR ¼ i i
(8)
NX
reactions

ni , j r j
j¼1

Permeation side: performance of a continuous stirred tank reactor

(CSTR), specifically, for the following points:
FSweep
i
FPermeate
i þ AMembrane J i Permeating ¼ 0
1. Higher conversion owing to the selective per-
AMembrane J i Permeating ¼ FPermeate
i
FSweep
i meation through the membrane
(9) 2. Higher reaction rate owing to the lower con-
centration of the products removed by the
Equation 8 also identifies the reaction volume. It selective membrane
results lower than the CSTR reaction volume 3. Lower reaction volume at the same productiv-
owing to the permeation through the membrane. ity owing to the species permeation
Therefore, a continuous stirred tank mem-
brane reactor (CST-MR) has a higher
4 Continuous Stirred Tank Membrane Reactor (CST-MR)

References Chapter 9-Mathematical modelling of pdalloy mem-

Barbieri G.; Scura F.; Brunetti A. Series Membrane Sci-
ence and Technology, Volume 13 Inorganic Mem-
branes: synthesis, Characterization and Applications;
brane reactors, 325–400
Raich, B. A., and Foley, H.C (1995). Supra-equilibrium
conversion in palladium membrane reactors: Kinetic
sensitivity and time dependence. Applied Catalysis A.:
General 129, 167–188
C
Copolyimide Precursors
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Pakistan
Polyimide Precursors
Polyimides are a class of thermally stable poly-
mers that are often based on stiff aromatic back-
bones derived from aromatic dianhydrides and
aromatic diamines. Polyimides due to their
unusual properties are finding a wide range of
applications and thus used as precursor
(a precursor is a compound that participates in
the chemical reaction that produces another com-
pound) to develop materials for various applica-
tions. The chemistry of polyimides is in itself a
vast area with a large variety of monomers avail-
able and several methodologies available for
synthesis.
The general formula and chemical structure of
polyimide is shown in Fig. 1.
Few of the specialty properties of polyimides
include:
High thermal and thermo-oxidative stability up to
400  C (750  F)
Excellent mechanical properties, both at room
temperature and elevated temperatures
Film- and fiber-forming ability
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_153-2
Excellent adhesive properties, both at room tem-
perature and elevated temperature
Nonflammability – will not support combustion
Applications of Polyimide Precursors
Owing to its excellent chemical and thermal sta-
bility, polyimides have wide range of applica-
tions such as in electronics, aircraft, automobile,
medical, machining, gas purification, aerospace,
and military applications.
For application in electronic and microelec-
tronics industry, fluorine may be introduced to
polyimides which reduced the dielectric constant
along with retaining the other characteristics
mentioned above (Hermciuc et al. 2000). Forma-
tion of nanofoam polyimides is a novel approach
for reducing the dielectric constant. Basically in
nanofoam formation, polyimide polymer
replaces with air which reduces the dielectric
constant (Hedrick and Charlier 1994). The mem-
brane developed by polyimide containing func-
tional or pendant groups in the backbone of the
aromatic dianhydride and/or diamine exhibits
good as well as selective gas permeability.
Hyperbranched polyimide (HBPI) precursors
were also studied to develop high-performance
carbon molecular sieve membranes for improved
gas separation applications. It was found that the
unique hyperbranched network structure found in
HBPI possesses great potential to produce carbon
molecular sieve membranes with superior
2 Copolyimide Precursors
Copolyimide Precursors,
Fig. 1 Chemical structure
of polyimide
performance (Sim et al. 2013). It is also reported
that the membrane produced from the pyrolysis
of a hollow-fiber polyimide precursor under suit-
able conditions has good separation properties
when applied to mixed gas pairs, such as O2/N2,
CO2/CH4, and H2/CH4 (Jones and Koros 1994).
Polyimide-based membranes have been exten-
sively studied for removal of CO2 particularly
from natural gas and found few of them quite
efficient (Xiao et al. 2009). Soluble and optically
transparent fluorine-containing photoreactive
polyimide precursors were developed. These pre-
cursors offer high-resolution patterns with aspect
ratio of more than 2.0. In these polyimide pre-
cursors, the polymers which have a benzophe-
none segment in the polymer backbone are self-
sensitized and show interesting photochemical
reactions (Omote et al. 1989).
Polyimide processability is one of the issues
associated which cause hurdle to manufacture
polyimide parts, such as composites, at costs
competitive to other metal parts. Improvement
in polyimide processability is essential which
could be achieved by reduction in its melt viscos-
ity. Low-molecular-weight end-capped oligo-
mers are potential candidates for the
development of polyimide oligomers for
improved processability (Smith and Connell
2000; Simone and Scola 2000).
References
Hedrick JL, Charlier Y (1994) High temperature
polyimide nanofoams. Polym Prepr 35:245–346
Hermciuc S, Hamciuc E, Sava I, Diaconu I, Bruma
M (2000) New fluorinated poly(imide-ether-amide)s.
High Perform Polym 12:205–276
Jones CW, Koros WJ (1994) Carbon molecular sieve gas
separation membranes-I. Preparation and characteriza-
tion based on polyimide precursors. Carbon
32:1419–1425
Omote T, Koseki K, Yamaoka T (1989) Soluble and
optically transparent fluorine-containing photoreactive
polyimide precursors: Spectral sensitization by
organic peroxide and organic dye combination.
Polym Eng Sci 29(14):945–949
Sim YH, Wang H, Li FY, Chua ML, Chung T-S,
Toriida M, Tamai S (2013) High performance carbon
molecular sieve membranes derived from
hyperbranched polyimide precursors for improved
gas separation applications. Carbon 53:101–111
Simone C, Scola DA (2000) Novel fluorinated
polyimidess. Proc Fluoro Polym Am Chem Soc 15–18
Smith JG Jr, Connell JW (2000) Chemistry and properties
of imide oligomers fom phenylethynyl containing
diamines. High Perform Polym 12:213–223
Xiao Y, Low BT, Hosseini SS, Chung TS, Paul DR
(2009) The strategies of molecular architecture and
modification of polyimide-based membranes for CO2
removal from natural gas – a review. Prog Polym Sci
34:561–580
C
Cost-Effective Gas Separations
Pushpinder S. Puri
PuriMem, LLC, Emmaus, PA, USA
The separation of gases is an essential unit oper-
ation for a large number of chemical processes.
The membrane-based gas separation processes
are one of the several options available to the
process engineers. Therefore, a membrane gas
separation process has to compete with the more
established gas separation processes such as
cryogenic distillation, absorption, and adsorp-
tion. Although gas separation membranes can be
used for a wide range of applications, they have
generally found their applications only in a few
niche markets. These applications are listed in
Table 1. In these markets membranes may not
be the most cost-effective gas separation process
but offer other advantages which make a compel-
ling case for their use. These non-tangible bene-
fits of the membrane gas separation processes are
listed in Table 2.
Two necessary but not sufficient properties of
the gas separation membranes are its selectivity
for a given pair of gases and the gas permeation
rate of the faster gas. The membrane selectivity is
associated with the energy usage and/or product
loss (energy cost), and the gas permeation rate is a
measure of the membrane area needed (capital
cost) for a given separation. Thus, these two
factors have a major impact on the economic
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_154-3
viability of a given membrane for a separation
of interest. In addition, these two properties dic-
tate the geometry of the membrane (tubular, hol-
low fiber of flat sheet), design of the membrane
module, configuration of the membrane cascade
(single stage or multiple stages), and process flow
schemes (parallel, series, recycle, sweep, etc.)
(Agrawal and Xu 1996). They also determine
the operational mode of the membrane such as
pressurized feed gas with or without intermediate
compression or membrane module operation
with vacuum on the permeate side while keeping
the feed gas a little over the atmospheric pressure.
All these factors contribute to the bottom line
economics of the gas separation process.
The life of the membrane and the replacement
cost of the membrane module are a major con-
tributor to the cost effectiveness of the membrane
gas separation. For commercial membrane gas
separations, the membrane life varies from appli-
cation to application. A major contributor to the
life of the membrane is its chemical compatibility
with the feed gases. A membrane material may be
chemically inert to the major gases in the feed
gas, but the trace impurities present in it may
damage the membrane over a period of time by
causing compaction or other defects. In those
cases, the feed gas may be pretreated to remove
trace impurities before the gases are fed to the
membrane separator. The type and extent of
cleaning of the feed gases has a major bearing
on the overall cost of gas separation by
membranes.
2 Cost-Effective Gas Separations

Cost-Effective Gas Separations, Table 1 Commercial therefore, they are not best suited to produce
applications of gas separation membranes high purity nitrogen. However, when a mem-
Nitrogen production from air brane air separation process is combined with an
Air-drying adsorption process, membrane separation pro-
H2/CO adjustment in synthesis gas duces 95–99 % nitrogen from which final traces
H2 recovery in ammonia synthesis of oxygen is removed by adsorption process
H2 recovery in petrochemical processes (Choe et al. 1987). The second application of
Acid gas removal from natural gas hybrid process is for the removal of acid gases
Recovery and recycle of olefins in olefin polymerization
from the natural gas. Here, a hybrid process
process
consisting of acid gas selective membrane
followed by an amine scrubbing process offers a
more economical process for natural gas
Cost-Effective Gas Lower foot print and
Separations, upgrading (Baker and Lokhandwala 2008).
weight
Table 2 Benefits of
No moving parts (except
membrane gas separation
for compressors)
process
Remote operation References
Easy turnup/turndown
Portability Agrawal R, Xu J (1996) Gas-separation membrane cas-
cades utilizing limited numbers of compressors.
No open flames
AIChE J 42:2141
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47(7):2109–2121
Choe JC et al (1987) Process for separating components of
a gas stream, US Patent 4,701,187
Hybrid processes consisting of a membrane
separation process with a conventional gas sepa- Further Reading
ration process sometimes offer a more cost- Drioli E, Barbieri G (eds) (2011). Membrane engineering
effective solution for gas separation. Two exam- for the treatment of gases, volume 1: gas-separation
ples of these processes which are commercially problems with membranes. RSC Publishing, Cam-
bridge, UK
used are in production of high purity nitrogen and Paul DR, Yampol’skii YP (1994) Polymer gas separation
in the treatment of natural gas. Air separation membranes. CRC Press, Boca Raton, Fl, USA
membranes have selectivity limitations;
C
Crown Ethers
P. K. Mohapatra
Radiochemistry Division, Bhabha Atomic
Research Centre, Mumbai, Maharashtra, India
Pedersen (1967) synthesized the crown ethers
(see Fig. 1a) for the first time in 1967 which
formed stable complexes with alkali/alkaline
earth metal ions and displayed a unique selectiv-
ity based on the size compatibility of the ligand
cavity size and the ionic size of these metal ions.
The crown ethers mimic the biological receptors
such as valinomycin (see Fig. 1b) which selec-
tively transports K+ ion as compared to Na+ ion
(by a factor of 105) across cell membranes. The
transport properties of the crown ethers depend
on the size of the crown ring, number of donor
atoms, nature of donor atoms, nature of lipo-
philic/ionizable side arms, etc. Crown ethers
have been overwhelmingly used for the transport
of alkali metal/alkaline earth ions, though there
have been quite a large number of reports on the
transport of Ag+, Hg2+ (with thia-crown ethers),
and Pb2+ which are proposed for heavy metal
removal from wastewaters (Lamb et al. 1980).
There have also been several reports on the use
of crown ethers for the selective transport of
lanthanides and actinides though size selective
factors are far less pronounced in such cases.
Another major application of crown ethers for
metal ion transport includes the recovery of
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_162-4
radio-cesium and radio-strontium from radioac-
tive wastes which can significantly reduce the
load on the vitrified glass blocks (Dozol
et al. 1995; Dozol and Casas 1994). Crown
ether-based supported liquid membranes have
shown large amounts of acid cotransport when
attempts have been made for the transport of
Cs-137 and Sr-90 from nitric acid feeds. This
has affected the overall efficiency of the transport
process, and appropriate selection of the diluent
has helped in overcoming this issue (Raut
et al. 2012). Though crown ethers have been
employed for the transport of Cs(I) in
laboratory-scale studies, calix crowns (where
crown ether structure has been appended to a
calix[4]arene) have been proposed as one of the
most efficient carrier extractants for the effective
transport of radio-cesium (Casnati et al. 1995).
Transport of organic/biological receptors like
cytochrome C (Paul et al. 2003) and amino
acids (Yamaguchi et al. 1988) has also been
facilitated by crown ethers.
Usually, the neutral macrocyclic ionophores
like crown ether, cryptand, calixarenes,
cavitands, etc. require a large lipophilic counter
anion like picrate, tetraphenyl borate, etc. for the
effective transport of the cationic species from
the aqueous phase to the membrane phase. The
ion pairs are subsequently transported across the
membrane phase which usually contains a polar
diluent such as chloroform, long-chain alcohols,
ethers, etc. for the stabilization of the charged
metal-carrier (crown ether) complex. However,
2 Crown Ethers
O O
HN
O O
O O
O O
O O
HN
O NH
Crown Ethers, Fig. 1 Structural formulae of (a) a typical crown ether, (b) valinomycin, and (c) an ionizable lariat
crown ether
the large molar volume counter anions can make
the diffusion of the ion pair rather slow.
Appending an ionizable pendent arm to the
crown ether ring (the ligand is called an ionizable
lariat ether; see Fig. 1c) can eliminate the need for
the counter anions making it a more efficient
transport system (Strzelbicki et al. 1989). Other
types of functionalization have been found to
impart exotic properties to the receptors. For
example, crown ethers with suitable functional
groups based on redox-switched (Shinkai
et al. 1985a), thermosensitive (Shinkai
et al. 1985b), and photoresponsive (Shinkai
et al. 1981) properties have also been used for
the transport of receptors. Functionalized crown
ether-type ligands with carboxylate groups have
been suggested for the recovery of U from sea-
water which is yet another exotic application of
the crown ether-based membrane transport
systems.
References
Casnati A, Pochini A, Ungaro R, Ugozzoli F, Arnaud F,
Fanni S, Schwing MJ, Egberink RJM, De Jong F,
Reinhoudt DN (1995) Synthesis, complexation and
membrane transport studies of 1,3-alternate calix[4]
arene-crown-6 conformers: a new class of cesium
selective ionophores. J Am Chem Soc 117:2767–2777
Dozol JF, Casas J (1994) Influence of the extractant on
strontium transport from reprocessing concentrate
solutions through flat-sheet supported liquid mem-
branes. Sep Sci Technol 29:1999–2018
Dozol JF, Casas J, Sastre AM (1995) Transport of cesium
from reprocessing concentrate solutions through flat-
O
H
N
H
O
OCH2COH
O
O O
NH
O O
O
O O
O
O O
O O O
O
N O
H O
sheet supported liquid membranes: influence of the
extractant. Sep Sci Technol 30:435–448
Lamb JD, Izatt RM, Robertson PA, Christensen JJ
(1980) Highly selective membrane transport of Pb2+
from aqueous metal ion mixtures using macrocyclic
carriers. J Am Chem Soc 102:2452–2454
Paul D, Suzumura A, Sugimoto H, Teraoka J, Shinoda S,
Tsukube H (2003) Chemical activation of cytochrome
c proteins via crown ether complexation: cold-active
synzymes for enantiomer-selective sulfoxide oxida-
tion in methanol. J Am Chem Soc
2003(125):11478–11479
Pedersen CJ (1967) Cyclic polyethers and their complexes
with metal salts. J Am Chem Soc 20:7017–7022
Raut DR, Mohapatra PK, Manchanda VK (2012) A highly
efficient supported liquid membrane system for selec-
tive strontium separation leading to radioactive waste
remediation. J. Membr. Sci. 390–391: 76–83
Shinkai S, Nakaji T, Ogawa T, Shigematsu K, Manabe
O (1981) Photoresponsive crown ethers.
2. Photocontrol of ion extraction and ion transport by
a bis(crown ether) with a butterfly-like motion. J Am
Chem Soc 103:111–115
Shinkai S, Inuzuka K, Miyazaki O, Manabe O (1985a)
Redox-switchable crown ethers. 3. Cyclic-acyclic
interconversion coupled with redox between dithiol
and disulfide and its application to membrane trans-
port. J Am Chem Soc 107:3950–3955
Shinkai S, Nakamura S, Tachiki S, Manabe O, Kajiyama
T (1985b) Thermocontrol of ion permeation through
ternary composition membranes composed of poly-
mer/liquid crystal/amphiphilic crown ethers. J Am
Chem Soc 107:3363–3365
Strzelbicki J, Charewicz WA, Liu Y, Bartsch RA
(1989) Solvent extraction and bulk liquid membrane
transport of Co(II) and Ni(II) ammine cations by
proton-ionizable crown ethers. J Incl Phenom Mol
Recognit Chem 7:349–361
Yamaguchi T, Nishimura K, Shinbo T, Sugiura M (1988)
Amino acid transport through supported liquid mem-
branes: mechanism and its application to enantiomeric
resolution. Bioelectrochem Bioenerg 20:109–123
C
Cryogels
Nilay Bereli, Handan Yavuz and Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Chromatography is the most powerful technol-
ogy in the downstream applications for the sepa-
ration of proteins both in the analytical and large
scale. Conventional packed bed columns have
been used for many applications; however, they
have some important drawbacks such as the slow
diffusional mass transfer and the large void vol-
ume between the beads (Gun’ko et al. 2013). In
order to resolve these problems, nonporous beads
and perfusion chromatography packing have
been designed and used as a carrier, but these
adsorbents are not sufficient to resolve these lim-
itations in essence. New-generation stationary
phases i.e., polymeric cryogels, are found to
have an increasing use in the separation science
due to their easy preparations, excellent flow
properties, and high performances compared
with the conventional beads. Cryogels are
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_163-1
mega-porous three-dimensional networks formed
under freezing conditions. The pore size of the
cryogels varies from 10 to 250 mm (Fig. 1), which
can be changed by optimizing the freezing
regime and type and concentrations of polymer-
ization precursors. The unique properties of
cryogels like osmotic, chemical, and mechanical
stability, large pores, short diffusion path,
low-pressure drop (Fig. 2), and short residence
time for both binding and elution stages make
them attractive matrices for affinity chromatog-
raphy of large molecules such as proteins, plas-
mids even whole cells, as well as small molecules
(Lozinsky et al. 2001; Stela and Valentina 2013;
Bereli et al. 2008, 2010; Tamahkar et al. 2011;
Derazshamshir et al. 2010). Therefore, cryogels
can be used in the various affinity chromatogra-
phy applications such as protein A affinity chro-
matography, histidine affinity chromatography,
thiophilic affinity chromatography, metal-chelate
affinity chromatography, dye affinity chromatog-
raphy, ion-exchange chromatography, DNA
affinity chromatography, cell affinity chromatog-
raphy, molecular imprinting technique, etc.
2 Cryogels

Cryogels, Fig. 1 SEM

images of the PHEMA
cryogel

coordinated molecularly imprinted supermacroporous

0.3 cryogels. J Chromatogr A 1190:18
Bereli N, Şener G, Altintaş EB, Yavuz H, Denizli
A (2010) Poly(glycidyl methacrylate) beads embed-
ded cryogels for pseudo-specific affinity depletion of
albumin and immunoglobulin G. Mater Sci Eng
Pressure (MPa)

0.2 30:323
Derazshamshir A, Baydemir G, Andaç M, Say R, Galaev
IY, Denizli A (2010) Molecularly imprinted PHEMA-
based cryogel for depletion of hemoglobin from
human blood. Macromol Chem Phys 211:657
0.1 Gun’ko VM, Savina IN, Mikhalovsky SV
(2013) Cryogels: morphological, structural and
adsorption characterization. Adv Colloid Interface
Sci 187–188:1
0.0 Lozinsky VI, Plieva FM, Galaev IY, Mattiasson B (2001)
0 100 200 300 400 The potential of polymeric cryogels in bioseparation.
Flow rate (cm/h) Bioseparation 10:163
Stela DE, Valentina DM (2013) Design, synthesis and
Cryogels, Fig. 2 Pressure drop at different flow rates interaction with Cu2+ ions of ice templated composite
hydrogels. Res J Chem Environ 17:4
Tamahkar E, Bereli N, Say R, Denizli A (2011) Molecu-
References larly imprinted supermacroporous cryogels for cyto-
chrome c recognition. J Sep Sci 34:3433
Bereli N, Andac M, Baydemir G, Say R, Galaev IY,
Denizli A (2008) Protein recognition via ion
D
Dehydration
Wei Liu
Energy and Environmental Technology,
Pacific Northwest National Laboratory,
Richland, WA, USA
Dehydration is a common terminology but often
has different meanings in different fields. In
chemistry, dehydration is a chemical reaction
process about conversion of one molecule into
another one by removing H and O atoms as a
water molecule, such as conversion of ethanol
(C2H5OH) into ethylene (C2H4). In physiology
and medicine, dehydration means the excessive
loss of body water. Dehydration in food
processing involves removal of water from vari-
ous types of food for long-term preservation.
In the membrane field, dehydration generally
refers to removal of water molecules from a
water-containing fluid or mixture, i.e., it is a
physical process. Two common membrane dehy-
dration processes are illustrated in Fig. 1. In
pervaporation, water molecules are removed
from water-containing liquid as water vapor and
thus, a phase change of water occurs during the
process. Due to significant heat of vaporization,
the liquid feed temperature will be reduced with-
out thermal energy inputs. Continuous supply of
thermal energy is necessary to conduct
pervaporation under a constant temperature. In
the vapor-phase separation process, water vapor
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_165-1
is separated out of a water vapor-containing fluid,
and no phase changes are involved. Vapor-phase
membrane separation is nearly an isothermal
process.
The driving force for water molecules to move
across the membrane is typically partial pressure
gradient of water vapor. For a given feed fluid,
partial pressure of water vapor in the permeate
side can be lowered by pulling vacuum and/or
introducing a sweep gas stream. Water transport
across the membrane can also be driven by chem-
ical potential gradient of water. For example, the
forward osmosis process involves water transport
from water-containing liquid of a lower solute
concentration to liquid of a higher solute concen-
tration, and a membrane gas/liquid contactor for
gas drying involves transport of water from water
vapor-containing gases into water-absorbing liq-
uid. However, those membrane processes are
viewed as different technologies from membrane
dehydration.
There are a variety of applications for mem-
brane dehydration. Dehydration is necessary for
production of pure or anhydrous alcohols,
because a water-alcohol mixture is often pro-
duced by fermentation or catalytic reactions
from feedstock of sugars, corn, cellulose, or syn-
gas. Ethanol fuel production represents one major
application of dehydration technologies, and its
worldwide production capacity reaches about
85 billion liters/year in 2012. Successful devel-
opment of cellulosic ethanol technologies is
expected to lead more growth of ethanol fuels.
2 Dehydration
a b
T2 <T1 Liquid-phase
raffinate
Water-
containing liquid
Membrane
T1
Water vapor
Dehydration, Fig. 1 Common membrane dehydration processes. (a) Pervaporation. (b) Vapor-phase separation
Methanol is another commodity chemical with a
large market. Water is miscible with a number of
solvents and chemicals, such as acetic acid, ace-
tone, and tetrahydrofuran. Dehydration of these
solvents is involved in a range of industrial chem-
ical conversion processes. The presence of water
in industrial gases is ubiquitous. Air dehumidifi-
cation and natural gas dehydration are examples
of significant industrial gas drying processes.
One salient feature for the membrane dehy-
dration process is molecular separation functions
of the membrane. Removal of free water from
slurry, i.e., separation of water from particulates,
is typically referred as dewatering processes. The
membrane allows permeation of water molecules
while blocking other molecules. Because of the
molecular separation function, the membrane
dehydration provides significant advantages
over conventional evaporation and gas drying
technologies. The vapor-phase membrane sepa-
ration is a steady-state process operating under
constant temperature and pressure, as compared
to periodic switches between adsorption
(or absorption) and regeneration required for the
solid (or liquid) desiccating process. For separa-
tion of a water-miscible liquid, the membrane
dehydration is not limited by thermodynamic
gas/liquid equilibrium such as co-boiling that
often occurs in alcohol-water distillation pro-
cesses. The membrane dehydration is considered
as an energy-efficient and compact process.
A number of membrane materials have been
studied, and some of them are commercially
developed for the dehydration application. They
can be classified into two groups (Fig. 2): dense
and microporous. The dense membrane provides
selective absorption of water over other mole-
cules. The separation mechanism can be
T2 ≈ T1 Raffinate
Water vapor-
containing fluid
T1
Water vapor
described by the solute diffusion model. Most
polymeric membrane materials fall into this cat-
egory, which include polyvinyl alcohol (PVA),
chitosan, alginate, polysulfone (PSF),
polyimides, polyamides, polyaniline, and poly-
electrolyte membranes such as cation-exchanged
Nafion. Separation in a microporous membrane is
mostly achieved through molecular sieving based
on molecular sizes and/or selective adsorption of
water at entrance of the membrane pore. Micro-
porous zeolite, silica, and carbon are common
membrane materials. Water molecule is often
the smallest one in a mixture, and selective sep-
aration can be realized by making the membrane
pore size small enough. However, the small pore
size reduces molecule diffusion rates and may
have a negative impact on flux. Molecular sieving
based on selective water adsorption enables
achievement of both high flux and selectivity
(Zhang and Liu 2011). Some of zeolite frame-
works, such as NaA, ZSM-5, and X-type and
Y-type zeolite, have the pore size larger than
that of water molecule but can be very selective
toward water adsorption over other molecules.
Permeation of the other molecules is blocked
due to adsorption of water molecules at the
entrance of the zeolite pore, although the pore
can be permeable to the other molecules in the
absence of moisture.
The membrane dehydration performances are
characterized by flux (Jw), permeance (Pw), and
separation factor (Sw/i), which can be calculated
from experimental measurements as follows:
Dnw
Jw ¼
Am  Dt
Dehydration
Dehydration,
Fig. 2 Separation
mechanisms of dehydration
membrane. (a) Solute
diffusion in dense
membrane. (b) Molecular
sieving in microporous
membrane
Jw
Pw ¼
p w, F  p w, P
ðyw =yi ÞP
aw=i ¼
ðxw =xi ÞF
where Dnw is the amount of water collected in the
permeate side of a membrane during a sampling
period of time Dt, Am is the membrane surface
area exposed to the feed, pw,F is partial pressure
of water in feed side, pw,P is partial pressure of
water in permeate side, yw and yi are the respec-
tive molar fraction of water and specie i in the
permeate side, and xw and xi are the respective
molar fraction of water and specie i in the
feed side.
The membrane materials and separation per-
formances studied for the dehydration applica-
tions are well summarized in recent reviewing
articles (Chapman et al. 2008; Wee et al. 2008;
Bolto et al. 2012). The flux and separation factor
reported for polymeric membranes are ranged
from 0.01 to 1.0 kg/m2/h and from 10 to 1000,
respectively, over a range of operation tempera-
ture from 25  C to 80  C. The microporous silica
membrane has a higher flux and separation factor
at comparable separation temperatures. The zeo-
lite membrane shows the highest flux and sepa-
ration factor. The flux and separation factor
reported for separation of 10 wt.% water in etha-
nol with zeolite membranes (Zhang and Liu
2011) can be as high as 10 kg/m2/h and 10,000,
respectively. The zeolite membrane can be used
3
for both pervaporation at low temperatures and
vapor-phase separation at high temperatures
(above 100  C). It should be noted that flux is a
strong function of testing conditions. For a given
membrane, water flux tends to increase with
water content in the feed and with the separation
temperature. Permeance should be a better
parameter to characterize a membrane’s through-
put. However, this parameter was seldom
reported in the literature. The permeance is esti-
mated to vary over a wide range from 1.0E-5 to
1.0E-9 mol/m2/s/Pa among different membranes.
Selection of a suitable membrane for a given
application depends on specific properties of the
water-containing fluid. The material has to be
chemically and physically stable under the sepa-
ration conditions that the membrane structure can
be maintained intact for a long time. For example,
NaA is a commonly studied zeolite membrane for
dehydration but it is not stable in acidic solutions.
For dehydration of acetic acids, the more stable
ZSM-5 and T-type zeolite materials are
suggested. Pure zeolite membranes were consid-
ered difficult to prepare. To overcome the short-
comings with pure polymeric and ceramic
membranes, researchers proposed mixed matrix
membranes (MMM) comprising a polymeric
base into which an inorganic material is dispersed
and locked. The rationale is that some drawback
associated with the polymeric material can be
mitigated by incorporation of inorganic particles
of durable structures, and MMM products may be
produced with the manufacturing processes
4 Dehydration
similar to polymeric membranes. There could be
a variety of combinations from two groups of
materials. Researchers have been actively explor-
ing unique performance attributes of the mixed
matrix membranes.
Membrane dehydration has found some indus-
trial applications at relatively small scales so far.
It is expected that widespread applications may
become possible by lowering the membrane cost
and enhancing productivity through continuing
innovations.
References
Bolto B, Hoang M, Xie Z (2012) A review of water
recovery by vapour permeation through membranes.
Water Res 46:259–266
Chapman PD, Oliveira T, Livingston AG, Li K (2008)
Membranes for the dehydration of solvents by
pervaporation. J Membr Sci 318:5–37
Wee S, Tye C, Bhatia S (2008) Membrane separation
process – pervaporation through zeolite membrane.
Sep Purif Technol 63:500–516
Zhang J, Liu W (2011) Thin porous metal sheet-supported
NA zeolite membrane for water/ethanol separation.
J Membr Sci 371:197–210
D
Dehydrogenation Reactions
Juergen Caro
Institut of Physical Chemistry and
Electrochemistry, Leibniz University Hannover,
Hannover, Germany
Dehydrogenations of aliphatic or cyclic hydro-
carbons are under technical condition thermody-
namically controlled, i.e., the reaction takes place
near at the equilibrium alkane D olefin + H2.
There are hundreds of papers describing an
increase of the alkane conversion and an increase
of the olefin yield, if hydrogen is removed
through a hydrogen-selective membrane from
the reactors. Numerous hydrogen-selective mem-
branes have been evaluated in dehydrogenation
reactions, most often Pd-based membranes as
compact foils or supported thin layer, pure Pd or
as alloy with Ag or Cu, zeolite-based membranes,
but also metal oxide membranes prepared via the
sol-gel route or carbon membranes prepared by
pyrolysis. For details, see (Dittmeyer and Caro
2008; Caro 2010). Interestingly, besides alkane
conversion and olefin yield, also the olefin selec-
tivity increased in comparison with classical
fixed or fluidized bed reactors since the removal
of hydrogen suppresses hydrogenolysis.
However, for all membrane-supported dehy-
drogenation reactions with hydrogen removal, it
was found that after an initial improvement of
alkane conversion and olefin yield, because of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_166-3
the hydrogen drain-off, a severe coking of the
catalyst and the membrane is observed which
causes the conversion and yield to be after
30 min–2 h below those of a packed bed reactor.
The development of coke-resistant catalysts and
membranes could not compensate this negative
influence. Therefore, the scientific interest in
dehydrogenation reaction dropped dramatically
within the last decade.
However, there is a new concept to support
dehydrogenation reactions by a selective in situ
combustion of the hydrogen using oxygen-
transporting membranes according to alkane +
oxygen ! olefin + water (steam) (Czuprat
et al. 2009, 2010). The problem to be solved
consists in the selective combustion of hydrogen
in the presence of the alkane and olefin mole-
cules. However, because of the higher reactivity
of hydrogen in comparison with the hydrocar-
bons, this problem could be used, by using two
catalysts: one catalyst for the dehydrogenation
and the other one for the selective hydrogen
combustion.
On the one-hand side, hydrogen is lost by
combustion; on the other hand, in addition, in
the boosting of alkane conversion and olefin
yield, there are three advantages:
1. Hydrogen combustion brings heat for the
endothermic dehydrogenation.
2. Steam suppresses coking of catalyst and
membrane.
2 Dehydrogenation Reactions

Dehydrogenation ethane
Reactions,
Fig. 1 Principle of a 2-step
oxidative ethane C2H4, H2O
C2H6 ← C2H4 + H2
→ non-consumed C2H6
dehydrogenation in an
oxygen-transporting perowskite membrane
membrane reactor with a
perovkite membrane O2-depleted O2
air

air

100
literature
this work
80 air N2
propene selectivity / %

60

O2
40

C3 H8 C3 H6 + H2 C3 H6 + H2O
20

0
0 20 40 60 80 100
propane conversion / %

Dehydrogenation Reactions, Fig. 2 2-step oxidative propane dehydrogenation as described in Figure 1 for ethane

3. Steam dilutes the reactants which is favorable References

for thermodynamic reasons (shift of the equi-
librium) (Fig. 1).
Principle of the oxidative ethane dehydroge-
nation in a membrane reactor with selective in
situ combustion of hydrogen using an oxygen-
transporting perovskite hollow fiber membrane
(Czuprat et al. 2009) (Fig. 2).
Propene selectivity as a function of the pro-
pane conversion in the membrane reactor with
oxygen-transporting hollow fiber perovskite
membrane (filled spheres) in comparison with
the best literature data for the oxidative dehydro-
genation of propane (empty spheres) (Czuprat
et al. 2010).
Caro J (2010) Comprehensive membrane science and
engineering. In: Drioli E, Giorno L (eds) Comprehen-
sive membrane science and engineering. Elsevier,
Oxford, pp 1–108
Czuprat O, Werth S, Schirrmeister S, Schiestel T, Caro
J (2009) ChemCatChem 1:401–405
Czuprat O, Werth S, Caro J, Schiestel T (2010) AIChE
J 56:2390–2396
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
In: Ertl G, Knözinger H, Sch€uth F, Weitkamp J (eds)
Handbook of heterogeneous catalysis. Wiley-VCH,
Weinheim, pp 2198–2248
D
Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Diafiltration (also called membrane filtration
in dilution mode) is an operation mode of a
pressure-driven membrane filtration process in
which a diluant (pure solvent) is added into the
process liqueur in order to facilitate the separa-
tion of macrosolutes from microsolutes.
Diafiltration may be performed either in batch
(discontinuous) or continuous processing mode
as schematically shown in Fig. 1. In both
processing modes, diluant is added to and perme-
ate is withdrawn from the system. The fundamen-
tal difference between the two configurations is
that in batch operation, the retentate stream is
recycled into the feed tank where it is mixed
with the content of the reservoir and with fresh
diluant. The concentration of membrane-
permeable microsolutes in the feed tank
decreases over time, and the final product is
obtained directly in the feed reservoir when oper-
ation is terminated. In contrast, continuous
processing is performed in a flow-through man-
ner with both permeate and retentate being with-
drawn. Thus, batch diafiltration is a dynamic
process in which the composition of fluid stream
fed into the membrane module is a function of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_171-5
time, while continuous diafiltration is essentially
a static (steady-state) process in which the feed
stream is of constant composition.
The benefits and disadvantages offered by the
two processing modes in industrial-scale ultrafil-
tration (UF) systems have been summarized by
Lipnizki et al. (2002) as shown in Table 1.
Diafiltration has found a vast number of indus-
trial applications in the chemical, pharmaceuti-
cal, environmental, biotech, and food and
beverage sectors. The requirement for an effec-
tive separation is the utilization of a membrane
that has a high rejection for macrosolute but
allows the passage of microsolute. The mass
transport, unlike in dialysis, is driven by pressure
differences across the membrane. Depending on
the particular application, either the retentate or
the permeate is the valuable phase of economic
importance (or both), and the applied membrane
can be a microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF), or reverse osmosis
(RO) membrane. Some typical applications
include:
• MF: enzyme recovery from fermentation
broths; cell harvest and debris removal; sepa-
ration of casein from serum milk proteins
• UF: protein purification and buffer exchange;
ethanol removal from human serum albumin
obtained from blood plasma; fruit juice
clarification; milk fractionation; Kraft black
liquor treatment; recovery of small molecules
2 Diafiltration

a
Diluant

Retentate
b
Diluant Retentate

Feed
Permeate Feed Permeate

Diafiltration, Fig. 1 Schematic flow diagram. (a) Batch diafiltration. (b) Continuous diafiltration

Diafiltration, Table 1 Comparison of batch and continuous diafiltration (Adopted from Lipnizki et al. 2002)
Batch Continuous
UF plant investment Low High
Batch tank investment High Low
Control investment Low High
Space requirement UF Low High
Space requirement tank High Low
Feed volume flexibility High Low
Antibiotic/protein concentration in permeate Variable Constant
Residence time High Low
Temperature flexibility Low High
Module efficiency Low High
Energy consumption High Low

(e.g., amino acids, antibiotics, organic acids,
etc.) from fermentation broth
• NF: desalination of dyes and optical bright-
eners; partial demineralization of whey; pro-
duction of desalted and concentrated
antibiotics; desalination of gelatin for
improved color and whipping properties
• RO: solvent replacement in herb extracts; beer
dealcoholization
Diafiltration is also called membrane filtration
in dilution mode in accordance with the terminol-
ogy recommendation of the former European
Society of Membrane Science and Technology
(now known as the European Membrane Society)
(Gekas 1988). Although the latter term is less
frequently used in the literature, it better reveals
that an operation mode of a filtration process is
considered.
Membrane filtration plants are rarely designed
exclusively for microsolute removal. Most appli-
cations require a simultaneous microsolute
removal (i.e., macrosolute purification) and
macrosolute concentration (i.e., feed volume
reduction). In many cases, the term diafiltration
stands for a process that is designed to achieve
these dual objectives. In continuous processing,
the different modes of operation (i.e., concentra-
tion and dilution modes) are assigned to different
stages which are connected in series. In batch
processing, the targeted twin aims of concentra-
tion and fractionation are obtained either in con-
secutive operational steps (e.g., in traditional
diafiltration, intermittent feed diafiltration,
sequential dilution diafiltration) or applying
Diafiltration
specific diluant utilization strategies (e.g.,
variable-volume diafiltration, dynamic-volume
diafiltration). Overall, these characteristics of
diafiltration put it in a favorable position in com-
parison with other separation techniques and
even with a sequence of competitive unit opera-
tions (Jönsson and Trägårdh 1990).
References
Gekas V (1988) Terminology for pressure-driven membrane
operations. Desalination 68(1):77–92. doi:10.1016/
0011-9164(88)80045-6. http://www.sciencedirect.com/
science/article/pii/0011916488800456
3
Jönsson AS, Trägårdh G (1990) Ultrafiltration applica-
tions. Desalination 77:135–179. doi:10.1016/0011-
9164(90)85024-5
Lipnizki F, Boelsmand J, Madsen RF (2002) Concepts of
industrial-scale diafiltration systems. Desalination
144:179–184
Further Reading
Beaton NC, Klinkowski PR (1983) Industrial ultrafiltra-
tion design and application of diafiltration processes.
J Sep Process Technol 4(2):1–10
Dutré B, Trägárdh G (1994) Macrosolute-microsolute sep-
aration by ultrafiltration: a review of diafiltration pro-
cesses and applications. Desalination 95:227–267
Madsen RF (2001) Design of sanitary and sterile UF- and
diafiltration plants. Sep Purif Technol 22–23:79–87
D
Dielectric Permittivity
Andrew Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
The dielectric permittivity («) provides a measure
of the ability of a material to be polarized in the
presence of an applied electric field (Cosgrove
2010; Hunter 2001). The ratio of the dielectric
permittivity of a material to that of a vacuum
(«o = 8.85
1012 F/m) is defined as the
dielectric constant (k). Water has a dielectric con-
stant of 80.1 at 20  C; this large value reflects the
highly polar nature of water.
The dielectric permittivity appears in a number
of important equations describing the surface
charge and electrostatic interactions in membrane
systems. For example, the membrane zeta poten-
tial (a measure of the membrane surface charge)
can be evaluated from the measured streaming
potential (Ez) using the Helmholtz-Smoluchowski
equation:


Ez ez
¼ University Press, New York
DP
Lo
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_172-3
where DP is the pressure difference across the
membrane, h is the solution viscosity, z is the
zeta potential, and Lo is the solution conductivity
(Burns and Zydney 2000).
The distance over which the electrical potential
varies in an electrolyte solution is described by the
Debye length (lD), which provides a measure of
the thickness of the electrical double layer (Hunter
2001):
 1=2
F2 X 2
lD ¼ Z i Ci
eRT
where F is Faraday’s constant, R is the ideal gas
constant, T is the absolute temperature, and zi and
Ci are the valence and concentration, respectively,
of each ion in solution.
References
Burns DB, Zydney AL (2000) Buffer effects on the zeta
potential of ultrafiltration membranes. J Membr Sci
172:39–48
Cosgrove T (2010) Colloid science: principles, methods,
and applications. Wiley, Chichester
Hunter RJ (2001) Foundations of colloid science. Oxford
D
Diffusion Dialysis
Heiner Strathmann
Institute for Chemical Technology, Stuttgart
University, Stuttgart, Germany
Diffusion dialysis with ion-exchange membranes
is mainly used today to recover acids or bases
from a mixture with salts. The process is based
on the fact that ion-exchange membranes gener-
ally show a high permeability for counterions
while being more or less impermeable for
co-ions. Exceptions are protons and hydroxide
ions which can easily permeate both cation- and
anion-exchange membranes. The transport mech-
anism in diffusion dialysis is more complex than
in conventional dialysis due to the electrostatic
interaction between positive and negative charges
and the electroneutrality requirement (Kobuchi
et al. 1987). The process and equipment design
is very similar to that used in conventional dialy-
sis. In diffusion dialysis, the driving forces for the
transport of ions through the ion-exchange mem-
brane are gradients in their chemical potentials
only. There is no external electrical potential
applied. The principle of the process is illustrated
in 1 showing part of a diffusion dialysis stack for
the recovery of HCl from a salt mixture. It is
composed of anion-exchange membranes
forming cells in which in alternating series a
feed solution of an HCl/FeCl2 mixture and a strip-
ping solution of water is introduced. Since anion-
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_173-1
exchange membranes are permeable for H+, Cl
and H+ permeate the membranes, while the other
cations (Fe2+) are retained (Fig. 1).
The mass transport in diffusion dialysis is
determined by the transport of ions and can be
determined by the respective mass balance equa-
tions described in the literature. A typical appli-
cation of diffusion dialysis is the recovery of acids
from spent pickling solutions used in the metal
industry. A typical diffusion dialysis plant is
shown in the process flow diagram of Fig. 2.
A stack with 100–200 cell pairs is operated with
countercurrent flow of the feed and the stripping
solutions, which allows high acid recovery rates.
The flow diagram shows a feed solution
containing an acid and a salt which often is the
effluent of metal surface treatment procedure.
This solution is fed by a pump from a reservoir
into a dialyser stack which contains only anion-
exchange membranes. A stripping solution, which
generally is water, is pumped in countercurrent
flow into the stack. During the pathway through
the stack, the acid diffuses from the feed solution
through the anion-exchange membrane into the
stripping solution and leaves the system as salt-
free product. The salt is retained and leaves the
stack as waste. The main application of diffusion
dialysis is in the treatment of spent metal surface
pickling solutions (Strathmann 2010; Oh
et al. 2000).
2 Diffusion Dialysis

Diffusion Dialysis, Repeating cell unit

Fig. 1 Schematic drawing Salt + Acid Acid
Acid
illustrating the principle of
diffusion dialysis utilizing
+ + + +
anion-exchange membranes
+ HCl + FeCl + HCl + HCl +
to recover an acid from a 2
mixture with salts + + + +
+ + + +
H+ + H+ + H+ + H+ + H+
− + − + − + − + −
Cl Cl Cl Cl Cl
+ + + +
+ + + +
+ + Fe ++ + +

Water Salt + Acid Water

Diffusion Dialysis, Dialyser

Fig. 2 Flow diagram of the
diffusion dialysis process
Waste
solution

Flow
meter

Recovered
acid

Receiving Feed
solution solution

References Oh SJ, Moon SH, Davis T (2000) Effects of metal ions on

Kobuchi Y, Motomura H, Noma Y, Hanada F (1987)
Application of ion-exchange membranes to recover
acids by diffusion dialysis. J Membr Sci 27:173–179
diffusion dialysis of inorganic acids. J Membr Sci
169:95–105
Strathmann H (2010) Electrodialysis, a mature technology
with a multitude of new applications. Desalination
264:268–288
D
Direct Membrane Emulsification
Emma Piacentini1, Alessandra Imbrogno1 and
Richard G. Holdich2
1
Institute on Membrane Technology
(ITM-CNR), University of Calabria, Rende (CS),
Italy
2
Department of Chemical Engineering,
Loughborough University, Loughborough,
Leicestershire, UK
In the early 1990s, Nakashima and Shimizu
(1991) introduced membrane technology for
emulsion preparation by the direct emulsification
method (DME). In DME, the dispersed phase is
directly fed through the membrane pores and
emulsion droplet formation takes place on the
other side of the membrane, which is in contact
with the continuous phase (Fig. 1). Here, droplets
can detach after reaching a critical dimension
either for spontaneous deformation (Static Mem-
brane Emulsification,) or as a consequence of the
shear stress generated by moving the membrane
or the continuous phase (Dynamic Membrane
Emulsification.
Usually, in the DME method, the membrane is
wetted by the continuous phase, and hydrophilic
and hydrophobic membranes are used in the prep-
aration of oil-in-water (O/W) and water-in-oil
(W/O) emulsions, respectively. The mean emul-
sion droplet size is controlled by the appropriate
selection of the pore size of the membrane, and a
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_182-1
factor of 2–10 is found between pore size and
droplets size. Additional parameters have to be
considered to tune the production of an emulsion
by DME:
• Shear stress. Uniform and small droplets are
obtained when the shear stress increases as a
consequence of their faster detachment at the
membrane pore surface. In general, the mean
droplet size decreases exponentially until it
reaches a size where it becomes, more or
less, independent of the applied shear. The
shear stress can be produced: (i) by flowing
the continuous phase tangentially to the mem-
brane surface (cross-flow ME), (ii) by pulsat-
ing the continuous phase in the lumen side of
the membrane (pulsed ME or pulsed back-
and-forward ME), (iii) by rotating or vibrating
the membrane, and (iv) by inducing azimuthal
oscillation of a tubular membrane.
• Transmembrane pressure. The transmem-
brane pressure needs to be higher than a crit-
ical pressure (capillary pressure) in order to
initiate dispersed phase intrusion in the pores.
The dispersed phase flux increases with an
increase of the transmembrane pressure as
more pores are gradually activated for droplet
production and the velocity increases in the
pores. Larger droplets are produced at higher
dispersed phase flux.
• Emulsifier. Droplet size decreases with lower
interfacial tension and, according to the time
needed by the emulsifier, is dissolved in the
2 Direct Membrane Emulsification
Dispersed Phase
Membrane
Continuous Phase
Direct Membrane Emulsification, Fig. 1 Direct mem-
brane emulsification method
dispersed phase to cover the forming droplet
surface area. Smaller droplets are produced
because of a faster decrease of retaining forces
and a reduction of coalescence between the
forming droplets at adjacent pores.
One of the main limitations of DME is the low
dispersed phase flux through conventional
matrix-type membranes (like SPG or ceramic
membranes) which have high thickness and tor-
tuous pore channels giving relatively high flow
resistance. As an alternative, higher dispersed
phase flux at low transmembrane pressure can
be achieved using microsieve-type membranes
due to their low thickness and well-defined recti-
linear pores. Another problem encountered when
the amount of the dispersed phase emulsified is
increased is the recirculation of the continuous
phase (including emulsion drops), giving rise to
poor control over the droplet size distribution.
This is due to the interactions of the newly
forming droplets with droplets in the emulsion,
as well as droplet breakup within the circuit. To
overcome this problem, advanced methods for
dynamic membrane emulsification like rotating,
vibrating, azimuthally oscillating membrane
emulsification, and pulsed flow have received
much attention.
The DME method is suitable for the prepara-
tion of simple and multiple emulsions as well as
polymeric particles. In the latter case, polymeri-
zation, gelation, or coacervation processes of the
formed droplets are carried out subsequently to
droplet generation.
References
Nakashima T, Shimizu M, Kukizaki M (1991) Membrane
emulsification by microporous glass, Key Engineering
Materials, 61/62: 513–516
D
Direct Methanol Fuel Cell (DMFC)
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
The core of a direct methanol fuel cell is a polymer
electrolyte ion-exchange membrane. The elec-
trodes (anode and cathode) are in intimate contact
with the membrane faces. A scanning electron
micrograph of a DMFC MEA is shown in Fig. 1
(Aricò et al. 2001). The electrodes usually consist
of three layers: catalytic layer, diffusion layer, and
backing layer. The catalytic layer is composed of a
mixture of catalyst and ionomer, and it is charac-
terized by a mixed electronic-ionic conductivity.
The catalysts are often based on carbon-supported
or carbon-unsupported PtRu and Pt materials at
the anode and cathode, respectively. The mem-
brane as well as the ionomer consists, in most
cases, of a perfluorosulfonic acid polymer. The
package formed by electrodes and membrane is
called “membrane and electrode assembly”
(MEA). The overall thickness of this package is
generally smaller than 1 mm. Each MEA forms a
cell. Several cells are usually connected in series
to form a fuel cell stack that is integrated in a
system which contains the auxiliaries allowing
stack operation and delivering of the electrical
power to the external load.
Typical perfluorosulfonic acid membranes
used in the present DMFCs, such as Nafion
(DuPont), are permeable to methanol transport
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_183-2
(Ren et al. 1996), thereby reducing significantly
the fuel utilization efficiency of the device.
A scheme of the overall reaction process occur-
ring in a DMFC equipped with a proton-
conducting electrolyte is outlined below:
CH3 OH þ H2 O ! CO2 þ 6Hþ
þ 6e ðanodeÞ (1)
3=2O2 þ 6 Hþ þ 6e ! 3H2 O ðcathodeÞ (2)
CH3 OH þ 3=2 O2 ! CO2
þ 2H2 OðoverallÞ (3)
In the presence of an alkaline electrolyte, the
process is outlined as follows:
CH3 OH þ 6 OH ! CO2 þ 5 H2 O
þ 6e ðanodeÞ (4)
3=2O2 þ 3H2 O þ 6e ! 6OH ðcathodeÞ (5)
CH3 OH þ 3=2O2 ! CO2
þ 2H2 OðoverallÞ (3’)
The thermodynamic efficiency of the process is
given by the ratio between the Gibbs free energy,
i.e., the maximum value of electrical work (DG )
that can be obtained, and the total available energy
for the process, i.e., the enthalpy (DH ). Under
standard conditions:
2 Direct Methanol Fuel Cell (DMFC)

Direct Methanol Fuel Cell

(DMFC), Fig. 1 SEM
micrograph of a DMFC
membrane and electrode
assembly equipped with
Nafion 112 membrane

Direct Methanol Fuel Cell 1

(DMFC), Fig. 2 Single-cell T = 60°C
and in situ half-cell Cell
electrode polarizations for a 0.8
Anode
DMFC operating at 60  C,
ambient pressure, with 1 M Cathode
Potential / V

methanol at the anode and 0.6

air feed at the cathode
0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Current density / A cm–2

rev ¼ DG =DH ; reversible energy efficiency potential for methanol oxidation is 1.18 V (Aricò
(6) et al. 2001). It does not vary significantly in the
operating range 20 –130  C and 1–3 bar abs.
with pressure.
Usually, the open-circuit voltage of a polymer
DG ¼ DH  ðT  DS Þ (7) electrolyte direct methanol fuel cell is signifi-
cantly lower than the thermodynamic or reversible
and potential for the overall process (Fig. 2). This is
mainly due to methanol crossover that causes a
DG ¼ nF  DErev (8) mixed potential at the cathode and to the irrevers-
ible adsorption of intermediate species at elec-
DErev is the electromotive force. At 25  C and trode potentials close to the reversible potential.
1 atm and with pure oxygen feed, the reversible Direct methanol fuel cells find application in
Direct Methanol Fuel Cell (DMFC)
portable power sources, assisted power units
(APU), and electrotraction (Dillon et al. 2004).
References
Arico AS, Srinivasan S, Antonucci V (2001) DMFCs:
From fundamental aspects to technology development.
Fuel Cells 1:133
3
Dillon R, Srinivasan S, Aricò AS, Antonucci V (2004)
International activities in DMFC R&D: Status of tech-
nologies and potential applications. J Power Sources
127:112
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells. J
Electrochem Soc 143:L12
D
Direct Contact Membrane
Distillation (DCMD)
Francesca Macedonio
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende
(CS), Italy
Direct contact membrane distillation (DCMD) is
one of the four main possible membrane distilla-
tion (MD) configurations. In DCMD process, an
aqueous solution colder than the feed aqueous
solution is maintained in direct contact with the
permeate side of the membrane. Both the feed
and permeate aqueous solutions are circulated
tangentially to the membrane surfaces (Fig. 1).
In this MD mode, the transmembrane tempera-
ture difference induces the required water vapor
pressure difference between both membrane
sides. Consequently, water molecules evaporate
at the hot liquid/vapor interface, diffuse in vapor
phase through the pores, and are condensed at the
pore-distillate interface on the other side of the
membrane at a lower temperature (Fig. 2).
Among the possible MD configurations,
DCMD is best suited for applications such as
desalination or the concentration of aqueous solu-
tions (orange juice), in which water is the major
permeating component. Advantages and draw-
backs of DCMD are similar to those of other
MD configurations (see Membrane Distillation
for a detailed description of benefits and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_185-1
disadvantages of DCMD) and summarized
briefly as follows: theoretically 100 % rejection
of nonvolatile solutes, lower operating tempera-
ture with respect to thermal evaporation pro-
cesses, and reduced membrane fouling problem
with respect to pressure-driven membrane pro-
cesses, weakly influenced by feed concentration.
Therefore, this thermal technique is relatively
free from flux reduction by concentrating feed,
which is inevitable in the reverse osmosis (RO)-
based process. Consequently, the DCMD process
is an appropriate alternative for achieving high
water recovery from brackish/seawater feeds,
managing the concentrate from desalination pro-
cesses including RO and recovering water from
industrial brines.
Heat and mass transfer phenomena occurring
in DCMD process are discussed in various recent
publications (Lawson and Lloyd 1997; Drioli
et al. 2015; Schofield and Fane 1987; Martınez-
Diez and Vázquez-González 2000; Gryta
et al. 1997; Ali et al. 2013 and see “▶ Membrane
Distillation”). The flux N can be represented by
the following simple correlation:


N ¼ C Pfm  Ppm
where C is the membrane characteristic parame-
ter and can be calculated by using various
models, depending upon the membrane features
and operating temperature applied.
DP ¼ Pfm  Ppm represents the vapor pressure
2 Direct Contact Membrane Distillation (DCMD)

Direct Contact
Membrane Distillation
(DCMD), Fig. 1 Typical
DCMD schema

Direct Contact
Membrane Distillation Tf
(DCMD), Fig. 2 DCMD vapour
m
process Tf

Tpm
vapour
Tp

FEED vapour DISTILLATE

or or
RETENTATE PERMEATE

difference across the membrane (function of tem- Km

peratures and compositions at the membrane sur-
face at feed f and permeate p side, respectively).
Mass transfer in direct contact membrane distil-
lation can be separated into three steps (e.g., mass
transfer in feed boundary layer, mass transfer
across the membrane, and mass transfer in per-
meate boundary layer, as in membrane distilla-
tion). The mass transfer in permeate boundary
layer is not taken into account since the mole
fraction of the transporting species in the perme-
ate stream is approximately equal to one. For
what concerns the mass transfer in boundary
layers, it is general to neglect surface diffusion
and viscous flow and to employ a Knudsen-
molecular diffusion transition model (Lawson
and Lloyd 1997; Srisurichan et al. 2006).
For what concerns heat transfer, the net heat
transported through conduction Qc and due to
evaporation Qv in DCMD can be calculated by
using the following relationships (Drioli
et al. 2015):
Q ¼ Qc þ Qv ¼ T fm  T pm þ Jl (1)
d
at steady state



Qf ¼ Qp ) hf T f  T fm ¼ hp T pm  T p (2)
where Qf and Qp represent the heat transferred at
bulk feed and permeate side, respectively. More-
over, each h and each T represent the
corresponding heat transfer coefficients and tem-
peratures shown in Fig. 2.
The real challenge is to calculate the temper-
atures at membrane surfaces (Tfm and Tpm). To
realize this, various approaches have been used
(Schofield and Fane 1987; Martınez-Diez and
Vázquez-González 2000; Gryta et al. 1997).
Schofield (Schofield and Fane 1987) suggests
the following approach valid when transmem-
brane surface temperature differences are not
greater than 10  C. In this case the pure water
flux can be represented by
Direct Contact Membrane Distillation (DCMD) 3

dP
Equation 1 was originally developed for

N¼C jT m T fm  T pm (3)
dT Tfm  Tpm  10o C and for pure water as feed
and permeate. A more general approach for the
where dPdT jT m can be expressed according to determination of up- and downstream heat trans-
Clausius-Clapeyron equation: fer coefficients is based on the use of various
empirical correlations. Recently some ambitious
dP MlP attempts have been observed in measuring the
jT ¼ jT (4)
dT m RT 2 m membrane surface temperature directly by using
different techniques. For example, Ali
where M is the molar mass of water molecules. et al. (2013) have used a cell equipped with
Assuming the same temperature polarization on 16 temperature sensors to measure the tempera-
up- and downstream, ture profiles on feed and permeate side in DCM-
D. The effect of different parameters on thermal
Tf þ Tp
Tm ¼ (5) polarization has been investigated by directly
2 monitoring the bulk and interfacial temperatures.
The authors have concluded that heat transfer
Thus Eq. 1 can be written in the following form:
coefficient can be predicted by using the relation-
  ship predicted by (Gryta et al. 1997).
Km dP

Q¼ þ C jT m l T f  T fm (6)
d dT

References
Q ¼ H T fm  T pm : (7)
Ali A, Macedonio F, Drioli E, Aljlil S, Alharbi O a
Combining Eqs. 2, 6, and 7 (2013) Experimental and theoretical evaluation of
temperature polarization phenomenon in direct contact

Tf  Tp membrane distillation. Chem Eng Res Des
T fm  T pm ¼ (8) 91(10):1966–1977
H H Drioli E, Ali A, Macedonio F (2015) Membrane distilla-
1þ þ
hf hp tion: recent developments and perspectives. Desalina-
tion 356:56–84


Gryta M, Tomaszewska M, Morawski AW (1997) Mem-
T fm  T pm ¼ y T f  T p (9) brane distillation with laminar flow. Sep Purif Technol
11:93–101
from Eqs. 3 and 8, Lawson KW, Lloyd DR (1997) Membrane distillation.
J Membr Sci 124:1–25
  Martınez-Diez L, Vázquez-González MI (2000) A method
DT 1 1 K m =dm 1 to evaluate coefficients affecting flux in membrane
¼ 1þ þ (10)
Nl dP=dT lC h h distillation. J Membr Sci 173:225–234
Schofield RW, Fane AG (1987) Heat and mass transfer in
membrane distillation. J Membr Sci 33:299–313
The permeability C and overall
heat transfer Srisurichan S, Jiraratananon R, Fane AG (2006) Mass
coefficient h 1=hf þ 1=hp can be determined transfer mechanisms and transport resistances in direct
by plotting DT 1
Nl versus dP=dT as illustrated by Eq. 10
contact membrane distillation process. J Membr Sci
(Drioli et al. 2015; Schofield and Fane 1987). 277:186–194
D
Direct Contact Membrane
Distillation (DCMD) Applications
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Poland
DCMD is a membrane distillation
(MD) configuration in which both solutions,
feed and permeate, are in a direct contact with a
hydrophobic porous membrane. Thus, the water
vapor transferred across the membrane is directly
condensed in a cold permeate inside the mem-
brane module. This configuration has been the
most frequently studied due to a simple operation
mode in comparison with other MD configura-
tions. DCMD is considered as the best choice for
applications in which water is the major compo-
nent of the feeding solution. DCMD can be
applied in chemical, food, or pharmaceutical
industry and in environmental protection.
The major area of DCMD application is desali-
nation focused on the production of high purity
water and freshwater from sea or brackish water.
The nature of DCMD driving force causes that
nonvolatile solutes such as salts, colloids, and mac-
romolecules that are almost completely retained by
a membrane. The permeate is pure water with elec-
trical conductivity of 0.2–2.5 mS/cm, which is suit-
able for medical, pharmaceutical, or semiconductor
industry purposes. Lower temperatures than those
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_186-1
usually used in the conventional distillation allow to
achieve the permeate fluxes up to 80 kg/m2h with
significant reduction in energy costs. Typical feed
temperatures (30–80  C) permit the efficient recy-
cle of low-grade or waste heat streams, as well as
the use of alternative energy sources (solar, wind, or
geothermal). In addition, the possibility of using
plastic equipment also reduces corrosion problems
(Drioli et al. 2005; Khayet and Matsuura 2011).
Integration of DCMD with pressure-driven
membrane processes such as microfiltration
(MF) or reverse osmosis (RO) creates the oppor-
tunity for enhancement of water productivity
from seawater up to 87.6 %. A development of
the system coupling nanofiltration (NF) and RO
with DCMD/membrane crystallizer (MCr) might
lead to an increase in the total water recovery
factor of a desalination plant up to 92.8 %
(Fig. 1). An application of the DCMD/MCr sys-
tem allows to recover both water and salts
(commercial products), reducing the environ-
mental problems related to brine disposal
(Drioli et al. 2011; Di Profio et al. 2010).
A DCMD system utilizing solar and wind
energy for water supply, designed for small
board and rural or coastal areas with a lack of
electricity, is presented in Fig. 2 (Susanto 2011).
DCMD has also been applied to surface or
groundwater treatment. It was found that mem-
brane scaling by CaCO3, CaSO4, and their mix-
ture occurring in the system can be significantly
limited by the feed acidification or antiscalant
addition. Moreover, it was found that scaling in
2 Direct Contact Membrane Distillation (DCMD) Applications

Sea MF/UF NF RO Fresh

water water

Fresh water membrane MD

crystallizer (crystallizer)
NaCl
NaCl, CaCO3,
MgSO4*7H2O

Direct Contact Membrane Distillation (DCMD) Appli- crystallization units operating on the brine from NF and/or
cations, Fig. 1 Scheme of sea water desalination plant RO stages (Based on Di Profio et al. (2010)).
using integrated membrane system containing membrane

Direct Contact Membrane Distillation (DCMD) Applications, Fig. 2 Schematic diagram of DCMD powered by
solar and wind energy (Reprinted from Susanto (2011), copyright (2011), with permission from Elsevier)

DCMD is less severe than in conventional desa-
lination processes (Khayet and Matsuura 2011).
DCMD can be operated with solutions of
extremely high concentration of salts, even
close to the supersaturated point, and the perme-
ate flux was satisfying. Therefore, DCMD has
also been successfully applied to wastewater
treatment, either to produce a permeate less haz-
ardous to the environment or to obtain a retentate
that contains high concentration of valuable
chemicals (Table 1) (Khayet and Matsuura
2011).
The main disadvantage of DCMD process is a
problem with membrane wetting, what limits the
Direct Contact Membrane Distillation (DCMD) Applications 3

Direct Contact Membrane Distillation (DCMD) Applications, Table 1 Examples of DCMD application in various
fields
Application area Examples of application
Water treatment Desalination of seawater and brackish water, removal of various contaminants (heavy metals,
arsenic, boron, humic acid) from surface and groundwater, production of high purity water,
removal of low concentrations of organics (ethanol, acetone, acetonitrile, n-butanol)
Wastewater Treatment of low- and medium-level radioactive wastewater, textile wastewater contaminated
treatment with dyes, oil-water emulsions, HCl removal from etching solutions from electrochemical
industry, separation of photocatalyst in the photocatalysis-DCMD system, reclamation in space
Medicine and Concentration of an extract of traditional Chinese medicine
biology Concentration of bovine plasma and bovine blood, bovine serum albumin, to ameliorate
treatment of uremia
Pharmacy Pharmaceutical wastewaters containing taurine
Food industry Concentration of fruit and juices, whey, sugarcane, etc.
Biotechnology Removal of toxic products from culture broth, production of ethanol in a bioreactor-DCMD
system
Chemical Concentration of acids, separation of a half-finished product (HCl) from the reaction mixture to
industry shift the reaction equilibrium in DCMD-chemical reactor system
Other Ethylene glycol removal from coolant liquids, breaking azeotropic mixtures HCl-water,
propionic acid-water, salt crystallization in DCMD/MCr

water
Hydrochloric acid
Metal objects
purified
Etching bath Rinsing objects

Concentration
Concentration of MD II
spent pickling
solution MD I
Crystallisation
HCl solution
salt
HCl concentration water
MD III

Direct Contact Membrane Distillation (DCMD) Appli- solution using DCMD (Reprinted from Tomaszewska
cations, Fig. 3 The flow – sheet diagram of integrated et al. 2001, copyright (2001) with permission from
processes of metal pickling with treatment of spent Elsevier)

concentration of organic compounds to diluted
aqueous solutions. The membranes used in MD
are chemically resistant; thus, they can tolerate
harsh operating conditions. DCMD is a promis-
ing method for recovery of HCl from metal pick-
ling solutions (Fig. 3) (Tomaszewska et al. 2001).
The process was also successfully applied in a
pilot scale to clean low- and medium-level radio-
active waste from a nuclear center.
Moreover, DCMD found success in the treat-
ment of solutions containing substances sensitive
to high temperature due to the risk of their deg-
radation, especially in biotechnology and food
4 Direct Contact Membrane Distillation (DCMD) Applications
Direct Contact
Membrane Distillation
(DCMD) Applications,
Fig. 4 Scheme of the
conversion of potassium
chloride into potassium
sulfate using integrated
Sulfuric acid
system: chemical reactor/
DCMD (Based on
Tomaszewska and Mientka
2009)
Solvent
Solvent
recovery
industry (fruit juices concentration) (Sotoft
et al. 2012).
Novel applications are bio- and chemical reac-
tors integrated with DCMD in which the volatile
products are continuously removed from the
reaction mixture to shift the equilibrium and
improve productivity. It was found that a contin-
uous extraction of ethanol from broth using
DCMD resulted in an increase of its productivity
by 87 % (Khayet and Matsuura 2011). The mem-
brane reactor based on DCMD was applied in the
production of potassium sulfate for fertilizer
industry (Tomaszewska and Mientka 2009). The
concentration of the reaction mixture containing
KCl and K2SO4 close to the saturated state in the
membrane reactor resulted in periodical precipi-
tation of KHSO4, whereas HCl was continuously
removed from the reaction mixture to shift the
equilibrium of the conversion (Fig. 4).
MD is generally recommended for special
purposes for which the application of other mem-
brane techniques was considered impossible.
Until now the DCMD process has been under
development due to high energy consumption
and problems with the membrane wettability dur-
ing long-time operation. However, it should be
pointed out that there are numerous calculations
KCl, H2SO4
MD REACTOR
KCl+H2SO4=
KHSO4+ HCl HCl
Retentate
Permeate
Hydrochloric
CRYSTALLIZER acid
KHSO4
DESALTING
2KHSO4 K2SO4+H2SO4
K2SO4 free of chlorides
showing that DCMD can be economically attrac-
tive especially when low-grade energy or alter-
native energy is used.
References
Di Profio G, Curcio E, Drioli E (2010) Membrane crystal-
lization technology. In: Drioli E, Giorno L (eds) Com-
prehensive membrane science and engineering,
vol 4. Academic Press/Elsevier, Oxford, pp 21–46
Drioli E, Curcio E, Di Profio G (2005) Review paper: state
of the art and recent progresses in membrane
contactors. Chem Eng Res Des 83(A3):223–233
Drioli E, Stankiewicz AI, Macedonio F (2011) Membrane
engineering in process intensification – an overview.
J Membr Sci 380:1–8
Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
Sotoft LF, Christensen KV, Andrésen R, Norddahl
B (2012) Full scale plant with membrane based con-
centration of blackcurrant juice on the basis of labora-
tory and pilot scale tests. Chem Eng Process 54:12–21
Susanto H (2011) Towards practical implementations of
membrane distillation. Chem Eng Process 50:139–150
Tomaszewska M, Mientka A (2009) Conversion of KCl
into KHSO4 in membrane reactor: long-term experi-
ments. Desalination 245:647–656
Tomaszewska M, Gryta M, Morawski AW (2001) Recov-
ery of hydrochloric acid from metal pickling solutions
by membrane distillation. Sep Purif Technol
22–23:591–600
D
Double Emulsion
Na Li
Department of Chemical Engineering, School of
Chemical Engineering and Technology, Xi’an
Jiaotong University, Xi’an City, China
Synonyms
Multiple emulsions
Double emulsion is a complex system of an emul-
sion in an emulsion, where the droplets of the
dispersed phase themselves contain even smaller
dispersed droplets. An emulsion is a dispersion of
droplets of one liquid in another one with which it
is incompletely miscible.
Two main types of double emulsion can be
distinguished: water-in-oil-in-water (W/O/W)
emulsion, in which a W/O emulsion is dispersed
as droplets in an aqueous phase, and oil-in-water-
in-oil (O/W/O) emulsion, in which an O/W emul-
sion is dispersed in an oil phase. W/O/W emul-
sion is more common than O/W/O emulsion.
Double emulsion contains more interface and is
even more thermodynamically unstable than sin-
gle emulsion (Graaf et al. 2005).
Double emulsions have significant potential in
many applications since, at least in theory, they
can serve as an entrapping reservoir for active
ingredients that can be released from the inner
phase to the outer phase by a controlled and a
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_190-5
sustained mechanism. The major area of applica-
tions concerns the human pharmaceutical field:
water-in-oil-in-water (W/O/W) emulsions have
been investigated as potential vehicles for various
hydrophilic drugs (vaccines, vitamins, enzymes,
hormones) which would be then slowly released.
Also, double emulsions have promising applica-
tions in other fields like the food industry (low
calorie products, improved sensoric characteris-
tics, taste masking), cosmetic industry (easily
spreadable creams with encapsulated ingredients
in both water and oil phases), separation science,
and agriculture.
In practice, double emulsions are thermody-
namically unstable systems with a strong ten-
dency for coalescence, flocculation, and
creaming. Most double emulsions consist of rel-
atively large droplets, cannot withstand storage
regimes, and have a strong tendency to release the
entrapped matter in an uncontrolled manner. Four
possible mechanisms are described for instability
of W/O/W emulsion: (1) coalescence of the inter-
nal aqueous droplets, (2) coalescence of the oil
drops, (3) rupture of the oil film separating the
internal and external aqueous phases, and (4) pas-
sage of water (and water-soluble material, e.g., a
drug) to and from internal droplets through the oil
layer (Graaf et al. 2005). Much work has been
devoted in the last decade in order to improve the
stability of the multiple emulsions and the control
of the release rates of the addenda. The most
recent achievements are the use of polymeric
emulsifiers to improve interface coverage and to
2 Double Emulsion
better anchor into the dispersed phase and the
decrease of droplet size by improving methods
of formation (Garti 1997).
Double emulsion is generally prepared in a
two-step emulsification process using two surfac-
tants of opposite solubility. To produce O/W/O
emulsion, a W/O emulsion is first prepared with a
large excess of hydrophobic surfactant (HLB
<10), by strong homogenization, to form the
smallest possible droplets. In the second step a
W/O/W double emulsion is further formed by
gentle addition of the W/O (termed inner emul-
sion) to water in which a hydrophilic one (HLB
>10) has been dissolved (Bibette et al. 1999).
The most important conventional emulsifica-
tion devices are stirring apparatuses, rotor–stator
systems, and high-pressure homogenizers. Mem-
brane emulsification is a relatively new method
for the production of emulsions that has received
increasing attention over the last 15 years. The
technique is attractive given the low energy con-
sumption, the better control of droplet size and
droplet size distribution and especially the mild-
ness of the process. Microchannel emulsification
is a novel method for producing monodisperse
emulsions. It is even more monodisperse than
usually obtained with membrane emulsification
(Graaf et al. 2005).
References
Bibette J, Calderon FL, Poulin P (1999) Emulsions: basic
principles. Rep Prog Phys 62:969–1033
Garti N (1997) Double emulsions-scope, imitations and
new achievements. Colloid Surf A 123–124:233–246
Graaf S, Schroën CGPH, Boom RM (2005) Preparation of
double emulsions by membrane emulsification-a
review. J Membr Sci 251:7–15
D
Double Emulsion Production,
Membrane Operations of
Na Li
Department of Chemical Engineering, School of
Chemical Engineering and Technology, Xi’an
Jiaotong University, Xi’an, China
Double emulsions are emulsions of emulsions.
The droplets of the dispersed phase themselves
contain even smaller dispersed droplets. Two
main types of double emulsions are water-in-
oil-in-water (W/O/W) emulsions and oil-in-
water-in-oil (O/W/O) emulsions. The former is
more common. Double emulsions have shown
significant promise in the food industry, cosmetic
industry, pharmacology industry, and other fields
like agriculture and separation science.
Double emulsions are usually prepared in a
two-step emulsion process. First, internal emul-
sion (e.g., water-in-oil (W/O)) is designed under
high-shear conditions to obtain small droplets.
Secondary emulsion step for double emulsion
(e.g., water-in-oil-in water (W/O/W)) is carried
out with mild shear to avoid rupture of the inter-
nal droplets. Usually, the primary step can be
produced by conventional method or also by
membrane emulsification, while the membrane
emulsification is especially suitable for the sec-
ond emulsification step.
For the conventional emulsification method,
the most commonly used devices are rotor–stator
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_191-5
systems and high-pressure homogenizers. In
rotor–stator systems (i.e., colloid mills), a high
shear is generated between a rotor and a station-
ary smooth, roughened, or grooved surface. Tur-
bulence is the primary cause of fluid disruption
leading to the formation of droplets (Graaf
et al. 2005). In a high-pressure homogenizer, the
droplets are broken up in a nozzle by turbulence
and cavitation. This process can be assisted with
the use of an ultrasonic or electric fields. Due to
their high throughput, rotor–stator systems and
high-pressure homogenizers are suitable for
large-scale production of emulsions. However,
energy requirements of these systems are high
because only a small part of the energy input is
used for droplet breakup; most of the energy
supplied is lost and converted into heat. Further-
more, shear stresses these systems applied may
cause loss of functional properties of heat- and
shear-sensitive components. In addition, they
show poor control over droplet size and
distribution.
In order to overcome the problems of tradi-
tional emulsification methods, a new technique
for making emulsions known as “membrane
emulsification” arouses people’s interest. This
method involves using a low pressure to force
the dispersed phase to permeate into the continu-
ous phase through a membrane which has a uni-
form pore-size distribution. Droplets grow at pore
outlets and then detach when reaching a certain
size (Joscelyne and Tragardh 2000). One of the
most significant advantages of membrane
2 Double Emulsion Production, Membrane Operations of
emulsification is the low energy consumption.
Also the better control of droplet size and distri-
bution and the mildness of the process are highly
attractive. Compared to conventional methods, a
disadvantage of membrane emulsification is that
the flux of the dispersed phase through the mem-
brane is fairly low. However, the flux of dispersed
phase could be increased by using a membrane
with a low hydraulic resistance (e.g.,
microsieves).
The commonly used membranes for mem-
brane emulsification are Shirasu porous glass
(SPG) membranes, ceramic aluminum oxide
(a-Al2O3) membranes, a-alumina- and zirconia-
coated membranes, macroporous silica glass
membranes, micro-fabricated metal membranes,
polytetrafluoroethylene (PTFE) membranes, and
hydrophobized silicon nitride microsieves.
For membrane emulsification two methods
of operation are used: cross-flow membrane
emulsification and premix membrane
emulsification.
Generally, the important process controlling
parameters are membrane pore size, porosity,
thickness, and surface type, the velocity of con-
tinuous phase, the transmembrane pressure, and
wall contact angle. It has been found that it is a
linear relationship between the droplet size and
membranes pore size. At high porosities, it is
more likely for droplets to coalesce at the mem-
brane surface before they detach. If the porosity is
too low, the dispersed phase flux may be not
sufficient for viable production of emulsions.
The thinner the membrane, the larger the flux
through the pores will be, which leads to a higher
droplet expansion rate. It has been observed that
hydrophilic membranes are fit for making O/W
emulsions and hydrophobic membranes for W/O
emulsions. The droplet size decreases sharply as
the cross-flow velocity increases from rest and
reaches a size where it becomes more or less
independent of the flow velocity. The permeating
flux is increased by increasing the transmem-
brane pressure. Another important parameter
affecting the droplet size is the wall contact
angle. Higher wall contact angle results in larger
droplets and a more polydisperse emulsion.
References
Graaf S et al (2005) Preparation of double emulsions by
membrane emulsification-a review. J Membr Sci
251:7–15
Joscelyne SM, Tragardh G (2000) Membrane
emulsification-a literature review. J Membr Sci
169:107–117
D
Dynamic Free Volume
Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Dynamic free volume appears in liquids (Frenkel
1946) and in polymers above their glass transition
temperatures Tg, i.e., in rubbers. In liquids, it
appears due to mobility of individual molecules,
while in rubbers due to segmental mobility.
Dynamic free volume influences such properties
of the medium as diffusion and self-diffusion
coefficients and viscosity. In glassy state, where
the segmental mobility is frozen, still some local
mobility of small side groups is possible as well
as the corresponding free volume. When a glassy
polymer is plasticized, that is, contains low
molecular mass additives, their mobility can
induce some mobility of the adjacent parts of
the main or side chains. So the fraction of
dynamic free volume in the total free volume
can increase, the polymer becomes more “rub-
berlike,” and its properties (gas permeation
parameters) become more similar to those of
rubbers: increase in permeability and decrease
in permselectivity. These phenomena are detri-
mental for separation of gas mixtures that contain
great concentration of highly sorbed components
like carbon dioxide (Sanders 1988). According to
molecular dynamics, the average time of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_193-4
“settled” life of free volume elements in rubbers
is very short – about several picoseconds
(Hofmann et al. 2000). The mobility of any
kinetic system is determined by the relaxation
time t: t(T) = to exp(U/kT), where U is the
activation energy and to = 10 12 s. It is often
assumed that U increases at decreased tempera-
tures and, hence, the relaxation times at the glass
transition temperature t(Tg) become longer than
the intrinsic times of cooling of the high elastic
system, i.e., vitrification occurs. These changes
of U are caused by the decreases in the dynamic
free volume in rubbers vf. The dynamic
(or fluctuation) free volume above Tg increases
with temperature according to the equation:
vf = vfg[1 + (ar ag)(T Tg)], where ar and ag
are the coefficients of thermal expansion above
and below Tg, respectively, and vfg is the free
volume at Tg. Originally, it has been assumed
that the fraction of free volume at Tg, fc = vf/v,
where v is the specific volume of the polymer, is
constant for most of the polymers and equal
0.025  0.003 (iso-free volume concept of
Simha-Boyer). Further studies showed that fc
varied in a much wider range and increases with
Tg (Yampolskii et al. 2000).
The variation of the dynamic free volume in
rubbers with temperature and as a function of Tg
has important implications for membrane sci-
ence: when the difference Texp-Tg increases
(at constant Texp), i.e., for the rubbers with
lower Tg, e.g., polydimethylsiloxane, the trans-
port parameters such as P(Texp) and D(Texp)
2 Dynamic Free Volume

strongly increase (van Amerongen 1964; References

Yampolskii et al. 1982). Here, Texp is the ambient
temperature at which the permeability and diffu- Frenkel YI (1946) Theory of liquids. Clarendon, Oxford
Hofmann D, Fritz L, Ulbricht J, Paul D (2000) Comput
sion coefficients are usually measured. It means
Theory Polym Sci 10:419–436
that the polymers with the lowest glass transition Sanders ES (1988) J Membr Sci 37:63–80
temperature have the greatest dynamic free vol- van Amerongen GJ (1964) Rubber Chem Technol
ume at ambient temperatures. 37:1065–1152
Yampolskii Y, Durgaryan S, Nametkin N (1982)
The size of the elements of dynamic free vol-
Vysokomol Soed A 24:536–541
ume in rubbers is relatively large: it should be Yampolskii Y, Kamiya Y, Alentiev A (2000) J Appl
compared with the size of kinetic segments, so Polym Sci 76:1691–1705
much larger than the size of the typical gaseous
penetrants. It means that the selectivity of diffu-
sion in rubbers is very weak, and, because of this,
in rubbers solubility-controlled permeation
regime is realized.
D
Dynamic Membrane Emulsification
E. Piacentini1, A. Imbrogno2 and R. G. Holdich3
1
Institute on Membrane Technology, (ITM-
CNR) c/o University of Calabria, Rende (CS),
Italy
2
Institute on Membrane Technology
(ITM-CNR), University of Calabria, Rende (CS),
Italy
3
Department of Chemical Engineering,
Loughborough University, Loughborough,
Leicestershire, UK
Dynamic membrane emulsification (ME) refers
to the formation of emulsion droplets by extrud-
ing the to-be-dispersed phase through the mem-
brane pores into the continuous phase, and the
droplet detachment occurs by a surface shear.
The regular droplet detachment from the pore
openings is obtained by:
(i) Moving the continuous phase in cross-flow,
stirred, or pulsed mode
(ii) Moving the membranes by rotation, vibra-
tion, or oscillation
In Table 1, techniques, shear stress profile, and
forces acting on a forming droplet for each mem-
brane emulsification process are illustrated.
In cross-flow mode, the shear stress is gener-
ated by the recirculation of the continuous phase
tangentially to the membrane surface. This
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_194-1
technique is called “cross-flow ME.” A typical
cross-flow ME apparatus includes a tubular or
flat-sheet microfiltration membrane, a pump for
the recirculation of the continuous phase along
the lumen side of the membrane, a feed vessel,
and a pressured nitrogen gas container for the
dispersed phase (Peng and Fellow 1998). Cross-
flow ME is suitable for large-scale production
and continuous or semicontinuous operation.
However, droplet breakup can occur over time
when concentrated emulsion is produced due to
the high cross-flow velocities used to obtain nar-
row droplet size distribution at high dispersed
phase flux or over long time of operation.
In pulsed-flow mode, a periodic flow pulsation
is generated in the continuous phase without
recirculation. This technique is called “pulsed-
flow ME.” In a typical pulsed-flow ME apparatus,
the dispersed and the continuous phases are
injected using a pump, while the pulsed flow in
the continuous phase is generated by a frequency
generator (Holdich et al. 2013) or by inverting the
flow direction back and forward within the mem-
brane lumen (Piacentini et al. 2014). Pulsed-flow
ME is advantageous for the production of emul-
sions with a high dispersed to continuous phase
ratio, and it is suitable for large-scale production
in continuous or semicontinuous mode.
In an alternative, the shear stress on the mem-
brane surface can be generated by stirring the
continuous phase. This technique is called “stirred
membrane emulsification.” In a typical stirred ME
device, the dispersed phase is injected through the
 2

Dynamic Membrane Emulsification, Table 1 Membrane emulsification techniques, shear stress profile, and forces acting on a forming droplet
Membrane emulsification based on moving the continuous phase
ME plant Forces acting on a drop at the pore level Shear stress profile
Dynamic Membrane Emulsification
 Dynamic Membrane Emulsification

Membrane emulsification based on moving the membrane

ME plant Forces acting on a drop at the pore level Shear stress profile

(continued)
3
 4

Dynamic Membrane Emulsification, Table 1 (continued)

Dynamic Membrane Emulsification
Dynamic Membrane Emulsification
membrane pores by using a pump or nitrogen gas
while stirring the continuous phase with a rotator
when a tube-shaped submerged membrane is used
or with a paddle blade stirrer in the case of a flat-
sheet membrane (Stillwell et al. 2007). Stirred ME
is useful for emulsion production at batch scale, in
the laboratory, and it is especially used to study the
effect of different experimental conditions and
chemistry on the formulation properties.
In rotating ME, the dispersed phase is intro-
duced into the center of a rotating tubular porous
membrane, and droplets are detached at the mem-
brane wall in the radial direction into the station-
ary continuous phase (Vladisavljević and
Williams 2006). The pressure is generated in the
membrane lumen by using nitrogen gas or a
pump, while the membrane is rotated in the con-
tinuous phase by an overhead stirrer. Rotating
ME is particularly advantageous for the produc-
tion of coarse emulsions and fragile structured
products in which the droplets and/or particles
are subject to breakage during the pump
recirculation. However, the use for large-scale
production is limited due to the complicated and
more expensive design and higher power con-
sumption compared to alternative designs.
The vibrating ME principle is similar to the
rotating ME except for the use of oscillation of
the membrane perpendicularly with respect to the
dispersed phase injection direction (Holdich
et al. 2010). The frequency and amplitude of the
axial oscillation of the membrane was generated
by an electrically driven vertical oscillator and
could be controlled separately.
In azimuthally oscillating ME, a tubular mem-
brane is periodically rotated back and forward in
a slowly cross-flowing continuous phase, while
the dispersed phase is radially injected in the
lumen side of the membrane using a pump
(Silva et al. 2015). The azimuthal (tangential)
oscillation of the membrane is controlled by a
control panel which is connected to the oscillator
motor providing separate control over the fre-
quency and membrane displacement. Azimuth-
ally oscillating ME operates in a continuous
mode, and it is suitable for large-scale production
providing high production rates, facilitating easy
process automation and reduced operation time.
5
In dynamic ME, the forces acting on a droplet
at the membrane pore level include detaching
forces, driving droplets off the pore, and retaining
forces, holding droplets on the pore. Detaching
forces are drag (FD), buoyancy (FBG), inertial
(FI), lift (FL), and static pressure (FSP) force,
while the main retaining force is the interfacial
tension (Fg). The drag force (FD) is created either
by moving the continuous phase parallel to the
membrane surface or by moving the membrane;
the buoyancy force (FBG) is due to the density
difference between the continuous phase and the
dispersed phase; the inertial force (FI) is caused by
the dispersed phase flow moving out from the pore
outlet; the dynamic lift force (FL) results from the
asymmetric velocity profile of the continuous
phase near the droplet; static pressure (FSP) force
is due to the pressure difference between the dis-
persed phase and the continuous phase at the
membrane surface; the interfacial tension force
(Fg) represents the effect of dispersed phase adhe-
sion around the edge of the pore opening. In the
case of “moving membrane” emulsification, addi-
tional (or enhanced) forces have to be considered.
For rotating membrane emulsification, com-
pared to a nonrotating system, the drag force cre-
ated by the membrane rotation (FDR) has to be
taken into account, and the gravitational body
force is replaced by the centrifugal force (FC)
resulting from centrifugal acceleration and density
difference of the two phases. High centrifugal force
may be responsible for polydisperse emulsion pro-
duction in the case of O/W emulsion due to defor-
mation of the emerging oil drops and induced flow
of oil drops toward the membrane surface causing
coalescence and wetting of the membrane.
For an oscillating membrane system where the
membrane is axially excited, an additional drag
force (FDE) and inertial force (FIE) appear in the
direction parallel to the membrane. This is due to
a sudden change in the direction of the membrane
which induces a velocity difference in the column
of liquid inside the membrane and localized high
pressure at the peak positions of the vertical
oscillation (i.e., top and bottom of the
membrane tube).
In dynamic ME, the droplet breakup process is
correlated with a dripping or jetting behavior
6 Dynamic Membrane Emulsification
depending on the relative strength of the different
forces acting on the process. In the dripping region,
the inertial force is negligible compared to the drag
force or unable to overcome the surface tension
force. Thus, the droplet size is affected mainly by
the drag force imparted by the continuous phase
flow or moving membrane and the surface tension
force. The inertial force of the dispersed phase has
negligible effect in drop detachment in the dripping
mode. It is shown that the droplet size becomes
smaller as the shear stress increases and the influ-
ence is more significant for low shear values and
smaller pore size. At high dispersed phase flow
rates, the inertial force exceeds the surface tension
force, leading to a transition to jetting behavior. In
this case, the droplet detachment point moves fur-
ther downstream from the pore usually resulting in
the formation of a larger droplet than when in the
dripping regime.
The different process conditions can be accu-
rately tuned to control the shear stress in dynamic
ME according to the mechanism used to generate
the drag force (flowing of continuous phase or
moving membrane); the following provides some
simplified equations for shear at the membrane
surface according to the method of generation of
that shear:
• In cross-flow ME, the shear stress (t) [Pa] is
constant over the tubular membrane area, and
it is correlated with the tangential velocity of
the flowing continuous phase (v) [ms
1], the
density of the emulsion (r) [kgm
3], and the
friction factor (l) which is calculated
depending on the Reynolds number
(l = 16/Re for Re < 2000; l = 0.0792
Re
0.25 for Re > 2000) Eq. 1:
lrn2
t¼ (1)
2
• In stirred ME, the shear stress (t) [Pa] depends
on the angular velocity (o) [s
1] of the stirrer.
The shear over the whole membrane area can
be calculated with the Eqs. 2 and 3:
1
tmax ¼ 0:825mc or trans for r < r trans (2)
d

r 0:6 1
t ¼ 0:825c or trans
trans
for r < r trans
r d
(3)
where mc [Pa s] is the continuous phase viscosity,
rtrans is the transitional radius, and d is the bound-
ary layer thickness
given 
qffiffiffiffiffiffiffiffifrom the Landau-
Lifshitz equation d ¼ m=or . The shear stress
is not uniformly distributed over the membrane
surface, and it can be assumed that the maximal
shear (tmax) is reached at distance rtrans from the
center of the membrane; rtrans is the transitional
radius in which the rotation changed from a free
vortex to a forced vortex.
• In rotating ME, the shear stress is directly pro-
portional to the membrane rotational speed (n)
[rpm] but depends also on the width of the
annular gap between the rotating membrane
and the stationary vessel. The shear at the sur-
face of the membrane is calculated using Eq. 4:
I?R2 n
I? ¼  2 1 2 (4)
15 R2
R1
where R1 is the radius of the rotating membrane
and R2 is the radius of the stationary vessel.
• Pulsed ME and vibrating and azimuthally
oscillating ME are based on the generation of
the shear stress by oscillation of either the
continuous phase or the membrane. Thus,
there are two parameters affecting shear stress
on the membrane surface: frequency (f)
[Hz] and amplitude (a) [m] of the oscillation.
During the oscillation, the shear is variable
and the emerging drop detaches when it expe-
riences the maximum shear stress which is
calculated using Eq. 5:
3= 1=
tmax ¼ 2aðpf Þ 2 ðmrÞ 2
(5)
where m is the viscosity and r is the density of the
continuous phase. A peak shear event occurs twice
per oscillation: once in each direction that the
Dynamic Membrane Emulsification
wave is moving, for a regular wave form such as a
sine wave.
References
Holdich RG, Dragosavac MM, Vladisavljevic GT
(2010) Membrane emulsification with oscillating and
stationary membranes. Ind Eng Chem Res
49(8):3810–3817
Holdich RG, Dragosavac MM, Vladisavljevic GT,
Piacentini E (2013) Continuous membrane emulsifica-
tion with pulsed (oscillatory) flow. Ind Eng Chem Res
52:507–515
Peng SJ, Fellow RAW (1998) Controlled production of
emulsions using a crossflow membrane: part II:
7
industrial scale manufacture. Chem Eng Res Des
76(8):902–910
Piacentini E, Drioli E, Giorno L (2014) Pulsed back-and-
forward cross-flow batch membrane emulsification
with high productivity to obtain highly uniform and
concentrate emulsions. J Membr Sci 453:119–125
Silva PS, Dragosavac MM, Vladisavljević GT,
Bandulasena HCH, Holdich RG, Stillwell M, Williams
B (2015) Azimuthally oscillating membrane emulsifi-
cation for controlled droplet production. AIChE
J. doi:10.1002/aic.14894
Stillwell MT, Holdich RG, Kosvintsev SR, Gasparini G,
Cumming IW (2007) Stirred cell membrane emulsifi-
cation and factors influencing dispersion drop size and
uniformity. Ind Eng Chem Res 46(3):965–972
Vladisavljević GT, Williams RA (2006) Manufacture of
large uniform droplets using rotating membrane emul-
sification. J Colloid Interface Sci 299(1):396–402
E
Electrochemical Processing
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
In electrochemical processing, electrical energy is
supplied to or obtained from the electrochemical
system in order for chemical production or energy
conversion to take place (Bard and Stratmann
2007). The first group of processes, also called
electrolytic, is not spontaneous. The second
group of processes, called galvanic, is spontane-
ous and it delivers electrical energy. Electrolytic
processes can be further divided into two catego-
ries: inorganic and organic. In inorganic electro-
chemical processing, important commodity
chemicals such as sodium hydroxide, chlorine,
and pure metals are produced. The major inor-
ganic electrochemical processing technologies
are chlor-alkali electrolysis and electrowinning
of metals like aluminum or copper. Nowadays,
hydrogen production by water electrolysis gets
more on importance in context of chemical storage
of renewable electrical energy (wind and photo-
voltaic) in hydrogen. The most significant com-
mercial electroorganic synthesis is Monsanto’s
electrohydrodimerization (EHD) of acrylonitrile
to adiponitrile. Adiponitrile has an importance in
production of nylon 6-6. Examples of galvanic
systems are fuel cells and batteries. The main
“product” of galvanic systems is electrical energy.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_198-2
Electrochemical systems have some intrinsic
advantages over other types of chemical systems
like better control of a reaction rate, operation at
lower temperatures, and less environmental
impact. They take place in an electrochemical
reactor. The design of an electrochemical reactor
is influenced by the state of aggregation of reac-
tants (gas, liquid, or solid), necessity of reactants
and/or products separation, required mass trans-
port conditions, and electrode materials. If prod-
uct or reactant separation is required, an
electrochemical reactor must contain a separator,
which is a membrane. Major requirements on a
membrane are good separation efficiency, low
electrical resistance, no electron conductivity,
low cost, long operating life time, good dimen-
sional stability, and resistance to plugging and
fouling. In general permeable and semipermeable
membranes have been applied in electrochemical
processing. Permeable membranes are porous
materials filled with liquid electrolyte which per-
mit the bulk flow of liquid through their structure
and are thus nonselective regarding transport of
ions or neutral molecules. In electrochemical pro-
cesses, these are also referred to as diaphragms.
Permeable membranes can be made of inorganic
and organic materials and composites. Examples
of these materials are asbestos (chlor-alkali elec-
trolysis), polymers like polyethylene and poly-
propylene (batteries), or composites like
polymer (polypropylene)-modified asbestos.
Semipermeable membranes permit the selective
passage of certain species by virtue of molecular
2 Electrochemical Processing

size or charge. In electrochemical processes, References

ion-conducting membranes (see solid electrolyte)
are broadly applied. In general, ion-conducting Bard AJ, Stratmann M (eds) (2007) Encyclopedia of elec-
trochemistry. Macdonald DD, Schmuki P (eds) Elec-
membranes have higher separation efficiency and
trochemical engineering, vol 5. Wiley-VCH Verlag
lower electrical resistance than diaphragms, but GmbH & Co. KGaA, Weinheim
they are also more costly and impose higher
requirements on system purity.
E
Electrochemical Regeneration
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
In electrochemical regeneration electrical energy
is applied to restore some important property, like
adsorption capacity or catalyst activity of a tech-
nical system. Electrochemical regeneration relies
on principles of electrochemistry and relates to
electrochemical processing. Electrochemical
regeneration is conveniently conducted in situ
with an electron as only reagent requiring simple
handling and equipment. A technical setup for
electrochemical regeneration requires in general
two electrodes, an electrolyte and a power supply.
In addition a membrane can be added to the setup
in order to separate anode and cathode depart-
ment. Some examples of electrochemical regen-
eration are electrochemical regeneration of
activated carbon-based adsorbents in wastewater
treatment and regeneration of enzymatic cofac-
tors in electroenzymatic processes.
Organic pollutants in wastewaters can be
removed by adsorption using, e.g., activated car-
bon as an adsorbent. This process is normally
operated using a batch of adsorbent with suffi-
cient capacity to operate for many months before
reaching saturation. Once loaded, adsorbent must
be disposed or regenerated. One option for adsor-
bent regeneration is electrochemical regeneration
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_199-2
(Brown et al. 2004). The loaded adsorbent is
located in a form of a packed or fluidized bed in
the anode (anodic regeneration) or cathode
(cathodic regeneration) compartment of the reac-
tor. The efficiency of the regeneration depends on
the processing time, voltage gradient, an electro-
lyte, and a compartment. According to literature
the efficiency of cathodic regeneration is higher
than of anodic regeneration. The mechanism of
electrochemical regeneration is ascribed at the
first place to local pH changes close to anode or
cathode. At the anode side due to oxygen evolu-
tion reaction a pH decrease can be expected,
while at the cathode side due to hydrogen evolu-
tion pH value will increase. This pH changes
induce organic pollutants desorption. In the next
step, dissolved pollutants can be oxidized at the
anode. In the case of the cathodic regeneration
they have first to mitigate from the cathode to the
anode. This might be mass transfer controlled
leaving some residues in the cathode, unless
very large currents or long regeneration times
are employed.
Further example of electrochemical regenera-
tion is regeneration of enzymatic cofactors in
electroenzymatic processes (Wichmann and
Vasic-Racki 2005). Redox enzymes are very
selective and specific catalysts, which can enable
a number of partial oxidation or reduction reac-
tions for industrial applications at mild condi-
tions. Broader industrial application of redox
enzymes has been so far hindered by their depen-
dence on expensive cofactors (e.g., nicotinamide
2 Electrochemical Regeneration
adenine dinucleotide (NAD)), which are con-
sumed in the reaction (e.g., Eq. 1) and have to
be regenerated for a process to be economical:
þ
CO2 þ NADH þ H ⇄ HCOOH
þ NADþ (1)
Electrochemical regeneration offers a possibility
of cofactor regeneration. In this respect espe-
cially regeneration of NAD has been studied
since NAD-dependent oxidoreductases are of
great industrial interest. The electrochemical
regeneration can be represented by this reaction:
þ þ 
NAD þ H þ 2e ⇄ NADH (2)
This reaction is however not selective enough and
the kinetics is very sluggish on most known elec-
trode materials. Some improvements have been
achieved by using surface-modified electrodes.
Another strategy is to add an additional mediator
according to
NADþ þ Medred ⇄ NADH þ Medox þ (3)
Medox þ þ Hþ þ 2e ⇄ Medred (4)
Electrochemical cofactor regeneration is still not
a mature technology, and further improvements
in electrode materials are needed to make this
option feasible.
References
Brown NW, Roberts EPL, Garforth AA, Dryfe RAW
(2004) Electrochemical regeneration of a carbon-
based adsorbent loaded with crystal violet dye.
Electrochim Acta 49:3269–3281
Wichmann R, Vasic-Racki D (2005) Cofactor regenera-
tion at the lab scale. Adv Biochem Eng Biotechnol
92:225–260
E
Electrochemistry
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Electrochemistry is a branch of chemistry which
studies charge transfer processes across an elec-
trified interface also called an electrochemical
double layer (Bockris and Reddy 1988, Hamann
et al. 2007). Applications of electrochemistry are
broad including electrochemical processing,
electroanalysis electrochemical sensors, electro-
chemical regeneration, and corrosion. In addi-
tion, many important processes in biological
systems like photosynthesis and cell respiration
are inherently electrochemical processes.
The main feature of an electrochemical system
is a separation of ionic- and electronic flows. Ions
are flowing through the electrolyte which is
exclusively an ionic conductor, while electrons
flow through an outer electrical circuit which is
exclusively an electron conductor. These two
flows are interconverted at the electrode/electro-
lyte interface across the electrochemical double
layer by means of an electrochemical reaction
The potential difference in the electrochemical
double layer is related to thermodynamics
(Nernst equation) and kinetics (Butler-Volmer
or Tafel equations) of an electrochemical reac-
tion and it is a driving force for the electrochem-
ical reaction to take place. This unique feature of
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_200-2
electrochemistry makes easy to control the reac-
tion rate by electrons at different energies.
Electrochemical processes can be spontaneous
(Gibbs free energy, DG <0), called galvanic, and
nonspontaneous DG>0, called
electrolytic. Instead in terms of Gibbs free
energy, spontaneity of an electrochemical pro-
cess can be expressed in terms of cell voltage,
where a positive value stands for a galvanic sys-
tem and a negative for an electrolytic. The rela-
tionship between the cell voltage and Gibbs
energy is given by equation DG = nFUr,
where n stands for number of exchanged elec-
trons, F for a Faraday constant, and Ur for an
equilibrium cell voltage.
Many electrochemical systems require pres-
ence of separators. This is usually a membrane
which can be a permeable, termed diaphragm, or
semipermeable, termed membrane. The latter
type usually in addition to separation serves as
an electrolyte, so-called solid electrolyte in elec-
trochemical systems. An example is ceramic
yttria-stabilized zirconia (YSZ) membrane
which has found an application in solid oxide
fuel cells. The ionic conductivity of this material
is provided by O2 ions.
References
Bockris JO’M, Reddy AKN (1988) Modern electrochem-
istry. Plenum Press, New York
2 Electrochemistry

Hamann CH, Hamnett A, Vielstich W (2007) Electro-

chemistry, 2nd edn. Wiley-VCH Verlag GmBH,
Weinheim
E
Electrodeionization
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technická 5,
Prague 6, Czech Republic
Electrodeionization represents a variant of elec-
trodialysis, modified in order to allow treatment
of low-salinity and low-conductivity media. This
technique is typically applied to produce high-
purity water suitable for use, for example, in
energetics. It combines the advantages of ion
exchange with those of electrodialysis.
This technology is based on an electrodialysis
unit with a diluate and also, in selected cases, a
concentrate chamber filled with ion-exchanger
particles. They can be arranged as monopolar
beds (formed by particles of one polarity ion
exchanger), as layered beds (cation- and anion-
exchanger particles filled separately in several
alternating layers), or as a mixed bed (uniform
mixture of both types of ion-changer particles).
The ion-exchange phase takes on the role of
electroconductive media, thus reducing ohmic
drop in the dilute chamber. At the same time it
provides a three-dimensional interface for the
removal of traces of ions present in the solution.
Two regions are typically distinguished in the
electrodeionization operation: (i) ions removal
and (ii) solvent splitting. Within the first region
the electrodeionization unit works bellow mass
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_201-1
transfer limitation. It means, flux of ions to the
solution – ion exchanger interface driven by the
current load used has a value well below mass
transfer limitation in a dilute chamber. The func-
tion of the ion-exchange bed consists in providing
a pathway for ions trapped in the dilute channel to
the ion-selective membranes separating dilute/
concentrate chambers. In a second domain, how-
ever, the current load exceeds limiting current
density, i.e. limiting flux of ions present from
solution to the solution – ion exchanger interface.
In such a case sufficient number of ions to trans-
port corresponding electrical charge is provided
by decomposition (dissociation) of the solvent
(typically water). In contrast to electrodialysis,
this splitting does not take place only at the
solution-membrane interface but also at the con-
tact of the cation- and anion-selective phase
(Alvarado and Chen 2014).
In the case of a concentrate chamber, the role
of the ion-exchange phase again consists in
reducing ohmic drop in the channel while
maintaining the concentration of the ions in the
liquid phase at a minimum to reduce back diffu-
sion from the concentrate to the dilute chamber.
The quality of the stream produced is compa-
rable to that of the ion-exchange process. The
advantage of electrodeionization is that it is a
continuous process that does not require a regular
regeneration phase of operation. This feature of
electrodeionization has a further important
advantage. It saves a significant amount of
corresponding chemicals and reduces the salinity
2 Electrodeionization

of the waste streams produced. Such technology References

is thus a suitable component for closed loop tech-
nologies which, on ending, discharge removed Alvarado L, Chen A, (2014) Electrodeionization: Princi-
ples, Strategies and Applications, Electrochim. Acta
salts in the solid form and avoids production of
132:583
contaminated liquid streams.
E
Electrofiltration
Karel Bouzek
University of Chemistry and Technology Prague,
Technická 5, Prague 6, Czech Republic
Electrofiltration represents a modification of
dead-end membrane micro- or ultrafiltration. It
targets a significant reduction of the filtration
time and focuses especially on the filtration
and/or concentration of colloidal substances that
otherwise rapidly build up a deposit of colloidal
particles on the surface of the membrane, which
strongly hinders permeation of the fluid phase.
The basic principle is that colloidal particles
usually carry an electric charge. Hence, by apply-
ing an appropriate electric field, colloidal
particles can be moved in the direction opposite
to the fluid flow, thus keeping the surface of the
filtrating membrane free of the deposit [1].
A schematic sketch of this arrangement is
shown in the Fig. 1.
As the filtrating membrane remains
unimpeded by a deposit of colloidal particles,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_202-1
the pressure drop across it remains relatively
low. In contrast, the separator covered by the
layer of colloidal particles attracted by the elec-
tric field does not permit a significant fluid flow.
This results in a reduction of the shear stress
forces in the deposited film of separated colloid.
These facts make electrofiltration especially
promising for the separation of biotechnology-
derived products, the reason being that such
products are typically sensitive to high shear
stress forces while at the same time they are
electrically charged. The mild conditions
of electrofiltration thus enable their properties
to be preserved during the process of their
separation [2].
References
Henry jr. JD, Lawler LF, Kuo CHA (1977) A solid/liquid
separation process based on cross flow and
electrofiltration. AIChE Journal 23:851
Gözke G, Posten C (2010) Electrofiltration of Biopoly-
mers. Food Eng. Rev. 2:131
2 Electrofiltration

Electrofiltration,
Fig. 1 Schematic sketch of
electrofiltration principle,
Fw stands for driving force
due to the friction between
the particle and flowing
solvent molecules and Fe
stands for driving force
resulting from action of the
applied electric field E on
the particle carrying
electrical charge
E
Electrolyzers
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
One of the main processes occurring in an
electrolyzer device is the water electrolysis. Elec-
trolysis of water is the dissociation of water mol-
ecules into hydrogen and oxygen gases. For this
process, in the presence of liquid water at 298 K
and 1 bar, DG is 237 kJ mol 1 (corresponding to
~1.23 V), DS is 163 J mol 1 K 1
(TDS ~0.25 V), whereas DH is 286 kJ mol 1.
The thermoneutral potential at which this reac-
tion occurs in the absence of external heat supply
is Eth,DH = 1.48 V (upper heating value
3.54 kWh
Nm 3 H2) (Millet et al. 2011). If
steam is fed to the device, the reaction enthalpy
is reduced by ~40 kJ mol 1 corresponding to the
vaporization enthalpy. Water electrolysis is tra-
ditionally carried out in alkaline media with sev-
eral commercial electrolyzers available on the
market. Water electrolyzers using a solid poly-
mer electrolyte are less common and generally
use expensive materials such as noble metal
electrocatalysts and Nafion membranes (Barbir
2005; Siracusano et al. 2010). Polymer
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_203-2
electrolyte membrane (PEM) electrolyzers repre-
sent a viable alternative to alkaline electrolyzer
using KOH or NaOH as electrolytes for hydrogen
generation. The advantages of SPE water
electrolyzers especially concern with increased
safety, high energy density, and low mainte-
nance. In the PEM water electrolyzer, water is
usually supplied to the anodic compartment
where oxygen evolution occurs, whereas hydro-
gen is produced at the cathode by protons
transported through the protonic membrane
(Fig. 1). The electrodes are usually composed of
a platinum electrocatalyst for hydrogen evolu-
tion, whereas metal oxides (e.g., IrO2, RuO2,
etc.) are used for the anode due to their enhanced
activity and stability than Pt for this reaction
(Marshall et al. 2007; Siracusano et al. 2010).
The performance of an SPE electrolyzer is
strongly related to the characteristics of the mem-
brane and electrode assembly (MEA) where the
electrochemical reactions take place at triple-
phase boundary. Therefore, the interface between
solid polymer electrolyte and electrocatalyst
layers should be characterized by a suitable
extension; furthermore, the contact resistance
between the catalytic layer and the membrane
should be as low as possible. Generally, Nafion®
2 Electrolyzers

Anode Cathode proper thickness is necessary for the polymer

H2O « 2H+ + 2e- + 0.5O2 2H+ + 2e- « H2 electrolyte separator (around 100 mm). For high-
Erev° = 1.23 V vs. RHE Erev° = 0.00 V vs. RHE pressure operation in PEM electrolyzers,
Metal reinforced PFSA membranes provide a proper
Pt/C
Oxides combination of good conductivity and high
O2 H2 mechanical strength.
Solid Polymer
Electrolyte C
A A References
N H+
T
O H+
H Barbir F (2005) PEM electrolysis for production of
D H+
O hydrogen from renewable energy sources. Sol Energy
E D 78:661
E Marshall A, Børresen B, Hagen G, Tsypkin M, Tunold
R (2007) Hydrogen production by advanced proton
Electron Flow exchange mebrane (PEM) water electrolysers –
H2O H2O
Reduced energy consumption by improved
H2O « H2 + 0.5O2 E rev° = 1.23 V electrocatalysis. Energy 32:431
Millet P, Mbemba N, Grigoriev SA, Fateev VN,
Aukauloo A, Etiévant C (2011) Electrochemical per-
Electrolyzers, Fig. 1 Principle of operation of a PEM
formances of PEM water electrolysis cells and per-
water electrolysis cell
spectives. Int J Hydrog Energy 36:4134
Siracusano S, Baglio V, Di Blasi A, Briguglio N, Stassi A,
membrane is used as conducting polymer elec- Ornelas R, Trifoni E, Antonucci V, Arico AS
trolyte in PEM electrolyzer systems. However, (2010) Electrochemical characterization of single cell
and short stack PEM electrolyzers based on a
low levels of H2 and O2 crossover are necessary
nanosized IrO2 anode electrocatalyst. Int J Hydrog
for PEMWE application due to the high-pressure Energy 35:5558
operation that may reach 50–100 bars. Thus, a
E
Electromembrane
Gerarld Pourcelly
Gérald Pourcelly, Institut Européen des
Membranes, CC 047, Université Montpellier II,
Place E.Bataillon, Montpellier, France
Electromembrane or “charged membrane” stands
for ion-exchange membrane [IEM]. They are
used in a number of processes which are rather
different in their basic concept, their practical
applications, and their technical relevance
(Strathmann 2004). All IEM separation processes
are based on the same fundamental principle
which is the coupling of the transport of electrical
charges, i.e., an electrical current with a transport
of mass, i.e., cations or anions, through a
permselective membrane due to an externally
applied or internally generated potential gradient.
There are two types of IEM: (i) monopolar and
(ii) bipolar membranes.
Monopolar membranes are either cation-
exchange membranes which contain negatively
charged groups fixed to the polymer matrix or
anion-exchange membranes which contain posi-
tively charged groups fixed to the polymer
matrix. In a cation-exchange membrane, the
fixed negative charges are in electrical equilib-
rium with mobile cations (counterions) in the
interstices of the polymer as shown in Fig. 1
(Strathmann 2010). In this case, the mobile
anions are referred to as coions. They are more
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_204-1
or less excluded from the polymer matrix because
of their electrical charge which is identical to that
of the fixed ions (Donnan exclusion (Donnan
1911)). Thus, the selectivity of an IEM results
from the exclusion of coions from the membrane
phase. The properties of IEM are determined by
different parameters such as the density of the
polymer network, the hydrophobic/hydrophilic
character of the polymer matrix, the nature and
the ratio of fixed ion-exchange groups, the cross-
linking ratio, etc.
The most desired properties of IEM are
(i) high chemical and thermal stabilities,
(ii) high mechanical and dimension stabilities,
(iii) high permselectivity, (iv) low electrical
resistance, (v) and a low cost.
Bipolar membranes (BPMs) are composed of
two layers of ion exchangers joined by a hydro-
philic junction (Pourcelly et al. 2009). The diffu-
sion of water from both sides of the BPM allows
its dissociation under the electrical field to gen-
erate protons and hydroxyl ions, which further
migrate from the junction layer through the
cation- and anion-exchange layers of the BPM
as depicted in Fig. 2. The requirements for suit-
ability of BPM include that for monopolar mem-
branes but also an experimental potential to
achieve the water-splitting capability as close as
possible as the theoretical value equal to 0.83 V at
25  C.
Nowadays, superior styrene-divinylbenzene
copolymer membranes can be easily purchased,
perfluorinated membranes with great chemical
2 Electromembrane

Electromembrane, a
Fig. 1 (a) Cation-
exchange membrane with a Counter-ion pathway
homogeneous structure; (b)
ion-exchange membrane
with a heterogeneous
structure prepared from an
ion-exchange resin powder
in a binder polymer (From Counter-ion Co-ion Fixed ion
Strathmann 2010)
Polymer matrix
b
Counter-ion pathway

Solution filled gaps

Ion-exchange resin Binder polymer

Electromembrane, Fig. 2 Principle of a bipolar membrane. Left hand: water dissociation under electrical field. Right
hand: the two ion-exchange layers bearing fixed anion- or cation- exchange groups

stability are on the market, and BPM with an
industrial-scale lifetime (>20,000 h) is available.
References
Donnan FG (1911) Theory of membrane equilibrium and
membrane potential in the presence of non-dialysing
electrolyte. Z Electrokem Angew Phys Chem
17:572–581
Pourcelly G, Bazinet L (2009) Developments of BPM
technology in food and bio-industries. In: Pabby AK,
Rizvi SSH, Sastre AM (eds) Handbook of membrane
separations, CRC Press, Boca Raton, pp 581–634
Strathmann H (ed) (2004) In: Ion exchange membrane
separation processes. Membrane technologies series,
Elsevier, Amsterdam
Strathmann H (2010) Electrodialysis: a mature technology
with a multitude of new applications. Desalination
264:268–288
E
Electrophoresis
Catherine Charcosset
Université Lyon 1, Lyon, Villeurbanne, France
The term electrophoresis refers to the motion of
suspended particles in an applied electric field.
Among separation techniques, electrophoresis is
widely used in research and development and
quality control in disciplines such as biochemis-
try, immunology, genetics, and molecular biol-
ogy (Westermeier 2001). Electrophoresis is
based on the differential migration of charged
species in a semiconductive medium under the
influence of an electric field. Separation of many
different kinds of species including proteins,
DNA, nucleotides, drugs, and many other bio-
chemicals is obtained upon differences in size,
charge, and hydrophobicity. The technique was
first reported in 1937 by Arne Tiselius who won
the Nobel Prize in Chemistry in 1948 for the
separation of different serum proteins by a
method called “moving-boundary electrophore-
sis.” Since then, a number of improved tech-
niques have been introduced such as gel
electrophoresis, capillary electrophoresis, and
two-dimensional electrophoresis.
Gel electrophoresis uses an electric current
passed through an agarose or polyacrylamide
gel (SDS-PAGE) to separate the molecules in a
sample on the basis of their differences in molec-
ular size and charge. As the sample migrates in
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_206-1
the gel in response to the electric current, the
smaller species move more quickly than the
larger species, which results in a distinct banded
pattern in the gel. This banded pattern may be
visualized via the application of staining agents,
such as ethidium bromide, which reveals the gel
bands under UV light, or silver stain, which is
typically used to detect proteins. The silver stain
is compatible with mass spectrometry techniques
for further analysis of the protein composition.
Capillary electrophoresis (CE) involves a combi-
nation of both polyacrylamide gel electrophoresis
(SDS-PAGE) and high-performance liquid chro-
matography (HPLC) (Ahuja and Jimidar 2008).
High voltages of 500 V/cm or greater are gener-
ated within narrow capillaries (20–200 mm). The
high voltages cause electroosmotic and electro-
phoretic movement of buffer solutions and ions,
respectively, within the capillary.
Two-dimensional gel electrophoresis (2-D elec-
trophoresis) separates species in two steps,
according to two independent properties. In a
common technique, the first dimension is isoelec-
tric focusing, which separates proteins according
to their isoelectric points; the second dimension
is SDS polyacrylamide gel electrophoresis
(SDS-PAGE), which separates proteins
according to their molecular size. The method
involves placing the sample in gel with a pH
gradient and applying a potential difference
across it.
Cellulose acetate membranes are other current
supporting media for electrophoresis separation
2 Electrophoresis

(Westermeier 2001). They are used for routine background. Nafion membrane electrophoresis
clinical analysis and related applications, as well is a potentially attractive technique for the sepa-
as for the analysis of molecules in physiological ration of small organic molecules like amino
fluids. These membranes have large pores and acids or ions.
therefore have a low sieving effect on molecules.
The electrophoretic separation is thus entirely
based on charge density. The matrix exerts little
Cross-References
effect on diffusion so that the separated zones are
relatively wide and the resolution and limit of
▶ Cellulose Acetate (CA) Membrane
detection area is low. For these reasons, cellulose
▶ Ion Exchange Membrane
acetate membranes are often replaced by gel
▶ Perfluorosulfonic Acid Polymer Membrane
electrophoresis.
Other supporting membranes for electropho-
resis include Nafion membranes, a type of
perfluorosulfonic acid membrane, and cation- References
exchange membranes, which are chemically
Ahuja S, Jimidar M (2008) Capillary electrophoresis
resistant and consist of a pore-structure cluster
methods for pharmaceutical analysis. Academic,
network (Fang et al. 2004). These membranes are Amsterdam
widely used in the field of chloralkali industry Fang C, Wu B, Zhou X (2004) Nafion membrane electro-
and in fuel cells. A Nafion membrane contains phoresis with direct and simplified end-column pulse
electrochemical detection of amino acids. Electropho-
hydrophilic pores (10–20 Å and 50–60 Å in size)
resis 25:375–380
acting as very narrow electrophoresis channels. Westermeier R (2001) Electrophoresis in practice,
The fixed-charge sites ( SO3 ) on the hydro- 3rd edn. Wiley-VCH, Weinheim
philic pore surface provide a strong charged
E
Electrophoretic Deposition
Catherine Charcosset
Université Lyon 1, Villeurbanne, France
Electrophoretic deposition (EPD), also called
electrocoating, e-coating, cathodic electrodeposi-
tion, or electrophoretic coating, is a simple and
effective technique for coating of charged parti-
cles on substrates (Besra and Liu 2007). It has
several advantages including continuous
processing, uniform deposition and control of
the thickness, and morphology of a deposited
film by adjustment of the deposition time and
applied potential. In EPD, charged powder parti-
cles, dispersed or suspended in a liquid medium,
are attracted and deposited onto a conductive
substrate of opposite charge on application of a
DC electric field. There are two types of electro-
phoretic deposition (Fig. 1). When the particles
are positively charged, the deposition happens on
the negative electrode (cathode) and the process
is termed cathodic electrophoretic deposition.
The deposition of negatively charged particles
on positive electrode (anode) is called anodic
electrophoretic deposition. By suitable modifica-
tion of the surface charge on the particles, any of
the two modes of deposition is possible. This
technique is convenient for stable suspensions
containing charged particles free to move when
an electric field is applied. Therefore, EPD can be
applied to any material that is available as a fine
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_207-2
powder (e.g., <30 mm particle size) or as a col-
loidal suspension, including metals, polymers,
ceramics, and glasses.
The fundamental mechanisms of EPD are
described in the literature mainly in the framework
of the Derjaguin–Landau–Verwey–Overbeek
(DLVO) theory and in relation to the distortion
of the particle double layer under the application
of a DC electric field (Corni et al. 2008). However,
numerous other theories (flocculation by particle
accumulation, particle charge neutralization, elec-
trochemical particle coagulation, electrical double
layer distortion, and thinning mechanism) have
been proposed to explain the particle interactions
and the kinetics of deposition.
Several examples of membrane preparation
using an EPD technique are reported. For exam-
ple, EPD is used as a seeding method for making
zeolite membranes (Abdollahi et al. 2007). Zeo-
lites are crystalline structures which possess uni-
form and molecular-sized pores. Zeolite
membranes have a great potential in separation
and catalysis processes owing to their unique
pore structures and adsorption properties and
their high thermal, mechanical, and chemical sta-
bility compared with polymeric membranes.
Since zeolites are negatively charged particles,
they can be effectively attracted to the substrates
of positive charge. By the aid of EPD, an oriented
continuous layer of nano-sized zeolite seeds is
formed on the support and acts as nuclei for the
next step which is crystal growth under hydro-
thermal situation.
2 Electrophoretic Deposition
Electrophoretic a b
Deposition,
Fig. 1 Schematic of
electrophoretic deposition
process. (a) Cathodic EPD
and (b) anodic EPD
− + −
The EPD technique is also used for the prep-
aration of membrane electrode assembly for fuel
cell (Morikawa et al. 2004). A membrane elec-
trode assembly can be prepared by EPD process
onto a Nafion membrane. A suspension
consisting of ethanol, carbon powders with Pt
catalyst, and Nafion polymer is used to obtain a
stable dispersed solution. The thickness of the
prepared catalyst layer is controlled by EPD dura-
tion or concentration of suspension. The cell
obtained may present a higher electrochemical
performance compared with ordinary cells.
Cross-References
▶ Electrophoretic Painting
▶ Fuel Cell Membrane
+ − −
+
+ −
−
+ +
− −
+
−
+ + −
+
▶ Zeolite Membrane
References
Abdollahi M, Ashrafizadeh SN, Malekpour A (2007)
Preparation of zeolite ZSM-5 membrane by electro-
phoretic deposition method. Microporous Mesoporous
Mater 106:192–200
Besra L, Liu M (2007) A review on fundamentals and
applications of electrophoretic deposition (EPD).
Prog Mater Sci 52:1–61
Corni I, Ryan MP, Boccaccini AR (2008) Electrophoretic
deposition: from traditional ceramics to nanotechnol-
ogy. J Eur Ceram Soc 28:1353–1367
Morikawa H, Tsuihiji N, Mitsui T, Kanamura K (2004)
Preparation of membrane electrode assembly for fuel
cell by using electrophoretic deposition process.
J Electrochem Soc 151:A1733–A1737
E

Electrophoretic Mobility The electrophoretic mobility of charged sol-

utes, including proteins, is predicted using the
Catherine Charcosset Debye-H€uckel-Henry theory (O’Connor
Université Lyon 1, Villeurbanne, France et al. 1996). This theory is valid only for spherical
nonconducting particles at low zeta potentials,
with ions present in the electrical double layer
When an electric field is applied across a given behaving as point charges. The Debye-H€uckel-
medium, charged solutes or particles suspended Henry theory gives the mobility as
in the electrolyte are attracted toward the elec-
trode of opposite charge. Viscous forces acting ze f ðkr Þ
m¼
on the component tend to oppose this movement. 6pr ð1 þ kr Þ
When equilibrium is reached between these two
opposing forces, the solutes or particles move where z is the net charge (dimensionless), e the
with constant velocity. The velocity is dependent elementary charge (C), r the particle radius (m), 
on factors such as the strength of electric field or the viscosity (kg m1 s1), and f(kr) is the Henry
voltage gradient, the dielectric constant of the correction factor, which has values between 1 and
medium, the viscosity of the medium, and the 1.5. The Debye-H€uckel parameter, k, is defined
zeta potential of the particles. by
The electrophoretic mobility, m (m2/Vs), is the
observed electrophoretic velocity, v (m/s), 2e2 N A I
k2 ¼
divided by electric field strength, E (V/m): ekT

m¼
v where NA is the Avogadro’s constant (kmol1),
E I is the ionic strength (kmol m3), e is the permit-
tivity (J1 C2 m1), k is the Boltzmann’s constant
The electrophoretic velocity is the distance of (J K1), and is T the temperature. O’Brien and
migration divided by time, also called velocity White (1978) obtained a more rigorous solution
of migration. Mobilities are sometimes expressed to the equations describing the electrophoretic
with a negative sign, because migration of the mobility of a rigid spherical particle with a uni-
solutes or particles generally occurs in the direc- form charge density. The predictions of this
tion opposite to the electrophoretic field (which is model coincide with those of the Debye-H€uckel-
taken as reference). Henry theory for systems with zeta potentials less
than 25 mV.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_208-2
2 Electrophoretic Mobility

The electrophoretic mobility of proteins has Cross-References

been determined through several microfiltration
membranes under conditions of zero concentra- ▶ Electrical Potential
tion driving force and with negligible adsorption ▶ Electrophoresis
on to the membranes occurring during the exper-
iment (O’Connor et al. 1996). The initial mobility
of both proteins is close to free-solution values at
References
the same pH, after correction for the ionic
strength of the buffer. This effect is explained O’Brien RW, White LR (1978) Electrophoretic mobility
by the effect of reduced free area in the mem- of a spherical colloidal particle. J Chem Soc Faraday
brane which is compensated by a corresponding Trans 1:1607–1626
increase in the potential gradient. Data were also O’Connor AJ, Pratt HRC, Stevens GW (1996) Electropho-
retic mobilities of proteins and protein mixtures in
obtained for mixtures of two proteins. Interac- porous membranes. Chem Eng Sci 51:3459–3477
tions occur when the two proteins are oppositely
charged, changing the apparent mobilities from
the free solution values.
E
Electrophoretic Painting
Catherine Charcosset
Université Lyon 1, Villeurbanne, France
Electrophoretic painting, also called electropho-
retic deposition of paint, electrodeposition paint-
ing, or E-coating, is an economical and corrosion-
resistant technique for applying coatings to elec-
trically conducting materials. It is widely used to
coat many industrial products such as automobile
bodies and parts, tractors and heavy equipment,
metal furniture, and beverage containers. The
process is carried out with the use of anodes and
cathodes in the painting tank. There are two types
of electrophoretic painting: anaphoretic and cat-
aphoretic painting. In anaphoretic painting the
profiles will be the anode, and in cataphoretic
painting the profiles will be the cathode. In the
electrophoretic painting process, evolution of
oxygen gas will take place at the anode, and
hydrogen gas will be evolved at the cathode.
The electrophoretic paint is continuously cir-
culated to avoid settling of the paint solids and
heat resulting from the pumping process as well
as from the passage of electric current. Dry coat-
ing thicknesses of the order of 20 mm are nor-
mally applied, using a voltage of 150–200 V for a
time of 1–2 min. After painting, the profiles are
rinsed before stowing at temperatures of
180–200  C for 20–30 min. The electrophoretic
paint may contain a water-soluble acrylic-based
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_209-2
paint, the resin being rendered soluble by the
addition of suitable amines such as melamine.
When current is passed through the paint, the
resin and pigments will migrate to the anode
while the amine will be discharged at the cathode.
During paint deposition the level of amine will
increase, and this causes a decrease in paint depo-
sition rate if allowed to continue. The most usual
processes used for removal of excess amine are
ultrafiltration often in combination with reverse
osmosis.
After electrophoretic painting, ultrafiltration
continuously treats the paint bath to produce per-
meate needed for rinsing metal parts (Agana
et al. 2011). While permeate is used for rinsing,
the mixture of paint and rinse water is returned to
the paint bath from the downstream rinse system.
The volume in the paint bath remains constant,
and the process leads to a closed loop cycle
including a multistage rinse system. No wastewa-
ter is produced and almost no deionized water is
required for the purpose of rinsing. Different
types of membranes are available for various
types of paint. The type and size of the membrane
modules are related to the needs of bath volume
and characteristic parameters of the paint bath,
such as total solids, pH, and temperature.
Cross-References
▶ Electrophoretic Deposition
▶ Permeate
2 Electrophoretic Painting

References membrane as applied to the ultrafiltration of post-

electrodeposition rinse wastewater. Desalination
Agana BA, Reeve D, Orbell JD (2011) Optimization of the 278:325–332
operational parameters for a 50 nm ZrO2 ceramic
E
Embryonic Stem (ES) Cell
Loredana De Bartolo
National Research Council of Italy, Institute on
Membrane Technology, ITM-CNR, Rende (CS),
Italy
Embryonic stem (ES) cell is a totipotent stem cell
derived from an early stage embryo, which is
called blastocyst. This stage is reached 4–5 days
after fertilization and contains from 64 to several
hundred cells organized in an outer shell, the
trophectoderm, and the inner cell mass (ICM).
The ICM is the locus of pluripotent cells destined
to yield all the tissues of the developed organism.
In the process of obtaining embryonic stem cells,
the trophectoderm is removed by
immunosurgery, and the ICM is disaggregated
and plated on feeder cells. Ethical issues surround
the derivation of human ES cells from in vitro
fertilized blastocysts.
Embryonic stem cells have pluripotency and
indefinite replication characteristics. These cells
have the capacity to give rise to differentiated
progeny representative of all three embryonic
germ layers (ectoderm, endoderm, and meso-
derm). ES cells are able to differentiate in all
cell types differently from adult stem cells that
can produce only a limited number of cell types.
It is possible to modulate the differentiation of
stem cells in a given phenotype by using specific
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_210-4
growth factors and molecules, which trigger the
differentiation process.
ES cells for their ability of propagating them-
selves indefinitely represent a valuable tool for
both research and regenerative medicine. They
can serve as an unlimited source of any cell type
in the body; human ES cells could yield highly
effective in vitro models for use in drug discovery
programs and provide a renewable source of cells
for use in transplantation therapy. Cell therapies
based on the use of ES cells have been proposed
for tissue replacement after injury or disease.
Adult stem cells, isolatable from bone mar-
row, adipose tissue, tooth pulp, and many other
locations of the body, are capable of self-renewal
and can be readily expanded ex vivo for several
passages without losing their self-renewal capac-
ity. Mesenchymal stem cells can differentiate
into multiple tissue-forming cell lineages such
as osteoblasts, chondrocytes, adipocytes,
tenocytes, and myocytes. Recent work on the
differentiation of bone marrow-derived mesen-
chymal stem cells into neuron-like cells is
another demonstration of considerable plasticity
of adult mesenchymal stem cells. Stem cells are
often a preferred cell source for regeneration of
multiple cell lineage tissues. The ability to
expand stem cells is desired to generate cells for
tissue engineering in clinical and pharmaceutical
applications (Rahaman and Mao 2005). Conven-
tional methods for expanding stem cells or pro-
genitor cells comprised polystyrene culture
dishes and component of extracellular matrix
2 Embryonic Stem (ES) Cell
such as collagen. Alternatively biocompatible
and biodegradable materials have been proposed
to support cells and promote their differentiation
and proliferation toward the formation of a tissue
(Piscioneri et al. 2011).
Advances in cell-based therapies would not
have been possible without the innovative design
and fabrication of several generations of bioma-
terials. Novel biomaterials with distinct proper-
ties are necessary to accommodate the growth
and interactions of multiple cell lineages in com-
posite tissue constructs (Griffith 2000). Mem-
brane systems provide the temporary structural
framework for tissue-forming cells to synthesize
extracellular matrices and other functional com-
ponents in the intended shape and dimensions
(De Bartolo and Bader 2013). They can respond
on the key demands for utilizing cell-based ther-
apies to engineer composite tissue constructs
with a purposeful orientation toward anatomic
structures that the tissue-engineered constructs
are intended to regenerate. Development of new
intelligent biomaterials in synergy with cell biol-
ogy will advance stem cell-based clinical thera-
peutics. Engineered membranes have the
potential to mimic and control the physical,
chemical, and biological factors necessary for
guiding stem cell differentiation (Pavlica
et al. 2009). They are currently being investigated
to act as scaffolds to guide and improve 3D tissue
formation, substrates to enhance cell culturing
techniques, vehicles for cell delivery, and sources
of immobilized and/or time-released factors.
They can be applied to the regeneration of numer-
ous tissue types, including the liver, pancreas,
bone, cartilage, skin, and nerves, and are being
used for the in vitro realization of physiological
models.
References
De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy: state of art and vision for the future. CRC
Press, Boca Raton
Griffith LG (2000) Polymeric biomaterials. Acta Mater
48:263–277
Pavlica S, Piscioneri A, Peinemann F, Keller M,
Milosevic J, Staeudte A, Heilmann A, Schulz-
Siegmund M, Laera S, Favia P, De Bartolo L, Bader
A (2009) Rat embryonic liver cell expansion and dif-
ferentiation on NH3 plasma-grafted PEEK-WC-PU
membranes. Biomaterials 30:6514–6521
Piscioneri A, Campana C, Salerno S, Morelli S, Bader A,
Giordano F, Drioli E, De Bartolo L (2011) Biodegrad-
able and synthetic membranes for the expansion and
functional differentiation of rat embryonic liver cells.
Acta Biomater 7:171–179
Rahaman MN, Mao JJ (2005) Stem cell-based composite
tissue constructs for regenerative medicine.
Biotechnol Bioeng 91(3):261–284
E
Emulsion Liquid Membrane (ELM)
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Emulsion liquid membrane, ELM, is a system in
the form of double emulsions (for details, see
Chakraborty et al. 2010). It may be of two
types: water-in-oil emulsion dispersed in an
external aqueous phase and oil-in-water emulsion
dispersed in an outer organic phase. The mem-
brane phase in the water-in-oil-in-water (W/O/
W) type is the immiscible oil phase separating
the aqueous phases, while in the O/W/O type, the
immiscible water phase separating the two
organic phases acts as the LM. Hence, the liquid
membrane serves here a dual purpose:
(a) permitting selective transfer of one or more
components through it from external phase to
internal droplets and vice versa a‘nd
(b) preventing mixing of external and internal
phases. The emulsion is dispersed in the feed
solution, and mass transfer from the feed to the
internal receiving phase takes place. ELMs were
first used for separation of hydrocarbons from
wastewater with high separation efficiency. Com-
pared to conventional processes, emulsion liquid
membrane (ELM) process has some attractive
features, for example, simple operation, high effi-
ciency, extraction and stripping in one stage,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_211-2
larger interfacial area, and scope of continuous
operation.
Since an ELM is a thin film of liquid (oil or
aqueous) composed of surfactants and their sol-
vents between a feed and a receiving phase, any
immiscible liquid can serve as a membrane
between two liquid or gas phases containing a
solute at different concentrations. If the solute is
soluble in the membrane phase and has a reason-
able diffusivity through the membrane, then its
selective transport through the membrane from
higher to lower concentration can be achieved.
This type of permeation has simple mechanism
and not of much technical importance.
At facilitated transport mechanism, liquid
membrane incorporates a reactive component or
carrier, reacting reversibly and selectively with
species of interest to carry the formed complexes
across the LM to the internal phase, and dissoci-
ates, discharging the solute to the internal phase.
The unchanged carrier then diffuses back to the
membrane-external phase interface (see Fig. 1).
A small amount of carrier is required in the mem-
brane phase even for achieving a high degree of
separation. At different proton concentrations in
the aqueous phase or using another ions, ion
exchange processes between two LM surfaces
occur. This phenomenon is called coupled mass
transport. If the transports of these two different
species occur in the same direction, it is called
cotransport, while transport in opposite direction
is called countertransport. Evidently the process
leads to the transport of targeted ionic species
2 Emulsion Liquid Membrane (ELM)

plants installed for zinc recovery from wastewa-

Organic ter in Austria, having a capacity of 75 m3/h and
700 m3/h, removing zinc selectively from 500 to
3 ppm. Bis(2-ethylhexyl) dithiophosphoric acid
M2+ has been used as carrier. One more plant with the
MR2 M2+ 200 m3/h capacity in Germany and the 200 m3/h
Strip
H+ capacity plant in the Netherlands.
Weak acids like phenol and cresol and weak
RH bases like ammonium and amines have been suc-
H + cessfully removed from wastewater. Among
Feed them, the separation-concentration of phenol
has been intensively investigated. Phenol
removal from wastewater was commercialized
Feed Phase Membrane Strip Phase
I Phase II III in China. Phenol is removed from about
H+
1,000 ppm to 0.5 ppm with an extraction effi-
Cm ciency of greater than 99.95 %.
Cmc ELM technology has been applied to a great
Ci
extent for separation of mixtures of saturated and
aromatic hydrocarbons, of amino acids, and of
strong acids like nitric acid and thiocyanate. Cya-
C’mc
H+ nide removal from wastewater in gold processing
Ci’ is commercialized in China. Cyanide is reduced
from about 130 ppm to 0.5 ppm with an extrac-
tion efficiency of 99.6 %.
Emulsion Liquid Membrane (ELM), Fig. 1 Schematic ELM has promise in the fields of biotechnol-
representation of the liquid membrane globule and con-
centration profile of solute through ELM
ogy and biomedicine and has found application in
the separation of organic acids, fatty acids, puri-
fication of antibiotics, enzyme-catalyzed reac-
across the membrane against their concentration
tions, and detoxification of blood.
gradient. This so-called “uphill” transport will
continue until one driving factor (difference of
chemical potentials) is balanced by the difference
between chemical potentials of another References
transported ion.
The ELM technique has great potential for Chakraborty M, Bhattacharya C, Datta S (2010) Emulsion
hybrid liquid membranes: definitions and classifica-
recovery and removal of different metal ions.
tion, theories, module design, applications, new direc-
Separation of metals like copper, zinc, cadmium, tions and perspectives. In: Kislik V (ed) Liquid
cobalt, nickel, mercury, uranium, chromium, rhe- membranes principles and applications in chemical
nium, and several others, including noble metals separations & wastewater treatment, 1st edn. Elsevier,
Boston, pp 141–200
like gold and silver, lanthanides, and rare earths,
was studied. To date, there are two industrial
E
Encapsulation
Goran Vladisavljevic and Richard Holdich
Chemical Engineering Department,
Loughborough University, Loughborough,
Leicestershire, UK
Synonyms
Encapsulation: entrapping, enclosing,
enveloping; Amphiphilic substances:
Amphiphiles
Definitions
Encapsulation: Coating or entrapping of active
ingredient inside a solid shell or within a liquid
or solid matrix of another material.
Complex coacervation: Coacervation caused
by the interaction of two oppositely charged
macromolecules.
Internal phase separation: Phase separation
within emulsion droplets consisted of a mixture
of polymer, good solvent and poor solvent, usu-
ally triggered by removal of good solvent.
Micelles: Spherical aggregates of surfactant
molecules dispersed in an aqueous solution.
Liposomes: Spherical vesicles whose shells
consist of single or multiple concentric bilayers
resulting from the self-assembly of phospholipids
in an aqueous solution.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_212-7
Colloidosomes: Shperical vesicles whose
shells consist of coagulated or fused colloid
particles.
Polymersomes: Shperical vesicles whose
shells consist of amphiphilic block copolymers.
Amphiphilic molecules: Surface active mole-
cules made up of two parts, a polar or electrically
charged hydrophilic part and a hydrophobic part,
most often an alkyl chain.
Polycondensation: A polymerization in which
the growth of polymer chains proceeds by con-
densation reactions between molecules of all
degrees of polymerization.
Layer-by-layer polyelectrolyte deposition: A
thin film fabrication technique based on deposit-
ing alternating layers of oppositely charged poly-
electrolytes with wash steps in between.
Encapsulation is a process of enclosing or
entrapping a core material (liquid, gas, solid par-
ticles, cells, dissolved active ingredients, etc.)
inside a solid shell or within a solid or liquid
matrix for the purpose of controlled or triggered
release, immobilization, isolation, or protection
of the encapsulated material. The material being
encapsulated is called the core material, and the
carrier material used for envelopment or entrap-
ment is called the shell material. Typical exam-
ples of core materials are ink or dye for
carbonless copy papers, liquid crystals for
microparticle-based displays, phase-change
material for smart textiles, high-molecular-
weight gases for ultrasound contrast imaging,
genetic material for in vitro
2 Encapsulation
a Core/shell b Matrix type
c Multiple cores d Multiple shells
Encapsulation, Fig. 1 Schematic diagrams of capsules
with different morphologies
compartmentalization, active food ingredients
for functional food products, enzymes for biocat-
alytic reactors, drugs, pesticides, fragrances, anti-
microbial agents, etc.
Encapsulation efficiency (EE) is defined as the
percentage of core material incorporated into the
microcapsules relative to the total amount of the
core material added during encapsulation pro-
cess: EE = (mE/mT) 100 %, where mE is the
mass of the core material incorporated and mT
is the total mass of the core material added. Load-
ing capacity refers to the percentage of core
material incorporated within the microcapsules
relative to the total mass of the microcapsules
(i.e., core + shell material).
Two main types of capsules can be distin-
guished, core/shell (reservoir) type and matrix
type. In the core/shell capsule (Fig. 1a), the
shell material completely surrounds and contains
an internal core material (the internal phase). The
strategies used for formation of shell are spray
coating, complex coacervation, polymer precipi-
tation by internal phase separation, interfacial
reaction that may include polycondensation or
cross-linking, and layer-by-layer polyelectrolyte
deposition (Yow and Routh 2006). The core
material can be released from core/shell capsules
by simple molecular diffusion through the shell
or by deliberately compromising the integrity of
the shell, e.g., by exposing the microcapsule to
environmental stresses such as mechanical
forces, change of pH, temperature, or ionic
strength, or by chemical or biochemical degrada-
tion of the shell. A special class of core/shell
capsules are micelles and vesicles (liposomes,
polymersomes, and colloidosomes), formed by
self-assembly of amphiphilic molecules
(phospholipids and diblock copolymers) or parti-
cles (Dinsmore et al. 2002). Micelles are formed
spontaneously when amphiphiles are dispersed in
a polar solvent at concentrations that exceed a
critical level, known as the “critical micelle con-
centration” (CMC). Micelles containing solubi-
lized materials are referred to as microemulsions.
A difference between micelles and vesicles is that
vesicles are not a thermodynamically stable state
of amphiphiles and do not form spontaneously,
e.g., without input of external energy (Tadros
1993).
In the matrix-type capsule (Fig. 1b) the core
material is distributed uniformly throughout a
matrix of shell material. The most common
release pattern from matrix-type capsules is first
order in which the release rate decreases expo-
nentially with time until the active ingredient is
exhausted. Typical matrix-type capsules are mul-
tiple emulsions, hydrogel particles, solid lipid
particles, polymeric particles, etc. Hybrid struc-
tures consisting of a number of hierarchically
assembled homogenous phases may be
engineered that allow for even finer control over
the functionality of microcapsules (Fig. 1c, d).
References
Dinsmore AD, Hsu MF, Nikolaides MG, Marquez M,
Bausch AR, Weitz DA (2002) Colloidosomes: selec-
tively permeable capsules composed of colloidal par-
ticles. Science 298:1006–1009
Tadros TF (1993) Industrial applications of dispersions.
Adv Colloid Interface Sci 46:1–47
Yow HN, Routh AF (2006) Formation of liquid
core–polymer shell microcapsules. Soft Matter
2:940–949
E
Enhanced Oil Recovery (EOR)
Arnaud Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
Enhanced oil recovery (EOR) aims at increasing
the oil field’s recovery yield, thanks to high-
pressure injection of water or carbon dioxide.
Injection of pressurized carbon dioxide leads to
the maintenance of high pressures in the reservoir
and to an improvement of oil displacement,
thanks to several physical effects: decrease of
oil viscosity due to carbon dioxide solubilization,
stripping effects, and modification of multiphase
equilibria due to CO2 solubilization in the reser-
voir aqueous phase. When the oil reaches the
surface, carbon dioxide is purged with the asso-
ciated gas. Since the volumes of concerned carbon
dioxide are very large – from 140 to 280 Nm3 par
extracted barrel (Mazur and Chan 1982) – it is
necessary to separate carbon dioxide from the
hydrocarbon gaseous phase in order to have it
recycled to the reservoir (after pressurization).
Since the quantity of CO2 dissolved in oil
varies over a large range of values during the
whole production of the reservoir (levels from
40 % up to 90 % can be observed after a few
years of production (Cooley and Dethloff 1985)),
it is rather difficult to design a cost-effective CO2
removal unit that could operate during the entire
life of the reservoir. Therefore, modular CO2
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_218-2
removal units such as membrane operations offer
much flexibility for such an operation (Table 1).
The first large-scale EOR project operating
membranes has been carried out in the Sacroc
oil field located in Western Texas. Carbon dioxide
injection was launched in 1972 (at a flow
range up to 240,000 Nm3/h). Three CO2 recovery
units were initially installed: two hot potassium
carbonate-based absorption units (operated by
Sun Explo with a 190,000 Nm3/h capacity lead-
ing to a reduction of carbon dioxide from 24 % to
0.5 % and Chevron, with a 54,000 Nm3/h lower-
ing CO2 content down to 1 %) and an amine
(MEA)-based absorption unit (operated by
Monsanto, with a 20,000 Nm3/h capacity). At
the end of the 1970s, realizing that the level of
CO2 was raising at a higher rate than expected,
Chevron contacted Cynara in order to install and
operate two gas permeation units upstream of the
hot potassium carbonate absorption columns. The
treatment capacities of the membrane units were,
respectively, 60,000 Nm3/h at 35 bar feed pres-
sure prior to the Sun unit and 25,000 Nm3/h at
33 bar feed pressure prior to the Chevron unit.
Cynara chose to operate a single-stage configura-
tion, the membrane module being installed in
parallel. The membrane operation proved to be
highly flexible and reliable, as the membrane
modules remained in operation twice longer
than the expected lifetime (more than 5 years
instead of 2–3 years) without any selectivity
decrease. A slight decrease in membrane perme-
ability has nevertheless been observed
 2

Enhanced Oil Recovery (EOR), Table 1 Comparison of relative investment costs (CAPEX) and operating costs (OPEX) of membrane-based, solvent-based, and hybrid
processes for carbon dioxide capture (EOR applications)
CAPEX réf. Cryo.a Mem.
Operating conditions Study realized by Year OPEX réf. + Mem. Mem. +DEA DEA Cryo.a TEA KCO3 chaud
175.000 m3/h Amoco (Goddin 1982) 1982 47 M$ 1 2.2 1.56 1.48
90 % CO2, 20.4 M$/a 1 1.76 1.39 1.12
18 bar
118.000 m3/h Permea (Boustany et al. 1983) 1983 16.1 M$ 1.50 1 1.31
80 % CO2 6.5 M$/a 1.31 1 1.82
190.000 m3/h Fluor Engineering Schendel and Seymour 1985) 1984 1 0.63 0.63b
40 % CO2 1 0.56 0.68b
a
Cryo.: cryogenic distillation (Ryan-Holmes process (Kohl and Nielsen 1997))
b
Hot potassium carbonate + membrane
Enhanced Oil Recovery (EOR)
Enhanced Oil Recovery (EOR) 3

Enhanced oil recovery 1 2 3 4 5 6

(Kvaerner Membrane Systems)
3
Flow rate (103 Nm3/h) 26.5 7.4 18.9 11.2 15.3 3.8
Pressure (bar) 16 25 20 26 5 1
5 6 2
CO2 70 10 93.4 35.4 95.2 86.2
CH4 9.6 26.9 2.9 20 2.0 6.7
C2 6.3 10.0 1.0 14.0 0.7 2.4 1
Composition (% mol.) C3 5.6 18.4 0.6 12.9 0.4 1.5
i-C4 2.5 8.6 - 6.0 - 0.2
n-C4 1.3 4.3 - 3.0 - 0.1
H2S 0.6 0.01 0.8 0.1 0.9 0.4 4
N2 4.1 11.8 1.1 8.6 0.7 2.5

CH4 (C2+) recovery yield = 77,8 % (73 %)

Enhanced Oil Recovery (EOR), Fig. 1 EOR example of permeation application (Spillman 1989)

throughout the operation, and it was necessary to
add more modules in order to maintain the pro-
duction level of the membrane operation
(Marquez and Hamaker 1986).
Since then, other membrane companies have
seen their products involved in other EOR
projects:
– Kvaerner membrane systems (Chapel
et al. 1999):
Dallas Production Inc. (Texas) treated
200,000 Nm3 of gases containing up to
25 % of carbon dioxide in 1994 during a
feasibility study that lasted for 18 months.
After this test, the membrane unit was in
operation treating 1200 Nm3/h.
Hydrocarbon Operating, Inc. (Texas)
processed 590 Nm3/h at 51 bar feed pres-
sure in 1994 on a pilot skid composed of
two tubular membrane modules.
– Medal:
A Medal membrane unit was operated at the
need of the 1990s to process 14,200 Nm3/h
at 56 bar, 48 % CO2, reducing the retentate
CO2 concentration down to 6 %.
– Cynara (Kohl and Nielsen 1995):
Amoco, Texas (1994): Cynara membranes
were used to process 35,000 up to
120,000 Nm3/h of gas containing 80 % CO2.
Mobil, Salt Creek (1992): Cynara membranes
were used to process 76,000 up to
120,000 Nm3/h of containing 70 % CO2.
Shell, Texas: Cynara membranes were used to
process 13,000 Nm3/h of gas containing
70 % CO2 (Fig. 1).
References
Boustany K, Narayan RS, Stookey DJ (1983) Economics
of removal of carbon dioxide from hydrocarbon gas
mixtures. In: Abstracts 62nd Annual Gas Processors
Association, San Francisco, CA, pp 146–149
Chapel DG, Mariz CL, Ernest J (1999) Recovery of CO2
from flue gases: commercial trends. In: Oral Presenta-
tion Canadian Society of Chemical Engineers Annual
Meeting, Saskatoon, Sakatchewan, Canada.
Cooley TE, Dethloff WL (1985) Field-tests show mem-
brane processing attractive. Chem Eng Prog 81:45–50
Goddin CS (1982) Comparison of processes for treating
gases with high CO2 content. In: Abstracts 61st
Annual Gas Processors Association Convention, Dal-
las, TX, pp 60–68
Kohl A, Nielsen R (1997) Gas purification, 5th edn. Gulf
Publishing Co, Houston, pp 1238–1295
Marquez JJ, Hamaker RJ (1986) Development of mem-
brane performances during SACROC operations. In:
Oral presentation at AIChE Spring National Meeting
and Petro. Expo’86. New Orleans, LA
Mazur WH, Chan MC (1982) Membranes for natural-gas
sweetening and CO2 enrichment. Chem Eng Prog
78:38–43
Schendel RL, Seymour JD (1985) Take care in picking
membranes to combine with other processes for CO2
removal. Oil Gas J 83:84–86
Spillman RW (1989) Economics of gas separation mem-
branes. Chem Eng Prog 85:41–62
E
Enzymatic Ultrafiltration
Membranes (Immobilization
of Urease and Trypsin)
Christophe Innocent
Institut Européen des Membranes, ENSCM,
CNRS, Université de Montpellier, Montpellier,
France
The sodium alginate was used as an anionic poly-
electrolyte. The polyethyleneimine was used as a
cationic polyelectrolyte. Trypsin (enzyme which
catalyzed the hydrolysis of peptide bonds in
which the carboxyl groups are contributed by
the lysine and arginine residues) was applied as
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_219-4
a positively charged polyelectrolyte and the ure-
ase (enzyme which catalyzes the hydrolysis of
urea to ammonium and carbon dioxide) as a neg-
atively charged polyelectrolyte. For adsorption of
the polyelectrolyte layers, the supporting mem-
brane (polyacrylonitrile-modified membrane
negatively charged) was immersed in the solution
of the cationic polyelectrolyte, rinsed with the
buffer solution to remove excess of polycations
on membrane surface, immersed in the solution
of the anionic polyelectrolyte, and rinsed with the
buffer solution again. These steps were repeated
to form multiple polyelectrolyte bilayers based
on the electrostatic layer-by-layer self-assembly
(Fig. 1).
2 Enzymatic Ultrafiltration Membranes (Immobilization of Urease and Trypsin)

Enzymatic Ultrafiltration Membranes (Immobilization of Urease and Trypsin), Fig. 1 Scheme of layer-by-layer
adsorption of polyelectrolytes on membrane

References

Decher G (1997) Fuzzy nanoassemblies: toward layered

polymeric multicomposites. Science 277:1232–1237
E
Extracellular Polymeric Substance
(EPS)
Loreen O. Villacorte
FMC Technologies, Separation Innovation and
Research Center, Arnhem, The Netherlands
Extracellular polymeric substances or EPSs are
biosynthetic polymers from prokaryotic
(bacteria, archaea) and eukaryotic (algae, fungi)
microorganisms, which either form (loose or
tight) slimes around the microbial cells or are
excreted as discrete gels to the surrounding envi-
ronment. Typically, EPSs are heterogeneous
mixtures of polysaccharides, proteins, nucleic
acids, lipids, and other polymeric compounds.
The highly diverse chemical composition of
EPS is a result of the different processes related
to their production and their immediate environ-
ment: active microbial secretion, shedding of cell
surface materials, cell lysis, and adsorption from
the environment (Wingender et al. 1999).
EPSs are often associated with the formation
of biofilms and microbial aggregates. In biofilm
systems, they are mainly responsible for binding
cells and other particulate materials together and
to the solid-liquid interface (Characklis and
Wilderer 1989). In surface water sources,
suspended EPSs are responsible for the formation
of large aggregates of organic and inorganic
suspended materials including living and dead
microorganisms in the water (e.g., marine snow
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_220-6
or mucilage). These aggregates are held together
by a type of EPS mainly comprising of surface-
active, algae-derived anionic polysaccharides
collectively known as transparent exopolymer
particles (Alldredge 2002). The latter has been
recently identified as one of the major initiators of
aquatic biofilms as it can form conditioning films
on the solid-liquid interface conducive for bacte-
rial attachment (Bar-Zeev et al. 2012).
Over the years, the important role of EPS in
the microbial activities in natural aquatic systems
is widely recognized. Moreover, it has also been
identified to cause serious problems in technical
systems ranging from the shipping industry,
power industry, microelectronics, and food
industries to water purification (Flemming
et al. 2009). In water supply systems, such prob-
lems are due to either organic or biological foul-
ing of reservoirs, pipelines, media filters, and
separation membranes.
EPS accumulation in membrane filtration sys-
tems can cause increase of operating pressure and
cleaning frequency due to blockage of membrane
pores as well congestion along the feed channel
(Flemming et al. 1997). In NF/RO systems, it can
directly cause decline in permeate water quality
(e.g., salt rejection) due to hindered back diffu-
sion of rejected salts and can indirectly cause
membrane damage due to long exposure of
cleaning chemicals and very high feed channel
pressure drop (Vrouwenvelder et al. 2011). It has
been proposed that the removal of planktonic
EPS from the feedwater by pretreatment with
2 Extracellular Polymeric Substance (EPS)
dissolved air flotation (DAF) and/or UF/MF
membranes can effectively minimize biofouling
in NF/RO systems. However, this is still subject
to extensive debate and investigations.
During algal blooms, very sticky EPS mate-
rials (including TEPs) produced by phytoplank-
ton and bacterioplankton can cause physically
irreversible (or non-backwashable) fouling in
dead-end MF/UF systems (Villacorte
et al. 2010). In this case, chemically enhanced
backwashing (CEB) can be effective in restoring
membrane permeability. However, applying an
optimal dose of coagulant (conventional or
in-line) prior to membrane filtration has been
found to effectively minimize the need for chem-
ical cleaning (e.g., Schurer et al. 2012).
Cross-References
▶ Algal Bloom
▶ Biofilm
▶ Biological Fouling
▶ Organic Fouling
▶ Polysaccharides
▶ Proteins
▶ Transparent Exopolymer Particles (TEP)
References
Alldredge AL (2002) Marine snow. In: Nybakken JW,
Broenkow WW, Vallier TL (eds) Interdisciplinary
encyclopedia of marine sciences. Grolier Academic
Reference, Danbury
Bar-Zeev E, Berman-Frank I, Girshevitz O, Berman
T (2012) Revised paradigm of aquatic biofilm forma-
tion facilitated by microgel transparent exopolymer
particles. Proc Natl Acad Sci USA 109(23):9119–9124
Characklis WG, Wilderer PA (1989) Glossary. In:
Characklis WG, Wilderer PA (eds) Structure and func-
tion of biofilms. Wiley, Chichester, pp 369–371
Flemming H-C, Schaule G, Griebe T, Schmitt J,
Tamachkiarowa A (1997) Biofouling – the Achilles
heel of membrane processes. Desalination
113:215–225
Flemming H-C, Murthy PS, Venkatesan R, Cooksey KE
(eds) (2009) Marine and industrial biofouling,
vol 4, Springer Series on Biofilms. Springer, Berlin
Lens P, O’Flaherty, Moran AP, Stoodley P, Mahony
T (eds) (2003) Biofilms in medicine, industry and
environmental biotechnology: characteristics, analysis
and control. IWA Publishing, London
Schurer R, Janssen A, Villacorte L, Kennedy MD
(2012) Performance of ultrafiltration & coagulation
in an UF-RO seawater desalination demonstration
plant. Desalination Water Treat 42:57–64
Villacorte LO, Schurer R, Kennedy MD, Amy G,
Schippers JC (2010) The fate of transparent
exopolymer particles in integrated membrane systems:
a pilot plant study in Zeeland, The Netherlands. Desa-
lination Water Treat 13:109–119
Vrouwenvelder JS, Kruithof J, Van Loosdrecht M (2011)
Biofouling of spiral wound membrane systems. IWA
Publishing, London
Wingender J, Neu TR, Flemming H-C (eds) (1999) Micro-
bial extracellular polymeric substances: characteriza-
tion, structure, and function. Springer, Berlin
E

Extraction Index for any involved species. It gives an indication

Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende(CS), Italy
The extraction index is a measure of membrane
operation performance of extracting a desired
species from the feed/retentate side in order to
have it as permeate. It can be defined/evaluated
about the real advantages offered by using a
membrane unit instead of conventional ones.
The higher the variable value, the higher the
performance of the membrane unit. It is defined
as the ratio (Eq. 1) of the permeate flow rate of the
species permeated through the membrane to that
totally fed to the membrane unit. Equation 1
shows different ways for evaluating the extrac-
tion index:

Permeate flow ratei

Extraction Indexi ¼
Feed flow ratei

Permeate flow rate Permeate molar fractioni

¼
Feed flow rate Feed molar fractioni

Permeate flow rate Permeate Partial Pressurei

¼ (1)
Feed flow rate Feed Partial Pressurei

Permeate flow rate Permeate concentrantioni

¼
Feed flow rate Feed concentrantioni

Permeate flow rate Permeate mass fractioni

¼
Feed flow rate Feed mass fractioni

The extraction index assumes a specific and more membrane reactors since a desired chemical can
interesting form when a chemical reaction takes be fed in it but also produced by reaction. In this
place inside the membrane unit such as in the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_221-1
2 Extraction Index

case, Eq. 1 has to take into account also the If the water-gas shift reaction is used as an exam-
production term: ple, the extraction index can be defined as the
ratio of the H2 permeated through the membrane
Extraction Indexi ¼ to that totally available in the feed stream both as
Permeate flow ratei H2 molecules and also obtainable from other
Feed flow ratei þ Production by Reaction for i  th chemicals (e.g., CO) by reaction, to the mem-
(2) brane unit (Eq. 3):

Flow ratePermeate
H2
H2 Extraction Index ¼
Flow rateAvailable
H2
in the feed

Flow ratePermeate
H2
in the MR¼ (3)
Flow rateFeed
H2 þ a  Flow rateFeed
CO


H2 O=CO feed molar ratio per H2 O=CO feed molar ratio < 1
a¼
1 per H2 O=CO feed molar ratio  1

The extraction index (Barbieri et al. 2008) takes
into account the hydrogen fed as H2 molecules
and that is contained in the feed stream in other
chemicals (e.g., H2O). The term (a flow rate CO
feed) of the Eq. 3 considers the maximum H2
extractable from the chemicals (other than hydro-
gen) present in the system. The coefficient
(a) takes into account the defecting reactant
(CO or H2O) by means of the feed molar ratio
H2O/CO. It (a) is equal to the feed molar ratio if
the latter is lower than 1 (CO in defect with
respect to H2O). It (a) will be equal to 1 when
the CO exceeds the H2O. As defined, the
extraction index is determined by the membrane
properties, feed molar ratio, and CO conversion
achieved in the membrane reactor, at set operat-
ing conditions.
References
Barbieri G, Brunetti A, Tricoli G, Drioli E (2008) An
innovative configuration of a Pd-based membrane
reactor for the production of pure hydrogen. Experi-
mental analysis of water gas shift. J Power Sources
182(1):160–167. doi:10.1016/j.jpowsour.2008.03.086
F
Facilitated Pervaporation
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
A facilitated pervaporation system usually refers
to the combination of a pervaporation as a sepa-
ration unit combined with a chemical reactor for
esterification reactions or other equilibrium reac-
tions. The “facilitation” then refers in fact to the
reaction, and not the separation. The
pervaporation unit removes the side product of
the reaction (in case of esterification, this is
water) so that the reaction equilibrium shifts to a
higher product yield (Van der Bruggen 2010).
Other reactions than esterifications can also be
facilitated, on condition that they concern an
equilibrium reaction and that the side product
can be easily removed by a pervaporation mem-
brane (as is the case for water in an organic
reaction mixture). For bioconversions, the reac-
tion product(s) are to be removed instead of the
by-products, in order to enhance the activity of
the microbial population. This is the case, for
example, in the production of bioethanol and in
ABE (acetone, butanol, ethanol) fermentations,
where ethanol (or butanol) is removed by a
hydrophobic pervaporation membrane. See also
pervaporation membrane reactor and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_222-4
pervaporation assisted reactor for further
explanation.
However, facilitated pervaporation may rather
be related to a hybrid membrane extraction sys-
tem, as described by Bessarabov et al. (1999) for
the separation of liquid olefin/paraffin mixtures in
the range up to C6. Nonporous polymeric mem-
branes are used in a membrane contactor and a
high-boiling-point selective liquid extractant
flowing along polymeric membranes between
the extractor and the membrane stripper. The
olefin components permeated through the poly-
meric films at elevated temperatures in a mem-
brane stripper, making it possible to obtain
pervaporation transport. This is schematically
shown in Fig. 1 (Bessarabov et al. 1999).
Another approach to obtain a pervaporation
effect is by the use of fixed recognition sites in
membrane contactors (Touil et al. 2006), so that
the selectivity needed for pervaporation is
obtained in a pertraction process (in which a
porous membrane without any selectivity is
used). The combination of selectivity character-
istic for pervaporation and the pertraction effect
results in an enhancement, which can be denoted
as facilitated pervaporation. Cyclodextrins, for
example, can be used to form inclusion com-
plexes of different stability with organic mole-
cules in the separation of p-xylene, m-xylene, and
o-xylene (Touil et al. 2006). Kusumosahyo
et al. (2004) made a similar study on polyacrylic
acid (PAA) membranes and concluded that the
native PAA membrane was almost impermeable
2 Facilitated Pervaporation

Inlet for extractant increased fluxes and separation factors.

A similar enhancement effect was obtained by
A the incorporation of carbon nanotubes (CNTs)
in the pores of a polyvinylidene fluoride
(PVDF) membrane (Sae-Khow and Mitra 2009),
and for polyvinyl alcohol (PVA) membranes
Contacting
Hydrocarbon (Bryant et al. 1997), and many other publications
spacers
feed layer can be found on similar effects in mixed matrix
membranes, nanoparticles-enhanced membranes,
and hybrid organic–inorganic membranes.
Extractant
layer Chemical modifications have also been studied
for enhancement of pervaporation. Wu
et al. (2002) studied cross-linked polydimethyl-
siloxane (PDMS) membranes modified by the
sequential introduction of two different side-arm
functional groups, -(CH2)(3)OC2H5 and -(CH2)
Pumping
Cooling B (3)NMe2, for the pervaporative recovery of
Heating
p-cresol from aqueous streams, which was
STRIPPER
successful.

Non-porous
membrane References

Bessarabov DG, Theron JP, Sanderson RD, Schwarz HH,

Degassing
C=C
Facilitated Pervaporation, Fig. 1 Facilitated
pervaporation using a hybrid membrane extraction system
(for olefin separation). A is an extraction module, B is a
membrane pervaporation cell (Reprinted with permission
of Elsevier from Bessarabov et al. 1999)
for the xylene isomers, and the incorporation of
cyclodextrins in the PAA membranes resulted in
membranes having a molecular recognition func-
tion, which selectively facilitated the transport of
the xylene isomers.
A further use of the term facilitated
pervaporation refers to the membrane material
itself. Liu et al. (2011) incorporated Ag(+) loaded
titania (TiO(2)) microspheres into a poly
(dimethyl siloxane) (PDMS) matrix for
pervaporative desulfurization of model gasoline
and demonstrated facilitated transport through
these membranes, as could be seen from
Schossig-Tiedemann M, Paul D (1999) Separation of
1-hexene/n-hexane mixtures using a hybrid mem-
brane/extraction system. Sep Purif Technol
16(2):167–174
Bryant DL, Noble RD, Koval CA (1997) Facilitated-
transport separation of benzene and cyclohexane with
poly(vinyl alcohol)-AgNO3 membranes. J Membr Sci
127(2):161–170
Kusumosahyo SP, Kanamori T, Sumaru K, Iwatsubo T,
Shinbo T (2004) Pervaporationof xylene isomer mix-
ture through cyclodextrins containing polyacrylic acid
membranes. J Membr Sci 231:127–132
Liu WP, Li B, Cao RJ, Jiang ZY, Yu SN, Liu GH, Wu
H (2011) Enhanced pervaporation performance of
poly (dimethyl siloxane) membrane by incorporating
titania microspheres with high silver ion loading.
J Membr Sci 378:382–392
Sae-Khow O, Mitra S (2009) Fabrication and characteri-
zation of carbon nanotubes immobilized in porous
polymeric membranes. J Mater Chem
19(22):3713–3718
Touil S, Tingry S, Bouchtalla S, Deratani A (2006) Selec-
tive pertraction of isomers using membranes having
fixed cyclodextrin as molecular recognition sites.
Desalination 193:291–298
Facilitated Pervaporation
Van der Bruggen B (2010) Pervaporation membrane reac-
tors. In: Enrico D, Lidietta G (eds) Comprehensive
membrane science and egineering, vol 3. Academic,
Oxford, pp 135–163
3
Wu P, Brisdon BJ, England R, Field RW (2002) Prepara-
tion of modified difunctional PDMS membranes and a
comparative evaluation of their performance for the
pervaporative recovery of p-cresol from aqueous solu-
tion. J Membr Sci 206:265–275
F
Fat Hydrolysis, Membrane
Operations of
Angela C. Macedo1 and F. Xavier Malcata2
1
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
2
DEQ – Department of Chemical Engineering &
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
Lipids that are solid at room temperature are
termed fats. In nature, most fats are
triglycerides – consisting of a glycerol backbone,
to which three individual fatty acid moieties are
attached. The variety of fats in nature and their
diversity in terms of physicochemical properties
come from the number of combinations of the
hundreds of existing fatty acid residues – which,
due to their underlying metabolic synthesis path-
way, are characterized by an even number of
carbon atoms.
In view of their insolubility and the relevance
to water-based life, fats often appear stabilized
via emulsification in aqueous media; this is nota-
ble in the case of milk fat, with globules
surrounded by a membrane containing proteins
and phospholipids. Said native globules range in
size from less than 1 mm to over 10 mm. The
uneven size distribution provides larger globules
with a tendency to float: under static conditions,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_223-2
that buoyancy effect leads to creaming at the top
of the container, but the process may be speeded
up by centrifugation or filtration. The major dis-
advantage of the latter is the difficulty in remov-
ing the fat layer once formed – coupled with
clogging of the membrane pores – which is par-
ticularly detrimental in the case of hydrophobic
matrices. Milk is often homogenized by forcing it
into a tiny nozzle under high pressure, so as to
reduce the average globule size to less than 1 mm;
this creates a more uniform distribution of glob-
ules that improves kinetic stability of the emul-
sion (Fox and McSweeney 1998).
Hydrolysis of fats can be effected by lipases
(and esterases, to a lesser extent), which require a
fat/water interface be present; this type of inter-
facial reaction is thus promoted by high specific
areas, which may be attained at the expense of
addition of emulsifiers and vigorous stirring.
However, lipases are typically much more expen-
sive than their fat substrates, so some form of
immobilization thereof is in order for economic
feasibility; this approach is particularly simple
because such enzymes do not require cofactors
for catalytic activity, while possessing a rela-
tively high hydrophobic nature that facilitates
spontaneous adhesion to hydrophobic materials
via adsorption.
Several immobilized microbial lipases are
available from industrial suppliers, using, e.g.,
ion exchange resins and polymeric materials as
supports; they have been applied to hydrolyze
fats in emulsified form, but show the
2 Fat Hydrolysis, Membrane Operations of
disadvantage that the fat and enzyme particles
must collide for catalysis to occur. Porous mem-
branes constitute an interesting alternative,
because lipase can be immobilized inside their
pores – with water pumped along one side and
(melted) fat along the other. Besides low rates of
fouling, said tangential membranes may offer
high volumetric efficiencies – especially if they
are manufactured in hollow-fiber form – and per-
mit the concentration of fat to remain at its max-
imum level ever by circumventing phase mixing.
Furthermore, immobilized lipase processes
offer fatty acid- and stereo-specificity advantages
over plain acid- or base-catalyzed hydrolysis of
fats – which are intrinsically
nonspecific. Considering the difference in metab-
olism of fatty acids depending on their original
regiodistribution and chain length, lipases have
been largely applied to produce tailor-made
derivatives of triacylglycerols with medium- or
short-chain fatty acid residues in external posi-
tions (sn-1 and sn-3) and long-chain fatty acids in
the internal position (sn-2) (Willis et al. 1998);
these are in higher and higher demand for nutri-
tional purposes.
Depending on the level of water in their vicin-
ity, membrane-immobilized lipases operating on
a fat substrate may also perform ester synthesis,
as well as interesterification – of the acidolysis,
alcoholysis, and transesterification
types – depending on whether the aqueous sub-
strate is replaced by a fatty acid, an alcohol, or
another fat, respectively. This process is rela-
tively easy to bring about, but suffers from two
major shortcomings: enzymes tend to deactivate
as time online elapses, thus calling for enzyme
makeup; and product separation is often difficult,
especially when only lipid phases are
involved – and resorts to distillation (which
should be carried out at low pressure in the case
of heat-labile fats).
References
Fox PF, McSweeney PLH (1998) Milk lipids. In: Fox PF,
McSweeney PLH (eds) Dairy chemistry and biochem-
istry. Blackie Academic and Professional Publishers,
London, pp 67–146
Willis W, Lencki E, Marangoni A (1998) Lipid modifica-
tion strategies in the production of nutritionally func-
tional fats and oils. Crit Rev Food Sci Nutr 38:639–674
F
Fat Processing, Membrane
Operations of
Angela C. Macedo1,2 and F. Xavier3
1
ISMAI – University Institute of Maia, Avenida
Carlos Oliveira Campos, Avioso S. Pedro,
Portugal
2
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
3
Department of Chemical Engineering,
University of Porto, Porto, Portugal
Fat processing is an active business, designed to
create added value from slaughter by-products
downstream the animal chain. It encompasses
activities dealing with production of animal fats
(and proteins) suitable for human consumption in
agreement with directive 77/99/EEC (EU 1997),
as well as processing of category 3 (formerly
labeled low risk) materials from animals
approved for human consumption in agreement
with regulation ABPR 1774/2002/EC (EU 2002).
Fat processing has historically been associated
with manufacture of high-grade animal fats for
specific markets, e.g., bakery industry, calf milk
replacers, and pet food – as well as commodities
for formulation in the oleo-chemical industry
(e.g., manufacture of soaps) and cosmetics; it
uses bovine tallow, porcine lard, and poultry fat
as major feedstocks.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_224-3
The basic operations in fat processing are wet
melting and dry rendering – or hybrid systems
thereof. Fat tissues are subjected to relatively
mild processing conditions to minimize their
decay – but high-quality final products hinge
critically on the quality and source of the raw
materials. They are usually collected from
slaughterhouses from animals slaughtered on
the same day and undergo strict food safety
steps according to HACCP
methodology – including monitoring of environ-
mental contaminants, growth hormones, and vet-
erinary drugs. Membrane processing is possible,
but only on clean melted fat – and chiefly to
deliver support for enzymes aimed at controlled
chemical modifications of such fat, e.g.,
interesterification.
Fat interesterification can be carried out via
chemical or enzymatic processes; the former
require metal alkalis as catalysts, but produce
random interchange of acyl groups, lead to con-
tamination of the final product with residual cat-
alyst, and allow formation of soaps – all of which
are viewed as drawbacks relative to their enzy-
matic counterparts (Erickson 1995). Lipase-
mediated interesterification with lipases is char-
acterized by great versatility, reasonable sub-
strate selectivity (including regio-and
enantioselectivity), possibility of operation at
room temperature and pressure, and the absence
of side reactions. To fully exploit the technical
advantages of such enzymes, economic feasibil-
ity recommends the use in immobilized form – to
2 Fat Processing, Membrane Operations of
extend their useful life, avoid product contami-
nation and consequent unstability, and circum-
vent the need for emulsification (James
et al. 2009). Lipase immobilization also facili-
tates product separation, enhances thermostabil-
ity, alleviates rate dependence on pH, and is more
flexible in terms of reactor configuration.
Unlike hydrolases at large that operate in plain
aqueous phases, lipases are activated only in the
presence of water/lipid interfaces – provided by
the contacting surface between the immiscible
aqueous and fat phases, which can be made to
coincide with a porous membrane. Techniques
that met with industrial success for immobiliza-
tion of lipases include adsorption, covalent bind-
ing, and entrapment/microencapsulation
(Knezevic et al. 2004). Note that the economic
feasibility is directly related to the volumetric
productivity on the long run, which depends in
turn not only on the operational stability of the
enzyme but also on its actual activity – which is
normally lower than that of free enzyme, in addi-
tion to mass transfer constraints (Vulfson 1994).
Physical adsorption is the simplest method for
lipase immobilization; binding occurs via hydro-
gen bonds, salt linkages, and van der Waals
forces. The process is carried out at mild condi-
tions, without (or with a marginal) support acti-
vation and in the absence of extraneous reagents;
it is thus prone to preserving enzyme activity and
specificity. The chemical nature of the carrier
(including the ratio of hydrophilic to hydrophobic
groups), the particle size and porosity, and the
surface area available determine the amount of
enzyme bound, as well as the enzyme behavior
following immobilization (Cao 2005).
Chemical reaction between activated amino
acid residues far from the catalytic and binding
site of the enzyme and active functionalities on
the carrier is the basis of (effective) covalent
attachment. This is clearly the most efficient
mode of immobilization – despite its being
much more detrimental for enzyme activity, com-
plex in terms of implementation, and heavily
dependent on the properties of the carrier (Cao
2005).
Finally, entrapment involves capture of
enzyme within a polymeric matrix during the
polymerization process – whereas (the related)
microencapsulation entails confinement by a
membrane-like physical barrier around the
enzyme preparation; entrapped enzymes may be
further microencapsulated. Both processes
require simple equipment and relatively inexpen-
sive reagents – and yield a better stability and an
activity similar to adsorbed enzymes (Cao 2005).
References
Cao L (2005) Carrier-bound immobilized enzymes. Prin-
ciples, application and design. Wiley-VCH, Weinheim
Erickson DR (1995) Practical handbook of soybean
processing and utilization. American Oil Chemists
Society, Champaign
EU (1997) Council Directive 77/99/EEC of 21 December
1976 on health problems affecting intra-community
trade in meat products. Off J Eur Commun L26
EU (2002) Regulation (EC) No. 1774/2002 of the Euro-
pean Parliament and of the Council laying down health
rules concerning animal by-products not intended for
human consumption. Off J Eur Commun L273:1–95
James J, Simpson BK, Marshall MR (2009) Application of
enzymes in food processing. Crit Rev Food Sci Nutr
36:437–463
Knezevic ZD, Siler-Marinkovic SS, Mojovic LV
(2004) Immobilized lipases as practical catalysts.
APTEFF 35:1–280
Vulfson EN (1994) Industrial applications of lipases. In:
Woolley P, Peterson SB (eds) Lipases: their structure,
biochemistry and application. Cambridge University
Press, Cambridge, UK, pp 271–288
F
Feed Pressure
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende (CS), Italy
Membrane operations, for instance, membrane
reactors, membrane gas separators, membrane
contactors, membrane emulsifiers, membrane
crystallizers, reverse osmosis, nanofiltration,
ultrafiltration, microfiltration, etc. as well the
more conventional unit operations, like reactors,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_225-1
distillation columns, adsorbers, absorbers, liquid-
liquid extractors, filters, pipelines, etc., are fed by
a stream entering the unit. The pressure of this
stream (to be treated by the unit operation) at the
entering section of each unit operation is defined
as feed pressure.
A further specification is required for mem-
brane systems. Often, an auxiliary stream named
“sweep” is fed to the membrane unit. This stream
is characterized by a different pressure named
“sweep pressure”; this pressure cannot be
referred to as “feed pressure.”
F
Fenton Test
P. Knauth
Madirel UMR 7246, Aix Marseille University-
CNRS, Marseille Cedex 20, France
Fenton’s reagent was developed in the 1890s by
Henry John Horstman Fenton as an analytical
reagent (Fenton and Jones 1900). It is a solution
of hydrogen peroxide and an iron catalyst. Iron
(II) sulfate is a typical iron compound in Fenton’s
reagent.
The mechanism mostly accepted today,
suggested by Haber and Weiss in the 1930s
(Haber and Weiss 1932), is that iron(II) is oxi-
dized by hydrogen peroxide to iron(III), a
hydroxyl radical and a hydroxide anion
(reaction 1):
Fe2þ þ H2 O2 ! Fe3þ þ OH  þ OH
Iron(III) is then reduced back to iron(II), a per-
oxide radical and a proton by the same hydrogen
peroxide (dismutation reaction 2):
Fe3þ þ H2 O2 ! Fe2þ þ OOH  þ Hþ
In the overall reaction, two molecules of hydro-
gen peroxide are converted into two radicals and
water by the presence of catalytic iron ions.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_226-1
The free radicals generated by Fenton’s
reagent induce then secondary reactions: the
free hydroxyl radical is a powerful,
non-selective oxidant used to oxidize organic
contaminants in waste waters to primarily carbon
dioxide and water.
Nowadays, Fenton’s test is applied for the
accelerated testing of the oxidation stability of
proton exchange membranes (PEM) for fuel cell
applications (Healy et al. 2005). Generally, the
weight loss after a defined treatment time is used
to monitor membrane degradation. Typical
Fenton’s test conditions for PEM membranes
are an aqueous solution with 30 % H2O2 and
20 ppm Fe2+ at 80–90  C with three treatment
cycles with fresh reagent and 24 h per cycle.
Given that the initial H2O2 concentration is
much higher than in an operating fuel cell,
“softer” alternative conditions are also used
with an aqueous 3 % H2O2 solution mixed with
(1) 4 ppm Fe2+ at 68  C (Ramaswamy et al. 2008).
Although Fenton’s test is straightforward and
considered as a benchmark for PEM evaluation, it
has inherent limitations, given that the membrane
degradation in this test is not related to an elec-
trode process and does not involve variations in
(2) fuel cell operating conditions, e.g., operating
potential, relative humidity, and the presence of
fuel and oxygen.
2 Fenton Test

References Healy J, Hayden C, Xie T, Olson K, Waldo R,

Fenton HJH, Jones HO (1900) The oxidation of organic
acids in presence of ferrous iron part I. J Chem Soc
77:69–76
Haber F, Weiss J (1932) On the catalysis of hydroperox-
ide. Naturwissenschaften 20:948–950
Brundage A, Gasteiger H, Abbott J (2005) Aspects of
the chemical degradation of PFSA ionomers used in
PEM fuel cells. Fuel Cells 5(2):302–308
Ramaswamy N, Hakim N, Mukerjee S (2008) Degrada-
tion mechanism study of perfluorinated proton
exchange membrane under fuel cell operating condi-
tions. Electrochim Acta 53(8):3279–3295
F
Fixed Carrier Membrane
Marius Sandru
Polymer Particles and Surface Chemistry,
Materials and Chemistry, SINTEF, Trondheim,
Norway
Fixed (site) carrier membranes (FSC) combine
the durability of a dense membrane with the
selectivity of a supported liquid membrane
(SLM) overcoming the limitation of SLM, deg-
radation due to the wash out of the carrier solu-
tion over time. The carrier is either covalently
bonded to the polymer chain (chained carrier) or
immobilized in the polymer matrix by physical
constraints or weaker ionic bonding. A fixed car-
rier membrane will separate mainly via facili-
tated transport mechanism, implying that the
carrier will react specifically with one of the
components to be separated.
Noble (1990, 1991) and Cussler (Cussler
et al. 1989) developed two different models to
describe the transport across fixed carrier mem-
branes. E. L. Cussler explained the transport by
“chained carrier” theory, when carriers are cova-
lently bonded, requiring a certain mobility of
polymeric chains and that a percolation threshold
appears when two chained carriers are too far
apart.
R. Noble described the transport of neutral
molecules such as O2 (Noble 1990) or ions
(Noble 1991) across membranes in the terms
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_229-2
dual-mode sorption model, assuming the pres-
ence of two distinct regions exhibiting gas solu-
bility based on Henry’s law and Langmuir
sorption isotherm. The model assumes also that
permeation is diffusion-limited. This model
shows the same behavior as facilitated transport
in liquid membranes and does not predict a per-
colation threshold as “chained carrier” model
does. The model implies that the effective diffu-
sion coefficient of the solute to be transported
depends on the morphology of membrane
between two reactive sites (“terrain”). Changes
in polymer morphology cause a change in this
effective diffusion coefficient.
The model presented by R. Noble is based on
the model presented by Barrer (1984) assuming
that a hole (microvoid) of the polymer free vol-
ume is equivalent to a complexing site (a carrier).
Barrer’s dual-mode transport for glassy polymers
contains four diffusion coefficients: diffusion of a
compound (A) through the polymer matrix, dif-
fusion of (A) from the polymer matrix to a hole in
the Langmuir region (excess of free volume),
diffusion of (A) between two holes, and diffusion
of (A) from a hole to the polymer matrix. The
significance of this analysis is that it predicts
facilitated transport even when there is no diffu-
sion or mobility of the complexing agent.
Both Noble’s and Cussler’s models have their
limitations. Dual sorption model presented by
Noble assumes that the concentration of the car-
rier is in large excess and consequently constant.
This implies that the model will start to deviate
2 Fixed Carrier Membrane
from experimental results at high loadings of the
carrier with the permeant (A) (carrier saturation).
Also the model does not take into account the
reaction kinetic between the carrier and permeant
(A).
The hopping mechanism proposed by Cussler
will strongly depend on the system permeant-
membrane material characteristics even though
it is taking into account the chemical reaction
between the carrier and component (A): high
diffusion coefficients of a compound (A) will
allow facilitation effect even at low concentration
of the carrier infirming a strict percolation thresh-
old predicted by the model.
References
Barrer RM (1984) Diffusivities in glassy polymers for the
dual mode sorption model. J Membr Sci 18:25
Cussler EL, Aris R, Bhown A (1989) On the limits of
facilitated diffusion. J Membr Sci 43:149–164
Noble RD (1990) Analysis of facilitated transport with
fixed site carrier membranes. J Membr Sci 50:207–214
Noble RD (1991) Analysis of ion transport with fixed site
carrier membranes. J Membr Sci 56:229–234
Further Reading
Baker RW (2004) Membrane technology and applica-
tions. McGraw- Hill, New York
Mulder M (2003) Basic principle of membrane technol-
ogy. Kluwer, London
F
Fixed Bed Catalytic Reactor
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
The fixed bed (or packed bed) membrane reactor
configuration is the first and most studied config-
uration for membrane reactors. This is because
the first studies on membrane reactors focused on
the effect of the gas permeation through mem-
branes on the reaction system (which is often a
conventional packed bed reactor).
In a packed bed membrane reactor, the cata-
lyst is confined in fixed bed configuration, and it
is in contact with a permselective membrane. The
most used packed bed configuration is the tubular
one where the catalyst may be packed either in
the membrane tube or in the shell side, while the
permeation stream is collected in the other side of
the membrane (in the case of hydrogen-selective
membranes) or one reactant is feed on the other
side of the membrane (in the case of oxygen-
selective membrane).
For multitubular membrane reactor configura-
tions, the catalyst in tube configuration can be
preferred especially for construction reason and
for the extent of bed-to-wall mass and heat trans-
fer limitations which can be very detrimental in
the catalyst in shell configuration.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_230-2
Often, a sweep gas can be used in the perme-
ation side of the membrane in order to keep the
permeation hydrogen partial pressure as low as
possible for minimizing the membrane area
required for the hydrogen separation. This prac-
tice is, for example, very useful if hydrogen for
ammonia plant is being produced, in which case
an amount of nitrogen can be used for sweeping
the permeation side producing a synthesis stream
(N2/H2 = 1/3) ready for the final reaction step. If
a sweep gas is used in the permeation side, then a
packed bed membrane reactor can be used in both
cocurrent or countercurrent modes.
An interesting feature of packed bed mem-
brane reactors is the possibility to operate them
in a reverse flow mode, integrating the reaction
and separation with the recuperative heat
exchange inside the reactor. This operational
mode is quite interesting for partial oxidation of
methane (POM) (Smit et al. 2005). In normal
POM systems air and CH4 feed streams have to
be preheated to the reaction temperature, while
being POM reaction only slightly exothermic, the
external heat transfer between feed and exhaust is
very expensive. Therefore, recuperative heat
exchange is preferably carried out inside the
reactor.
Although the tube in tube configuration is
quite useful to work in lab scale and for proof of
principle of membrane reactors, for industrial
scale some other configurations need to be used
in order to increase the membrane area per vol-
ume of vessel used. In fact, the amount of
2 Fixed Bed Catalytic Reactor
hydrogen produced is directly related to the
amount of membrane area installed in the reactor.
Starting for the tube in tube configuration, a
straightforward way to increase the membrane
area in packed bed is the tube in shell configura-
tion (Buxbaum 2002; Tosti et al. 2008).
Although the packed bed configuration is very
advantageous and easy to operate, the production
of thin membranes brought under the spotlight
one of the disadvantages of fixed bed membrane
reactors: the influence of bed-to-wall mass trans-
fer limitations on the membrane area required.
Briefly, as long as the hydrogen flux through the
membrane is a limiting step, the effect of external
mass transfer limitations such as the limitations
to hydrogen transport between the bulk of the
catalytic bed (where hydrogen is produced) and
the membrane wall (where hydrogen is recov-
ered) can be neglected. However, by increasing
the membrane flux, the external mass transfer
limitations became limiting and determine the
extent of membrane area. This has been demon-
strated both experimentally (Peters et al. 2008)
and numerically (Gallucci et al. 2010). This
important drawback has driven the research
toward new reactor concepts such as micro-
membrane reactors or fluidized bed membrane
reactors.
References
Buxbaum RE (2002) Patent US20026461408
Gallucci F, Van Sint Annaland M, Kuipers JAM
(2010) Theoretical comparison of packed bed and flu-
idized bed membrane reactors for methane reforming.
Int J Hydrog Energy 35:7142–7150
Peters TA, Stange M, Klette H, Bredesen R (2008) High
pressure performance of thin Pd-23%Ag/stainless steel
composite membranes in water gas shift gas mixtures;
influence of dilution, mass transfer and surface effects
on the hydrogen flux. J Membr Sci 316(1–2):119–127
Smit J, Bekink GJ, Van Sint Annaland M, Kuipers JAM
(2005) A reverse flow catalytic membrane reactor for
the production of syngas: an experimental study. Int
J Chem React Eng 3
Tosti S, Basile A, Bettinali L, Borgognoni F, Gallucci F,
Rizzello C (2008) Design and process study of Pd
membrane reactors. Int J Hydrog Energy
33(19):5098–5105
F
Fixed-Site (Chained-Carrier)
Membranes
Marius Sandru
Polymer Particles and Surface Chemistry,
Materials and Chemistry, SINTEF, Trondheim,
Norway
Carrier-facilitated transport processes in liquid
membranes often achieve spectacular separations
between closely related species because of carrier
selectivity. The instability of supported liquid
membranes (SLM) or emulsion type of mem-
branes (ELM) is a major technical challenge for
their implementation at large industrial scale
(Mulder 2003; Baker 2004; Koros and Mahajan
2000). One approach to stabilize the membranes
is to covalently link the carrier complex to the
matrix polymer resulting in fixed-site carrier
(chained) membranes.
The term chained carrier refers to transport
mechanism theory rather than to position of the
carrier on the membrane. E. L. Cussler (Cussler
et al. 1989) explained the facilitated transport by
a “chained carrier” theory that implies a certain
mobility of polymeric chains and that a percola-
tion threshold appears when two chained carriers
are too far apart. Chained carriers, by comparison
to mobile carriers diffusing freely within a liquid
membrane, have limited diffusion because they
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_231-2
are covalently bound in the polymer membrane.
The solute is transported via a hopping (“Tarzan”)
mechanism from one carrier to the next one
between the two interfaces, feed and permeate
sides of the membrane.
In order to transport components via facilitated
transport, the polymeric chains must have a cer-
tain mobility degree, and the concentration of the
carrier must be higher than the percolation thresh-
old (Cussler et al. 1989).
The hopping mechanism proposed by Cussler
will strongly depend on the system permeant-
membrane material characteristics even though it
is taking into account the chemical reaction
between the carrier and a component (A): high
diffusion coefficients of a compound (A) will
allow facilitation effect even at low concentration
of the carrier infirming a strict percolation thresh-
old predicted by the model.
A particular case of “chained carrier” for CO2
transport is presented by KT.J. Kim et al (2013).
The carrier is represented by the amine groups
covalently bonded to the polymeric chain of
polyvinylamine.
References
Baker RW (2004) Membrane technology and applications.
McGraw- Hill, New York
2 Fixed-Site (Chained-Carrier) Membranes

Cussler EL, Aris R, Bhown A (1989) On the limits of
facilitated diffusion. J Membr Sci 43:149–164
Kim TJ et al. (2013) Separation performance of PVAm
composite membrane for CO2 capture at different pH
levels, J. of Mem. Sci 428:218–224
Koros WJ, Mahajan R (2000) Pushing the limits on possi-
bilities for large scale gas separation: which strategies?
J Membr Sci 175:181–196
Mulder M (2003) Basic principle of membrane technology.
Kluwer, Dordrecht
F
Fluidized Bed Membrane Reactors
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
A fluidized bed membrane reactor, also indicated
as membrane-assisted fluidized bed (MAFBR), is
an integrated reactor where membranes (in form
of tubes, hollow fibers, or planar modules) are
immersed in a fluidized bed of catalyst particles.
Typical example of MAFBR for hydrogen pro-
duction is reported in (Gallucci et al. 2010a) and
consists in a bundle of hydrogen-selective mem-
branes immersed in a catalytic bed operated in
bubbling regime. The use of fluidized bed mem-
brane reactors makes possible the reduction of
bed-to-wall mass transfer limitations, but also
allows operating the reactor at a virtually isother-
mal condition (due to the movement of catalyst).
This possibility can be used for operating the
autothermal reforming of hydrocarbons inside
the membrane reactor. In fact, as indicated by
Tiemersma et al. (2006), the autothermal
reforming of methane in a packed bed membrane
reactor is quite difficult due to the hot spot at the
reactor inlet which can melt down the membrane.
This problem is completely circumvented in flu-
idized bed membrane reactors. In this case both
autothermal reforming and hydrogen recovery
can be performed in a single reactor.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_232-2
According to Deshmukh et al. (2007) the main
advantages of the MAFBR can be listed as
follows:
• Negligible pressure drop, which allows using
small particle sizes resulting in limited inter-
nal mass and heat transfer limitations (higher
effectiveness factors)
• (Virtual) Isothermal conditions
• Flexibility in membrane and heat transfer sur-
face area and arrangement of the membrane
bundles
• Improved fluidization behavior as a result of:
• Compartmentalization, i.e., reduced axial
gas back-mixing.
Reduced average bubble size due to enhanced
bubble breakage, resulting in improved bubble to
emulsion mass transfer.
MAFBR for hydrogen production also cir-
cumvent the bed-to-wall mass transfer limitations
affecting packed bed membrane reactors. It has
been demonstrated that higher membrane fluxes
(possible with nowadays membranes) will cause
a significant increase of the concentration polar-
ization in packed bed membrane reactors, even in
membrane tubes with a diameter as small as 1 cm.
By using the MAFBR, the membrane area
required for a fixed hydrogen flux can be
decreased by 50 % if compared with packed bed
reactors (Gallucci et al. 2010a).
2 Fluidized Bed Membrane Reactors
Even though Rahimpour and coworkers often
used fluidized bed membrane reactor for distrib-
utive hydrogen feeding in methanol reactors (see
Rahimpour and Lotfinejad 2008), most of the
literature has focused on pure hydrogen produc-
tion through Pd-based membranes (see among
others Adris et al. 1991; Prasad and Elnashaie
2002) and on autothermal reforming reactions
(see a.o. Grace et al. 2001; Gallucci et al. 2010b).
References
Adris AM, Elnashaie SSEH, Hughes R (1991) A fluidized
bed reactor for steam reforming of methane. Can
J Chem Eng 69:1061
Deshmukh SARK, Heinrich S, Mörl L, van Sint
Annaland M, Kuipers JAM (2007) Membrane assisted
fluidized bed reactors: potentials and hurdles. Chem
Eng Sci 62:416–436
Gallucci F, Van Sint Annaland M, Kuipers JAM (2010a)
Theoretical comparison of packed bed and fluidized
bed membrane reactors for methane reforming. Int
J Hydrog Energy 35:7142–7150
Gallucci F, Van Sint Annaland M, Kuipers JAM (2010b)
Pure hydrogen production via autothermal reforming
of ethanol in a fluidized bed membrane reactor. Int
J Hydrog Energy 35:1659–1668
Grace JR, Li X, Lim CJ (2001) Equilibrium modelling of
catalytic steam reforming of methane in membrane
reactors with oxygen addition. Catal Today
64:141–149
Prasad P, Elnashaie SSEH (2002) Novel circulating
fluidized-bed membrane reformer for the efficient pro-
duction of ultraclean fuels from hydrocarbons. Ind Eng
Chem Res 41:6518–6527
Rahimpour MR, Lotfinejad M (2008) Co-current and
countercurrent configurations for a membrane dual
type methanol reactor. Chem Eng Technol
31(1):38–57
Tiemersma TP, Patil CS, Sint Annaland MV, Kuipers
JAM (2006) Modelling of packed bed membrane reac-
tors for autothermal production of ultrapure hydrogen.
Chem Eng Sci 61(5):1602–1616
F
Food Processing by Membrane
Operations
Angela C. Macedo1,2 and F. Xavier3
1
ISMAI – University Institute of Maia, Avenida
Carlos Oliveira Campos, Avioso S. Pedro,
Portugal
2
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
3
Department of Chemical Engineering,
University of Porto, Porto, Portugal
Food processing consists of transformation of
raw ingredients into food, or food itself into
other forms. Food processing typically starts
with clean, harvested crops or butchered animal
products and uses them to produce safe and
attractive products – along the food chain, down
to the consumer at home (Marsh and Angold
2004). Various unit operations are part of the
current practice, which rely on either thermal
processing or mechanical work: the former are
less appropriate to heat-labile items and are also
characterized by poor thermodynamic efficiency.
Mechanical work is, to advantage, applied in
membrane-based processes: they take advantage
of a physical barrier (i.e., a porous membrane or
filter) to separate particles from a fluid based on
their size and shape and resort to high pressure
and tailor-made membranes with specific pore
sizes. The pore size distribution allows indeed
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_233-3
different possibilities in terms of separation to
be attained – via microfiltration, ultrafiltration,
nanofiltration, and reverse osmosis (sorted by
decreasing pore size) (Drioli et al. 2011).
Membrane processing has met with industrial
success in clarification and concentration of liq-
uid foods because it operates at room tempera-
ture, entails low energy consumption, and is
highly preformant with regard to a wide range
of contaminants – besides scaling up easily
(Sant’Anna et al. 2012); it may also increase
yield, and its high selectivity can be taken advan-
tage to improve control (Drioli et al. 2011). Mem-
branes are able to remove sediments,
microorganisms, and large-sized compounds;
they offer indeed an efficient way to gain superior
quality and safety without disturbing the basic
sensory profile of a food product. As major dis-
advantages, one should outline high hydraulic
pressure drops, limited maximum attainable con-
centration, and concentration
polarization – especially in media with high
loads of organic compounds (Petrotos
et al. 2010).
Microfiltration separates suspended particles,
typically from 0.1 to 10 mm (thus including bac-
teria); for sterilization purposes, 0.4–0.6 mm
membranes in dead-end and cross-flow filtration
modes are recommended. Permeate fluxes of the
order of 100,000 L.m 2.h 1 are typically
observed when processing (clean) water; liquid
foods usually reduce such a permeate flux to
100–200 L.m 2.h 1, owing primarily to
2 Food Processing by Membrane Operations
viscosity, fouling, and concentration polarization
(Accomazzo et al. 1988).
Ultrafiltration resorts to membranes with pore
sizes in the range of 0.1–0.001 mm; it is typically
intended for removal of high molecular weight
substances, colloidal materials, and polymeric
molecules of organic or inorganic nature. Ultra-
filtration is a cross-flow separation process – i.e.,
the liquid feed flows tangentially along the mem-
brane surface with a pressure drop across it, caus-
ing part of that stream to percolate the membrane
(thus producing a permeate). The type and
amount of species left in the remaining stream
(retentate) depend on the characteristics of the
membrane and the operating conditions, as well
as the composition of the original feed. Optimum
design and operation should take into account the
flow velocity, the pressure drop, the power con-
sumption, the rate of membrane fouling, and the
module cost. Since only high molecular weight
species are removed, the differential in osmotic
pressure across an ultrafiltration membrane is
usually negligible (Accomazzo et al. 1988).
Nanofiltration is a ▶ cross-flow filtration tech-
nology, usually listed between ultrafiltration and
reverse osmosis; the nominal pore size of the
membrane is typically ca. 1 nm, but the ▶ molec-
ular weight cutoff – which is typically less than
1,000 Da, rather than the nominal pore size – is to
be used for a more meaningful characterization.
Transmembrane pressures can go up to 3 MPa,
which require powerful pumping equipment; fur-
thermore, nanofilter membranes are quite suscep-
tible to scaling and fouling, so such modifiers as
antiscalants are often required.
Finally, reverse osmosis goes one step further
in filtration and allows separation of small
dissolved molecules in the Angstrom range; this
includes salts, sugars, and organic acids. The only
driving force for this process is the osmotic pres-
sure difference between the solutions lying on the
two sides of the permeable membrane. The cross-
flow configuration allows the membranes to self-
clean continually; further advantages encompass
relatively low hydraulic pressure and easy scale-
up (Sant’Anna et al. 2012).
Membrane contactors represent another
approach to membrane operations in food
processing – where separation does not rely spe-
cifically on the membrane acting as selective
barrier, but is instead based on phase equilibria.
Hence, mass transfer between phases is promoted
without dispersing one phase into the other, and
such disadvantages as flooding at high flow rates,
unloading at low flow rates, requirement for
emulsified state and density differences, and
high interfacial area are dramatically alleviated.
In principle, all traditional stripping, scrubbing,
absorption, evaporation, distillation, crystalliza-
tion, emulsification and liquid-liquid extraction,
as well as enzymatic catalysis can be carried out
following this configuration. This type of
contactor technology has found applications in
purification of water, wine fermentation, protein
extraction, and beverage carbonation (Stanojevíc
et al. 2003).
References
Accomazzo M, Ganzi G, Kaiser R (1988) Deionized (di)
water filtration technology. In: Tolliver D -
(ed) Handbook of contamination control in
microelectronic. Noyes Publications, Park Ridge,
pp 210–254
Drioli E, Stankiewicz A, Mecdonio F (2011) Membrane
engineering in process intensification – an overview.
J Membr Sci 380:1–8
Marsh R, Angold R (2004) Sources of contamination in
the food chain. In: Edwards M (ed) Detecting foreign
bodies in food. CRC Press, Boca Raton, pp 3–11
Petrotos K, Tsiadi A, Poirazis A, Papadopoulus D,
Petropakis H, Gkoutsidis P (2010) A description of a
flat geometry direct osmotic concentrator to concen-
trate tomato juice at ambient temperature and low
pressure. J Food Eng 97:235–242
Sant’Anna V, Marczacl L, Tessaro I (2012) Membrane
concentration of liquids foods by forward osmosis:
process and quality view. J Food Eng 11:483–489
Stanojevíc M, Lazarevíc B, Radíc D (2003) Review of
membrane contactor designs and applications of dif-
ferent modules in industry. FME Trans 31:91–98
F
Formulation by Membrane
Emulsification
Goran T. Vladisavljevic and Richard Holdich
Chemical Engineering Department,
Loughborough University, Leicestershire, UK
Membrane emulsification (ME) is a process of
forming emulsion by passing a pure dispersed
phase or pre-emulsion through a microporous
membrane (Fig. 1). The most commonly used
membranes for ME are Shirasu porous glass
(SPG) membrane and microsieve membranes. In
direct ME, fine droplets are produced at the mem-
brane/continuous phase interface by injecting a
pure liquid (the dispersed phase) through the
membrane into a second immiscible liquid (the
continuous phase) (Nakashima et al. 1991). The
dispersed phase should not wet the membrane
wall, i.e., hydrophobic and hydrophilic mem-
branes are used to produce water-in-oil and
oil-in-water emulsions, respectively. At low
transmembrane fluxes, uniform droplets can be
formed without applying any shear on the mem-
brane surface, solely by the action of interfacial
tension (Kukizaki 2009). In order to achieve
commercially significant throughputs in ME, the
shear stress is applied at the continuous phase/
membrane interface, usually by cross flow or
stirring (Fig. 2a–d). Cross-flow systems are easy
to scale up and can offer a continuous operation
and constant shear stress along the membrane
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_235-6
surface. Stirring systems are operated batchwise
and do not provide constant shear stress on the
membrane surface, but are easier to operate
because a closed loop recirculation of the contin-
uous phase stream is not needed and a batch size
can be very low, just 10 mL or even less.
The shear stress can also be generated by a
dynamic membrane (Fig. 1e) or pulsed flow
(Fig. 1f), in which case the droplet detachment
from the membrane surface is facilitated by rotat-
ing (Vladisavljević and Williams 2006) or vibrat-
ing (Holdich et al. 2010) the membrane within the
otherwise static continuous phase or providing
periodic flow pulsations in the continuous phase
(Holdich et al., 2013). In the dynamic and pulsed
flow membrane systems, the shear stress on the
membrane surface is decoupled from the cross-
flow velocity, and consequently, sufficiently high
shear stress can be achieved at any cross-flow
velocity, and emulsions with high dispersed
phase concentrations can be produced in a single
pass through the module.
In the dripping regime, the droplet size is
determined by a balance between the shear
force and the capillary force. The size of the
droplets produced is mainly affected by the
microstructure of the membrane (the pore size
distribution, pore shape, and pore spacing), trans-
membrane flux, surface shear stress, physical
properties of the continuous and dispersed
phase, and emulsion formulation. Surfactant mol-
ecules must not adsorb to the membrane surface,
and thus, cationic surfactants must not be used in
2 Formulation by Membrane Emulsification

Formulation by Membrane Emulsification, emulsification (ME): a “bottom-up” approach (direct

Fig. 1 Two different approaches used to obtain fine ME); b “Top-down” approach (premix ME)
droplets of oil-in-water emulsion in membrane

Formulation by Membrane Emulsification, Fig. 2 Different ME systems used to control shear stress on membrane
surface (Vladisavljević and Williams 2005)
Formulation by Membrane Emulsification
association with negatively charged membrane
(such as SPG membrane and oxidized silicon
microsieves) (Nakashima et al. 1993). The trans-
membrane pressure should not exceed ten times
the capillary pressure and the shear stress on the
membrane surface is usually in the range from
2 to 10 Pa (Vladisavljević et al. 2004). The drop-
let size is typically two to ten times higher than
the pore size and decreases with increasing the
shear stress on the membrane surface.
References
Holdich RG, Dragosavac MM, Vladisavljević GT,
Kosvintsev SR (2010) Membrane emulsification with
oscillating and stationary membranes. Ind Eng Chem
Res 49:3810–3817
Holdich RG, Dragosavac M, Vladisavljević GT,
Piacentini, E (2013) Continuous membrane emulsifi-
cation with pulsed (oscillatory) flow. Ind Eng Chem
Res 52:507–515
3
Kukizaki M (2009) Shirasu porous glass (SPG) membrane
emulsification in the absence of shear flow at the
membrane surface: influence of surfactant type and
concentration, viscosities of dispersed and continuous
phases, and transmembrane pressure. J Membr Sci
327:234–243
Nakashima T, Shimizu M, Kukizaki M (1991) Membrane
emulsification by microporous glass. Key Eng Mater
61–62:513–516
Nakashima T, Shimizu M, Kukizaki M (1993) Effect of
surfactant on production of monodispersed O/W emul-
sion in membrane emulsification. Kag Kog Ronbunshu
19:991–997
Vladisavljević GT, Williams RA (2005) Recent develop-
ments in manufacturing emulsions and particulate
products using membranes. Adv Colloid Interf Sci
113:1–20
Vladisavljević GT, Williams RA (2006) Manufacture of
large uniform droplets using rotating membrane emul-
sification. J Colloid Interface Sci 299:396–402
Vladisavljević GT, Lambrich U, Nakajima M, Schubert
H (2004) Production of O/W emulsions using SPG
membranes, ceramic a-Al2O3 membranes,
microfluidizer and a microchannel plate: a compara-
tive study. Colloid Surf A 232:199–207
F
Forward Osmosis (FO)
Abaynesh Yihdego Gebreyohannes1 and Lidietta
Giorno2
1
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
2
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, University
of Calabria, Rende (CS), Calabria, Italy
In literature, osmotic pressure-driven membrane
processes are known as direct osmosis (DO) or
forward osmosis (FO). FO dating back to the
early 1960s is a membrane contactor process
that utilizes osmotic pressure difference (Dp)
across the membrane for water transport through
a semipermeable membrane (Cartinella
et al. 2006; Cath et al. 2006) than a hydraulic
pressure as in RO. The osmotic pressure differ-
ence across the membrane arises from the use of
concentrated solution called draw solution
(DS) on the permeate side of the membrane
(Fig. 3a). Apparently FO may be a viable and
sustainable alternative to thermal-driven
(membrane distillation) and pressure-driven
(reverse osmosis) concentrating methods, which
are highly energy intensive, hence very expen-
sive. In the presence of natural sources of con-
centrated DS, e.g., seawater, FO can be very
attractive due to its significantly lower energy
demand for pumping (Tang et al. 2010). The
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_237-1
equation below is generally used to describe
water transport in FO:
J w ¼ AðsDp  DPÞ (1)
where Jw is the water flux, A the water perme-
ability constant of the membrane, s the reflection
coefficient, and DP is the applied pressure. For
FO, DP is zero.
Currently many researchers are focusing on
the use of FO for different applications, and
remarkable progresses are observed in optimiz-
ing the process through testing different DS, con-
figurations, and development of model equations
that could best explain the phenomena.
Hence, FO is reemerging as low-energy
demanding membrane operation (<30 kwh/m3)
(Beaudry et al. 1999) for dehydration of aqueous
solution (Klaysom et al. 2013), seawater desali-
nation (McCutcheon et al. 2005), wastewater
treatment and concentration of diluted streams
(Holloway et al. 2007), food processing
(Petrotos et al. 1998), removal of trace organic
matter (Cartinella et al. 2006), and for use in
membrane bioreactor (Zhang et al. 2012). As
shown in Fig. 1, there is an exponential rise in
the number of FO-related publications in the last
5 years. Similarly, the number of patents released
from 2009 to 2014 is significantly high (Fig. 2),
providing a pertinent prospect to its application in
various fields.
The following are summaries of the range of
potential advantages of FO process:
2 Forward Osmosis (FO)

Forward Osmosis (FO), Fig. 1 The number of publica- do?product=UA&search_mode=CitationReport&SID=

tions excluding patents retrieved from web of science T1GuVqD4QDADmHXOVbu&page=1&cr_pqid=1&
between the year 1996 and 2015 using the keyword “forward viewType=summary
osmosis.” http://apps.webofknowledge.com/CitationReport.

Forward Osmosis (FO), 30

Fig. 2 Number of patents
No of patenets per annum

related to FO from 2009 to

2014 retrieved from http://
worldwide.espacenet.com/ 20
using the key word
“forward osmosis”
10

0
2009 2010 2011
2012
2013
2014
Year

• Requires low/no hydraulic pressure since it is • Membrane fouling in FO is relatively low and
an osmotically driven process. more reversible and can be minimized by opti-
• Low energy consumption, thereby lowing mizing the hydrodynamics.
costs, if suitable draw solutes and their regen- • Numerous contaminants can be effectively
eration methods can be economically and rejected by the FO process.
technically developed. • Has the potential to help achieve high water
• Energy can be harvested from the mixing of recovery, which reduces the volume of desali-
freshwater and saline water by pressure- nation brine, a major environmental concern
retarded FO (PRO). for current desalination.
Forward Osmosis (FO)
• In the food and pharmaceutical processing, FO
can maintain color, taste, aroma, and nutrition
of the feed.
• In the medical applications, FO can help in the
controlled release of drugs with low oral bio-
availability in a controlled manner by osmotic
pumps.
FO Membranes, Membrane
Configurations, and Modeling
Membrane Transport
Except for a few authors such as McCutcheon
et al. (2005) which used a thin-film composite
polyamide membrane, most publications are
based on cellulose or cellulose derivate (cellulose
acetate) membranes mainly from Hydration Tech-
nology Inc. In addition, in most cases reverse
osmosis (RO) was used to reconcentrate the DS
which gets diluted in the course of FO.
Of the different membrane modules, spiral
wound modules are one of the most common
packing configurations in the membrane industry.
However, it cannot be used in its current design
for FO because a liquid stream cannot be forced
to flow on the support side (inside the envelope)
(Cath et al. 2006). Hence, for a continuous FO
operation, flat-sheet membrane and specially
designed spiral wound membrane are used.
Although applied in limited number, tubular
membranes are also very suitable for continuous
FO processing since they are self-supported, can
be fabricated easily, and allow free flow of liquid
on both sides of the membrane.
There are a number of papers discussing the
transport phenomena in FO process in particular
related to solution physicochemical properties, con-
centration polarization, and membrane fouling. For
detailed reading, the reader is referred to Tang
et al. (2010), McCutcheon and Elimelech (2006),
Tan and Ng (2008), and Zhao and Zou (2011).
Draw Solutions
In FO process, a concentrated solution on the
permeate side of the membrane is the source of
3
the osmotic driving force. In literature, various
names are given to this solution including: draw
solution, osmotic agent, osmotic media, driving
solution, osmotic engine, sample solution, or
brine (Cath et al. 2006). The main criterion for
selecting the type of draw solution (DS) is its
potential to create higher chemical potential
than the feed solution.
The DS and related osmotic pressures in the
FO process are important factors influencing
overall process performance. Many researchers
used salt solution as DS (Cartinella et al. 2006;
Cornelissen et al. 2008; Yong et al. 2012), while
in some cases sugars or ammonia–carbon dioxide
(McCutcheon et al. 2005) solutions were used.
According to Lutchmiah et al. (2014), based on
publication from 2005 to 2013, 40 % of the cases
utilized NaCl as DS. This is mainly attributed by
its high solubility (Cath et al. 2006), low cost
(Achilli et al. 2010), and relatively high osmotic
potential. The same author indicated that 12 %
used MgCl2, 8 % sugars, 10 % sulfates, and other
7 % used magnetic nanoparticles, real wastewa-
ter, carbonates, etc. In addition to these, seawater
has frequently been used as a DS (Cath
et al. 2010). However, its use was mostly affected
by abundant presence of particles and microor-
ganisms which may foul the subsequent system
used to reconcentrate the DS (in closed-loop sys-
tems) or cause fouling/biofouling in the FO unit,
hampering performance.
Concentration Polarization
and Membrane Fouling
Unlike pressure-driven membrane process, in FO
there are both dilutive and concentrative polari-
zation effects that result in a lower-than-expected
water flux. Furthermore, the concentration polar-
ization could be either external which occurs near
the surface of the active layer and the porous
support layer or internal which occurs inside the
substructure of porous support layer. As a result,
the process is always accompanied by great
reduction from the bulk osmotic pressure (Dpbulk)
to the effective osmotic pressure (Dpeffective) as
shown in Fig. 3b.
4 Forward Osmosis (FO)
a b
Δπ
Feed
DS
FO
Forward Osmosis (FO), Fig. 3 Water flows in FO sys-
tem where (a) water diffuses to the more saline side of the
membrane due to osmotic driving force under approxi-
mately zero hydraulic pressure and (b) the course of bulk
External Concentration Polarization
When the process is in FO mode of operation, i.e.,
feed solution facing the active side of the mem-
brane, there is accumulation of solute that is
rejected by the membrane. This will result in the
phenomena of concentrative external concentra-
tion polarization (ECP). At the same time, the DS
in contact with the permeate side of the mem-
brane gets diluted by the permeating water at the
permeate–membrane interface resulting in dilu-
tive external concentration polarization (ECP).
Due to these phenomena, the effective osmotic
driving force near the membrane is significantly
lower than the bulk (apparent) osmotic pressure
(Cath et al. 2006).
Interestingly, several studies have shown that
fouling induced by ECP in FO in most part is
reversible due to low foulant compaction as a
result of the negligible hydraulic pressure gradi-
ent. Therefore, FO holds a great potential to treat
wastewater (Lutchmiah et al. 2014), including
wastewater with high fouling propensity (Cicci
et al. 2013; Karaouzas et al. 2011). The main
strategy utilized to reduce the effect of ECP is
increased turbulence or cross flow velocity.
Moreover, recovering FO membrane perfor-
mance was possible using simple osmotic back
flush, after it is fouled. For example, an
FEED J
solute
Jw
ACTIVE LAYER
Δπmembrane
Δπbulk
POROUS SUPPORT
Δπeffective
DRAW SOLUTION
osmotic driving force reduction to effective osmotic driv-
ing force due to concentration polarization phenomena
intermittent osmotic back flush has given the
possibility to use a single FO membrane over
several cycles bringing the total membrane use
to 172 h, during the treatment of vegetation
wastewater (Gebreyohannes et al. 2015). This is
an important savings in lifetime, compared to the
complete performance loss observed in various
pressure-driven membrane operations. The FO
fouling is generally more pronounced when the
porous support layer is facing feed solution, since
this orientation is prone to sever internal pore
clogging.
Internal Concentration Polarization
The asymmetric FO membrane consists of a
dense active layer and a porous support layer,
which adds a more complex situation of concen-
tration polarization in FO. In FO applications,
where the active layer of the membrane faces
the feed solution and the porous support layer
faces the DS, there is also dilutive internal con-
centration polarization (ICP) within the porous
substructure. This phenomenon happens when
water diffuses through the active layer; the DS
within the porous substructure becomes diluted,
hence dramatically reduced effective osmotic
driving force. Unlike the external concentration
polarization, playing with the hydrodynamic
Forward Osmosis (FO) 5

Forward Osmosis (FO), Table 1 Examples of industrial plants that employed FO process
Water Pollutant rejection
Stream Plant name/location recovery DS (%)
Landfill leachate (Osmotek Coffin Butte RO: DS NaCl 99
Inc. 2003) Landfill, Corvallis, and water
Oregon 92 %
Direct potable reuse for advanced DOC NASA long – NaCl Direct potable reuse
life-support systems (Beaudry mission life-support
et al. 1999) system
Concentration of digested sludge Truckee Meadows RO NaCl 87–99
liquids (Holloway et al. 2007) Water Reclamation
Facility, Reno,
Nevada
Hydration bags (Hydration Hydration – Edibles, e.g., Free of
Technologies Inc. n.d.) Technology Inc. sugar, beverage microorganism,
powder macromolecules, and
ions

condition will not alleviate the problem of ICP.
Thus, an engineered solution for reduced internal
concentration polarization is optimization of the
thickness, porosity, and tortuosity of the porous
substructure (Cornelissen et al. 2008). It is worth
noting that compared to ECP, ICP has a more
prominent effect in significantly reducing the
effective driving force across the dense layer
from the bulk osmotic difference.
of the recovered pharmaceutically interesting
compounds.
Table 1 gives summary of industrial practices
on the use of FO process in various fields. It is
worth noting that in most wastewater treatment
applications, FO is used as a high-level
pretreatment step before an ultimate purification
step. An exception for this is a hydration bag,
which serves as a final treatment step to produce
potable water from wastewater.

Promising Application Areas

FO has been studied for a number of applications
including commercial applications, in the water and
wastewater treatment (e.g., extraction bags) and in
the pharmaceutical industry (e.g., osmotic pumps),
seawater/brackish water desalination, food
processing, drug delivery, and electric power gen-
eration. For instance, FO was used to concentrate
an oily wastewater from olive millings after remov-
ing courser particles in two different configurations.
In the first case the pre-filtered wastewater directly
fed to the FO process, while in another case perme-
ate of biocatalytic membrane reactor was used as
feed. In both cases, FO helped to reduce up to 70 %
of the initial volume while completely rejecting all
pollutants in the course of reclaiming purified water
and pharmacologically important compounds. As a
result it reduced the size of downstream process
required to further fractionation and concentration
Concluding Remark
Regardless of the limited presence of robust
membranes and membrane modules for FO, fun-
damental research on FO and the development of
new applications of FO are growing fast. How-
ever, the following points need to be addressed to
have a reliable commercial success:
• Development of new membranes in both flat-
sheet and hollow fiber configurations: The
development needs to orient in the production
of membrane and modules with high water
permeability, high solute rejection, limited
ICP, high chemical and mechanical stability,
and high-density packing methods for well-
performing flat-sheet FO membranes.
• Development of DS: Most desirable DS needs
to induce high osmotic pressure, requires low
6 Forward Osmosis (FO)
energy for reconcentration, and must be easily
separable from the product freshwater and
nonreactive with low or no toxicity.
References
Achilli A, Cath TY, Childress AE (2010) Selection of
inorganic-based draw solutions for forward osmosis
applications. J Membr Sci 364:233–241
Beaudry EG, Herron JR, Peterson SW (1999) Direct
osmosis concentration of waste water: final report.
Osmotek, Corvallis
Cartinella JL, Cath TY, Flynn MT, Miller GC, Hunter
KW, Childress AE (2006) Removal of natural steroid
hormones from wastewater using membrane contactor
processes. Environ Sci Technol 40:7381–7386
Cath TY, Childress AE, Elimelech M (2006) Forward
osmosis: principles, applications, and recent develop-
ments. J Membr Sci 281:70–87
Cath TY, Hancock NT, Lundin CD, Hoppe-Jones C,
Drewes JE (2010) A multi-barrier osmotic dilution
process for simultaneous desalination and purification
of impaired water. J Membr Sci 362:417–426
Cicci A, Stoller M, Bravi M (2013) Microalgal biomass
production by using ultra- and nanofiltration mem-
brane fractions of olive mill wastewater. Water Res
47:4710–4718
Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin
J-J, Oo H, Wessels LP (2008) Membrane fouling and
process performance of forward osmosis membranes
on activated sludge. J Membr Sci 319:158–168
Gebreyohannes AY, Curcio E, Poerio T, Mazzei R, Di
Profio G, Drioli E, Giorno L (2015) Treatment of olive
mill wastewater by forward osmosis. Sep Purif
Technol 147:292–302
Holloway RW, Childress AE, Dennett KE, Cath TY
(2007) Forward osmosis for concentration of anaero-
bic digester centrate. Water Res 41:4005–4014
Hydration Technologies Inc. (n.d.) Hydration bags-
technology overview: http://www.hydrationtech.com/
merchant.mv?Screen=CTGY&StoreCode=MHTI&
CategoryCode=TECH-FO
Karaouzas I, Skoulikidis NT, Giannakou U, Albanis TA
(2011) Spatial and temporal effects of olive mill
wastewaters to stream macroinvertebrates and aquatic
ecosystems status. Water Res 45:6334–6346
Klaysom C, Cath TY, Depuydt T, Vankelecom IFJ
(2013) Forward and pressure retarded osmosis: poten-
tial solutions for global challenges in energy and water
supply. Chem Soc Rev 42:6959–6989
Lutchmiah K, Verliefde ARD, Roest K, Rietveld LC,
Cornelissen ER (2014) Forward osmosis for applica-
tion in wastewater treatment: a review. Water Res
58:179–197
McCutcheon JR, Elimelech M (2006) Influence of con-
centrative and dilutive internal concentration polariza-
tion on flux behavior in forward osmosis. J Membr Sci
284:237–247
McCutcheon JR, McGinnis RL, Elimelech M (2005)
A novel ammonia—carbon dioxide forward (direct)
osmosis desalination process. Desalination 174:1–11
Osmotek Inc. (2003) Landfill leachate treatment http://
www.rimnetics.com/osmotek.htm
Petrotos KB, Quantick P, Petropakis H (1998) A study of
the direct osmotic concentration of tomato juice in
tubular membrane – module configuration. I. The
effect of certain basic process parameters on the pro-
cess performance. J Membr Sci 150:99–110
Tan CH, Ng HY (2008) Modified models to predict flux
behavior in forward osmosis in consideration of exter-
nal and internal concentration polarizations. J Membr
Sci 324:209–219
Tang CY, She Q, Lay WCL, Wang R, Fane AG
(2010) Coupled effects of internal concentration polar-
ization and fouling on flux behavior of forward osmo-
sis membranes during humic acid filtration. J Membr
Sci 354:123–133
Yong JS, Phillip WA, Elimelech M (2012) Coupled
reverse draw solute permeation and water flux in for-
ward osmosis with neutral draw solutes. J Membr Sci
392–393:9–17
Zhang J, Loong WLC, Chou S, Tang C, Wang R, Fane AG
(2012) Membrane biofouling and scaling in forward
osmosis membrane bioreactor. J Membr Sci
403–404:8–14
Zhao S, Zou L (2011) Relating solution physicochemical
properties to internal concentration polarization in for-
ward osmosis. J Membr Sci 379:459–467
F
Fouling Index
Napoleone D’Agostino and Lidietta Giorno
Institute on Membrane Technology, National
Research Council (ITM-CNR), University of
Calabria, Rende (CS), Italy
Synonyms
Combined Fouling Index (CFI); Membrane Foul-
ing Index; Modified Fouling Index (MFI); Silt
Fouling Index (SFI)
Membrane fouling is an inevitable phenomenon
in membrane processes and reduces the effi-
ciency and the economic viability of the mem-
brane processes. All the fouling stages such as
pore blocking and cake layer not only decrease
the permeate flux during a membrane process but
they could influence negatively the permeate
quality. Understanding the membrane fouling
means that it is possible to develop a method to
measure and predict the fouling potential with
respect to a membrane. There is a pressing need
for a reliable method able to do that.
Simple membrane experiments such as Silt
Density Index (SDI) and Modified Fouling
Index (MFI) are fouling index methods used to
evaluate the particulate fouling potential of a feed
water on reverse osmosis (RO) and nanofiltration
(NF) membrane process (Salinas-Rodriguez SG
et al. 2015). The utilization of fouling indices
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_239-1
enables to determine, e.g., the pretreatment
requirements without conducting a pilot study
which needs considerable time and expenses.
Although these indices are the standardized
parameters and widely used in engineering prac-
tices, they are considered to be unsatisfactory
indicators that often fail to reflect the true fouling
strength of the feed water.
SDI and MFI are performed using a membrane
with 0.45 mm pores. The SDI test, defined by a
standard method instructed in ASTM-D4189-07
(2014), is a dead-end filtration conducted on the
feed at 207 psi through a 47 mm diameter
microfiltration membrane with 0.45 mm pores.
The rate of plugging is measured and expressed
as % flux decline per minute. Fouling index by
SDI is obtained by Eq. 1:


1  ti =tf
SDI ¼  100 (1)
t
In Eq. 1, ti is the initial time interval to collect
500 ml of permeate, and tf is the final time inter-
val to collect the same volume of permeate after a
time interval t of 5, 10, and/or 15 min.
The limitations of the SDI test are well
documented (Alhadidi et al. 2011; Rachman
et al. 2013; Nahrstedt et al. 2008), and include: no
correction for test water temperature; the result is
heavily dependent on the test membrane perme-
ability; not applicable for testing high fouling
feed water, e.g., raw water(ASTM recommends
that turbidity should be <1 NTU); not applicable
2 Fouling Index
for testing UF permeate, which is increasingly
being used in desalination pretreatment; no linear
relation with colloidal/suspended matter; fouling
potential of particles smaller than 0.45 mm is not
measured; and it is not based on any filtration
mechanism.
To overcome these deficiencies, the Modified
Fouling Index using the same 0.45 mm membrane
filters (MFI0.45) was developed. The MFI0.45 can
achieve the linear relationship between concen-
tration and flux decline, but still cannot accu-
rately predict flux decline. Boerlage
et al. (2002) confirmed that this is due to the
fact that in RO, fouling is caused by smaller
colloids that are not retained by the
microfiltration membranes used in the MF-
I. Seeing the above complexities of fouling mech-
anisms, this is not unexpected. The MFI0.45 test is
similar to the SDI test (Schippers and Verdouw
1980), but the volume is recorded every 20 s for
20 min. It takes into account that initially pore
blocking occurs, followed by cake/gel filtration,
and finally cake/gel blocking and/or enhanced
compression occurs. The cake filtration can be
identified by plotting t/V versus V, where t is the
time and V is the volume. The slope in this region
is the fouling index. The obtained MFI0.45 value
is corrected for temperature and pressure and
shows a linear relation with colloidal/suspended
matter concentration. MFI is derived in Eq. 2, and
it is defined as the slope of an inverse flow rate
(1/Q) versus cumulative volume (V) curve:
1 Index (MFI), and the linear correlation of the
¼ a þ MFI  V (2)
Q water mass transfer coefficient (MTC). Three
Predicting the rate of fouling in RO systems
based on the MFI0.45 is possible, assuming that
cake/gel filtration is the dominant mechanism.
However, the predicted rate of fouling turns out
to be very low for MFI of 1 s/L2 (equivalent to
SDI15 1–3). A pressure increase of 1 bar is
predicted to occur in more than 100 years with
RO feed water with an MFI = 1 s/L2.
Both MFI0.45 and SDI underestimate the foul-
ing observed in practice.
As the SDI and the MFI0.45 do not include
smaller colloid sizes, a new index using an
ultrafiltration (UF) membrane has been devel-
oped. Boerlage et al. tested this MFI-UF as a
function of molecular weight cutoff (MWCO,
1–100 kDa) of the UF membranes and obtained
values ranging from 2000 to 13,000 s/L2
(as compared to MFI0.45 values of 1–5 s/L2).
Higher values were linked to the retention of
smaller colloids as well as cake filtration of the
retained particles, although a correlation with the
MWCO was not apparent. While other mem-
brane characteristics may be partly responsible
for those varied results, it is also important to note
that fouling at such MWCOs is complex and
cannot be solely attributed to particulates.
A 13 kDa membrane was established to be the
best membrane for such tests.
Boerlage et al. used a 13 kDa UF membrane
(estimated pore dimension 9 nm) to measure
fouling potential and effectiveness of
pretreatment and compare the results with the
SDI and the MFI0.45. MFI-UF can be operated
in constant flow or pressure mode. The MFI-UF
values were in fact 400–1400 times higher than
the MFI0.45 due to the smaller particles captured.
The MFI-UF can also be used to determine the
effectiveness of pretreatment with regard to
reduction of fouling potential. Roorda and van
der Graaf (2001) used the MFI-UF to determine
the fouling potential of UF membranes and con-
firmed the dependence on membrane type. As a
general evaluation, Reiss and Taylor compared
three parameters used to investigate fouling: the
Silt Density Index (SDI), the Modified Fouling
different NF pilot systems were used with differ-
ent pretreatments including activated carbon and
MF. No correlation between the different param-
eters was obtained, indicating that the filtration
laws on which the models are based might not be
valid for NF. Hence, these parameters need to be
used with caution.
SDI and MFI seem to be difficult if there is
more than one type of fouling mechanisms.
Another approach to estimate fouling potential
due to various fouling mechanisms is attempted
by combining MFI values measured using multi-
ple test membranes. This method, which is
Fouling Index
designated as the Combined Fouling Index (CFI),
allows considering the contribution of particles,
hydrophobic matters, colloids, and organics to
RO/NF fouling at the same time. J.-S. Choi
et al. (2009) used three different membranes: a
hydrophilic microfiltration membrane, a hydro-
phobic microfiltration membrane, and a hydro-
phobic ultrafiltration membrane in order to study
the efficiency of different pretreatments. The
Combined Fouling Index value was obtained
using Eq. 3:
CFI ¼ o1 M1 þ o2 M2 þ o3 M3 þ o4 (3)
where M1, M2, and M3 are the MFI values of the
three membranes and o1, o2, o3, and o4 are
weighting factors depending on the characteris-
tics of RO/NF membrane because they are
closely related to fouling mechanisms. The
weighting factors were calculated from the flux
decline rate of each membrane.
CFI values are in good agreement with
nanofiltration flux decline because with this test
is possible considering the impact of different
foulants.
In addition, it is also possible to use more than
three test membranes to obtain more information
on the characteristics of feed water.
3
References
Alhadidi A, Kemperman AJB, Schippers JC, Wessling M,
Van Der Meer WGJ (2011) The influence of mem-
brane properties on the Silt Density Index. J Membr
Sci 384:205–218
ASTM, D4189-07 (2014) Standard test method for Slit
Density Index (SDI) of water, ASTM International,
West Conshohocken, PA, 2014
Boerlage SFE, Kennedy MD, Dickson M, El-Hodali DEY,
Schippers JC (2002) The modified fouling index using
ultrafiltration membranes (MFI-UF): characterisation,
filtration mechanisms and proposed reference mem-
brane. J Membr Sci 197:1–21
Choi J-S, Hwang T-M, Lee H, Hong S (2009)
A systematic approach to determine the fouling index
for a RO/NF membrane process. Desalination
238:117–127
Nahrstedt A, Camargo Schmale J (2008) New insights into
SDI and MFI measurements. Water Sci Technol Water
Supply 8:401–412
Rachman RM, Ghaffour N, Waly F, Amy GL
(2013) Assessment of Silt Density Index (SDI) as
fouling propensity parameter in reverse osmosis
(RO) desalination systems. Desalination Water Treat
51:1091–1103
Roorda JH, van derGraaf JHJM (2001) New parameter for
monitoring fouling during ultrafiltration of WWTP
effluent. Water Sci Technol 43(10):241–248
Salinas-Rodriguez SG, Amy GL, Schippers JC, Kennedy
MD (2015) The Modified Fouling Index Ultrafiltration
constant flux for assessing particulate/colloidal fouling
of RO systems. Desalination 365:79–91
Schippers JC, Verdouw J (1980) The Modified Fouling
Index, a method of determining the fouling character-
istic of water. Desalination 32:137–148
F
Fractional Free Volume (FFV)
Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Fractional free volume (FFV) is an empirical
dimensionless parameter that characterizes free
volume in polymers. FFV can be defined as the
ratio Vf/Vsp, where Vf (cm3/g) is the free volume
andVsp (cm3/g) is the specific volume of the poly-
mer, the latter parameter being the reciprocal
density r. The value of Vf can be calculated
using Bondi (1968) formula Vf = Vsp – Voc,
where Voc is the occupied volume, and it can be
estimated as Voc = 1.3 Vw, where Vw is van der
Waals volume of the repeat unit of the polymer.
Such an estimate gives the FFV values of most
polymers in the range of 10–25 %. However there
are examples when FFV is as large as 35 %
(polytrimethylsilyl propyne). In spite of its wide
usefulness, such definition of FFV has many dis-
advantages and is being often criticized. In the
case of glassy polymers, the density may depend
on prior history of the sample and, to some extent,
on the method of determination. The coefficient
1.3 in calculating Voc is estimated from packing
density of molecular crystals at 0 K and cannot
adequately describe polymers at room tempera-
ture. In addition, calculation of Vw of a repeat
unit as the sum of the increments of van der
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_243-4
Waals volumes of atoms that form this repeat
unit can lead to some inaccuracies. Since this
approach poorly takes into account the dead vol-
ume which depends on conformations of the
chain and is different for different gases, quantum
chemical corrections are desirable. More reliable
results were reported by Ronova et al. (2003). So
FFV found in this way can be considered as a
semiquantitative parameter suitable for compari-
son of series of polymers. Park and Paul (1997)
assumed that FFV can be considered not as a
universal property of polymers. Gases with dif-
ferent molecular dimensions can “feel” different
parts of the size distribution of free volume. So an
empirical method for calculation of occupied
volume specific for each gas was proposed. This
group contribution method allows better predic-
tions of the permeability coefficients based on
modified FFV.
Positron annihilation lifetime spectroscopy
(PALS) also allows an estimation of fractional
free volume as FFV = Nvf, where N is hole
number density (concentration of holes) and vf
is the mean volume of the spherical hole with the
radius R in the polymer or vf = 4/3 (pR3). The
FFV values found in this manner are usually
smaller than FFV estimated via Bondi by a factor
3–4. It is explained by the fact that a big fraction
of size distribution of free volume in polymers
consists of holes with the radii inaccessible to
o-positronium having the size of 1.06 Å. This is
confirmed by the calculations using molecular
dynamics method (Hofmann et al. 2002):
2 Fractional Free Volume (FFV)
extrapolation of FFV to the zero radius of probe
results in FFV values much greater than those
found via PALS.
References
Bondi A (1968) Physical properties of molecular crystals,
liquids, and gases. Wiley, New York
Hofmann D, Heuchel M, Yampolskii Y, Khotimskii V,
Shantarovich V (2002) Free volume distribution in
ultrahigh and lower free volume polymers: compari-
son between molecular modeling and positron lifetime
studies. Macromolecules 35:2129–2140
Park JY, Paul DR (1997) Correlation and prediction of gas
permeability of glassy polymer membrane materials
via a modified free volume based group contribution
method. J Membr Sci 125:23–39
Ronova I, Rozhkov E, Alentiev A, Yampolskii Y (2003)
Occupied and accessible volumes in glassy polymers
and their relation with gas permeation parameters.
Macromol Theory Simul 12:425–439
F
Fractionation of Fish Protein
Hydrolysates
Marie-Pierre Belleville
Institut Européen des Membranes (IEM): UMR
CNRS 5635, Université de Montpellier II,
Montpellier, France
Each year the processing industry of marine spe-
cies generates large amounts of solid by-products
such as filleting wastes, heads, etc. which are
usually converted to fish meal and oil for feed.
However, these by-products often contain high
concentrations of proteins that can be transformed
into peptides through enzymatic hydrolysis. Fish
protein hydrolysates (FPH) possess good nutri-
tional properties and biological activities such as
antioxidative, anticarcinogenic, immunological
activities, etc. (Chalamaiah et al. 2012). They
can thus represent marketable and value-added
products to be used as food and feed. Although
biological properties of peptides are related to
various characteristics, molecular weight (MW),
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_245-5
amino acid sequence, hydrophobicity, charge, and
acidobasic character, the MW seems to be one of
the most important ones. In particular peptides
with MW between 1 and 4 kDa have been identi-
fied as the most bioactive ones (Hsu 2010). The
pressure-driven membrane processes thus appear
to be good candidates to fractionate and concen-
trate FPHs in view to produce peptide fractions
with high specific activity. Firstly peptides can be
separated from nonhydrolysed proteins owing to
UF with high molecular weight cutoff (MWCO)
membranes (~20 kDa). Then peptide hydrolysates
can be fractionated according to their size with UF
membranes of intermediate MWCO (4–8 kDa);
the recovery yields are improved if UF is com-
bined with diafiltration. Finally the concentration
of selected fractions can be carried out with
nanofiltration (NF) membranes of low MWCO
(200–300 Da) (Chabeaud et al. 2009; Vandanjon
et al. 2009). Figure 1 shows the molecular weight
distribution of different peptide fractions obtained
after UF/NF fractionation of a tuna dark muscle
hydrolysate.
2 Fractionation of Fish Protein Hydrolysates

a
0.3 kDa FPH
0.40 1 kDa
UF permeate
0.35 UF Retentate

0.30

0.25
AU

0.20

0.15 4 kDa

0.10 7 kDa

0.05

0.00
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
Minutes
b
1.80 0.3 kDa
UF permeate
1.60 1 kDa
NF permeate
NF Retentate
1.40

1.20

1.00
AU

0.80

0.60
4 kDa
0.40

0.20

0.00
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
Minutes

Fractionation of Fish Protein Hydrolysates,
Fig. 1 Molecular weight distribution of peptides obtained
by enzymatic hydrolysis of tuna dark muscle – (a) Com-
parison of permeate and retentate obtained by UF com-
bined with diafiltration (8 kDa ceramic membrane, (Inside
CéRAMTM, Tami Industries)) with the raw fish protein
hydrolysate (FPH) (feed of the UF step) – (b) Comparison
of permeate and retentate obtained by NF (NP010,
Microdyn Nadir) with the UF permeate (feed of the NF
step) (Superdex-peptide HR 10/300 – Eluant: Water/TFA/
ACN: 70/0.1/30)

References proximate composition, amino acid composition, anti-

Chabeaud A, Vandanjon L, Bourseau P, Jaouen P,
Chaplain-Derouiniot M, Guerard F (2009) Perfor-
mances of ultrafiltration membranes for fractionating
a fish protein hydrolysate: application to the refining of
bioactive peptidic fractions. Sep Purif Technol
66:463–471
Chalamaiah M, Dinesh kumar B, Hemalatha R,
Jyothirmayi T (2012) Fish protein hydrolysates:
oxidant activities and applications: a review. Food
Chem 135:3020–3038
Hsu K-C (2010) Purification of antioxidative peptides pre-
pared from enzymatic hydrolysates of tuna dark muscle
by-product. Food Chem 122:42–48
Vandanjon L, Grignon M, Courois E, Bourseau P, Jaouen
P (2009) Fractionating white fish fillet hydrolysates by
ultrafiltration and nanofiltration. J Food Eng 95:36–44
F
Fractionation of Milk by Membrane
Operations
Marie-Pierre Belleville
Institut Européen des Membranes (IEM): UMR
CNRS 5635, Université de Montpellier II,
Montpellier, France
Milk is a complex colloidal suspension
containing many classes of different size compo-
nents (salts, soluble proteins, casein micelles, fat
globules, microorganisms, etc. (see Table 1))
which can be well separated from others
according to their size or charge, thanks to mem-
brane techniques (Brans et al. 2004; Pouliot
2008; Gésan-Guiziou 2010).
Since the 1980s, ultrafiltration (UF) has been
widely used in dairy industries in order to con-
centrate the protein fraction of milk without any
denaturation. This operation is generally carried
out on spiral wound polymer membranes or to a
lesser extent on tubular ceramic membranes with
molecular weight cutoff (MWCO) 10–50 kDa
and at a transmembrane pressure of
200–400 kPa. According to the concentration
level, different types of concentrate can be dis-
tinguished. UF of skimmed milk with low vol-
ume reduction factors (VRF up to 1.7 (the ratio
between either the volumes of feed and retentate
in discontinuous mode or flow rates of feed and
retentate in continuous mode)) leads to the pro-
tein standardization of both drinking and cheese
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_246-5
milks. The use of such milks permits a better
process control of continuous cheese-making
processes and leads to a constant quality of prod-
ucts throughout the year. The use of intermediate-
concentrated retentates (1.7 < VRF <5) and
high-concentrated retentates (VRF 5–7) permits
the continuous production of numerous cheese
varieties (fresh unripened cheeses, soft and
semihard cheeses) with high yield and very little
whey drainage. All these cheese-making pro-
cesses are derived from the famous worldwide
process known as MMV process after the inves-
tigators Maubois, Mocquot, and Vassal (Gésan-
Guiziou 2010).
Microfiltration (MF) is an alternative to cen-
trifugation for the removal of bacteria and spores
from skimmed milk in order to extend its shelf
life without applying a time-temperature treat-
ment. MF is thus carried out with multichannel
ceramic membranes with a pore diameter of
1.4 mm at high tangential velocity (6–9 m s 1)
and low transmembrane pressure (TMP)
(50 kPa). In order to limit the fouling phenomena,
a uniform TMP is applied all along the mem-
brane, thanks to the circulation of the permeate
cocurrent of the retentate (Bactocatch system ®,
AlphaLaval; Invesys ® APV) or thanks to the use
of ceramic membranes with linear hydraulic-
resistance gradient (GP Membralox ® membrane
Pall-Exekia; Isoflux ® membranes Tami-
Industries). MF of skimmed milk on a 0.2 mm
ceramic membrane permits the concentration of
casein micelles. One hundred percent of the
2 Fractionation of Milk by Membrane Operations

Fractionation of Milk by Membrane Operations, (WPI). Finally MF can be also used for the sep-
Table 1 Approximate composition of milk aration of milk fat into small (<3 mm) and large
Size (mm) or (>5 mm) globules. This operation is achieved
Concentration molecular weight with ceramic membranes with nominal pore size
Components (g L 1) (Da)
higher than 2 mm. The permeate which is
Water 870–875
enriched in small globule fraction leads to the
Fat 34–44 0.15–15 mm
production of cheeses with smoother and finer
Lactose 48–50 342 Da
Proteins 32–35
texture.
Caseins 25–28 50–500 mm
(micelles)
Soluble 5–7 14.2–150 kDa
proteins
References
Ashes 8–9
(mineral and Brans G, Schroën CGPH, van der Sman RGM, Boom RM
salts) (2004) Membrane fractionation of milk: state of the art
and challenges. J Membr Sci 243:263–272
Gésan-Guiziou G (2010) Separation technologies in dairy
and egg processing. In: Rizvi SSH (ed) Separation,
extraction and concentration processes in the food,
caseins are recovered in the retentate without any beverage and nutraceutical industries. Woodhead
Food Series, Oxford, pp 341–380
denaturation, while the permeate which is sterile Pouliot Y (2008) Membrane processes in dairy
and free of phage particles presents a composition technology – from a simple idea to worldwide pana-
close to that of whey. It can be used to prepare cea. Int Dairy J 18:735–740
whey protein concentrate (WPC) and isolate
F
Fractionation of Whey by Membrane (gelling, foaming, water binding, etc.), and phys-
Operations iological functionalities.
Marie-Pierre Belleville
Institut Européen des Membranes (IEM): UMR
CNRS 5635, Université de Montpellier II,
Montpellier, France
Whey is a coproduct of cheese-making and casein
manufacture in the dairy industry; it is the liquid
drained from the curd obtained after addition of
rennet (chymosin) or mineral/organic, or the per-
meate obtained during skimmed milk
microfiltration (MF) in view of casein concentra-
tion. Whey contains many classes of different-
size components (salts, lactose, soluble proteins
(mainly b-lactoglobulin and a-lactalbumin),
residual casein, microorganisms, etc. (see
Table 1)), but its composition depends on the
cheese-making process. The addition of enzyme
or rennet milk leads to sweet whey (pH 6.2–6.4),
whereas acid whey (pH 4.6–5) is obtained after
acidic coagulation of milk. Considered as waste
for years, whey is now widely used as food ingre-
dients in many goods and infant and dietetic
foods. Owing to chromatographic, electrodia-
lytic, and membrane techniques which permit
whey fractionation, it is possible to prepare valu-
able proteins and peptides with high nutritional
qualities (high biological value (BV), amino acid
profile, etc.), interesting physical properties
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_247-3
Whey protein concentrates (WPC) containing
35–85 % protein are prepared by ultrafiltration
(UF) with 10–20 kDa molecular weight cutoff
(MWCO) membranes. According to the concen-
tration level, different types of concentrate can be
distinguished. For 35 % WPC, the volume reduc-
tion factor (VRF) – the ratio between either the
volumes of feed and retentate in discontinuous
mode, or flow rates of feed and retentate in con-
tinuous mode – is about 4–7, whereas VRF of
13–50 are required to prepare 50–60 % WPC.
75–85 % WPC are obtained owing UF (VRF
30–35) combined with diafiltration in order to
remove minerals and lactose. Whey protein iso-
lates (WPI) containing more than 90 % of pro-
teins are generally produced from the
microfiltration permeate of skimmed milk using
ion-exchange chromatography (IEC).
Reverse osmosis (RO) permits the concentra-
tion of whey and its derivatives before dehydra-
tion. Compared to vacuum evaporation, the
energy consumption is lower, however, the con-
centration level is limited to about 25–28 % dry
matter (VRF 4) due to the increase of osmotic
pressure and viscosity and in order to avoid salt
precipitation and lactose crystallization.
As the high salt content of whey decreases its
nutritional value and generates processing diffi-
culties, demineralization of whey is carried out
before drying. Electrodialysis (ED) and/or
ion-exchange chromatography (IEC) are
2 Fractionation of Whey by Membrane Operations

Fractionation of Whey by Membrane Operations, whey to be demineralized should be previously

Table 1 Approximate composition of sweet and concentrated by RO, these techniques involve
acid whey
high investment and running costs and generate
Sweet whey Acid whey large volumes of polluting effluents. On the con-
Components (%) (%)
trary, nanofiltration (NF) appears to be more
Water 93–94 94–95
attractive even if this process leads to a lower
Lactose 4.5–5 3.8–4.3
level of demineralization. NF permits to concen-
Lactic acid Traces Up to 0.8
Fat Traces Traces
trate and demineralize the whey simultaneously
Total proteins 0.8–1.0 0.8–1.0 at low transmembrane pressure. The process is
Soluble proteins 0.6–0.65 0.6–0.65 thus more cost-effective and environmentally
Ashes (mineral and 0.5–0.7 0.5–0.7 friendly compared to ED and IEC. In addition,
salts) as nutrition value ions such as calcium are more
retained by the membrane than monovalent ions
(such as Cl ), the final products show higher
nutritional and technological properties.
currently used to achieve demineralization of
whey in the range 50–90 %. However, as the
F
Fractionation of White Wine Proteins been developed to achieve a selective separation
by Membrane Operations of wine proteins.
Johannes De Bruijn
Department of Agroindustry, Food Engineering
Group, Universidad de Concepcion, Chillan,
Chile
Fractionation is a separation process in which a
certain amount of a mixture is divided up into a
smaller number of quantities or fractions with
different molecular composition. Fractionation
is based on the difference in specific properties
between the individual components. Commonly
equilibrium has to be aimed between the recovery
of a specific compound and the desired purity of
each fraction.
Proteins from white wines differ in molecular
weight, ranging from 9 to 72 kDa, isoelectric
point with pI between 3 and 9, hydrophobicity,
degree of glycosylation, and thermal stability.
Proteins can exhibit positive effects such as the
stabilization of foam in sparkling wines, the inter-
action with aroma compounds, the protection of
wine against precipitation of tartaric salts, and the
interactions with other wine compounds such as
ethanol, polyphenols, and polysaccharides. How-
ever, they are also involved in some aspects that
can impair the acceptance of the final product by
consumers, such as haze formation during bottle
storage and wine allergy (Ferreira et al. 2002).
Therefore, several fractionation methods have
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_248-4
First some preparative separation methods are
often used such as dialysis (3.5 kDa cutoff mem-
branes) to eliminate low molecular weight com-
pounds, ultrafiltration (10 kDa cutoff
membranes) to isolate and concentrate proteins,
or protein precipitation by adding high concen-
tration of salts (ammonium sulfate) or organic
solvents (ethanol, methanol, or acetone). After-
wards, several chromatographic, electrophoretic,
and membrane separations are usually combined
that results into enriched protein fractions.
A number of different chromatographic tech-
niques, such as ion exchange, gel filtration/size
exclusion, hydrophobic interaction, affinity, and
chromatofocusing, have been developed for the
fractionation and purification of wine proteins. In
addition to chromatographic techniques, electro-
phoresis such as capillary electrophoresis and
capillary gel electrophoresis can be used to
achieve protein fractionation on a preparative
scale (Le Bourse et al. 2010).
Sequential fractionation of white wines
(Fig. 1) by using a series of ultrafiltration mem-
branes with decreasing molecular weight cutoff
ranging from 300, 100, 30 to 10 kDa allows to
study foam stability of champagne wines
(Abdallah et al. 2010) and protein haze stability
of white wines (De Bruijn et al. 2011a, b).
Ultracel PLC membranes of composite
regenerated cellulose within a stirred frontal cell
or a cross-flow unit should be preferred due to
2 Fractionation of White Wine Proteins by Membrane Operations

Fractionation of White
Wine Proteins by MWCO Colloids
Membrane Operations,
300 kDa
Fig. 1 Protein
fractionation by High MW macromolecules
ultrafiltration membranes
100 kDa

Intermediate MW macromolecules

30 kDa

Low MW macromolecules

10 kDa

Low MW compounds

their ultralow protein binding capacity. Although
the purity of protein fractions improves during
membrane fractionation, a decrease of protein
stability has been observed due to the retention
of high macromolecular species (glycoproteins
superior of 100 kDa) by the ultrafiltration mem-
brane. This changing composition of the wine
matrix makes membrane fractionation a complex
process.
References
Abdallah Z, Aguié-Béghin V, Abou-Saleh K, Douillard R,
Bliard C (2010) Isolation and analysis of macromolec-
ular fractions responsible for the surface properties in
native champagne wines. Food Res Int 43:982–987
De Bruijn J, Martínez-Oyanedel J, Loyola C, Seiter J,
Lobos F, Pérez-Arias R (2011a) Fractionation of
Sauvignon wine macromolecules by ultrafiltration
and diafiltration: impact of protein composition on
white wine haze stability. Int J Food Sci Technol
46:1691–1698
De Bruijn J, Martínez-Oyanedel J, Loyola C, Lobos F,
Seiter J, Pérez R (2011b) Impact of white wine mac-
romolecules on fractionation performance of ultrafil-
tration membranes. J Int Sci Vigne Vin 45:181–4188
Ferreira RB, Piçarra-Pereira MA, Monteiro S, Loureiro
VB, Teixeira AR (2002) The wine proteins. Trends
Food Sci Technol 12:230–239
Le Bourse D, Jégou S, Conreux A, Villaume S, Jeandet
P (2010) Review of preparative and analytical proce-
dures for the study of proteins in grape juice and wine.
Anal Chim Acta 667:33–42
F
Free Diffusion
Karel Friess
Department of Physical Chemistry, University of
Chemistry and Technology Prague, Prague,
Czech Republic
Free diffusion is a random nonrestricted walk or
shift of atoms, ions, or particles on distances
higher than those of the interatomic ones. From
the atomistic point of view, diffusion is consid-
ered as a result of the random walk of the diffus-
ing particles, self-propelled by thermal energy
(Brownian motion); from the phenomenological
(macroscopic) point of view, such (diffusion)
flux, which can be described by Fick’s laws, is
proportional to the minus gradient of chemical
potential and goes from regions of higher con-
centration to regions of lower concentration of
diffusant in appropriate (motionless) environ-
ment or solvent till concentration equalizing.
From thermodynamic point of view, diffusion
(mixing) in chemical system increases its entropy
(a rate of disorder) and tends to state with the
lowest inner energy.
An example of free diffusion is as follows (see
Fig. 1). If we consider infinite cylinder of unit
cross section, not with an instantaneous plane
source at x = 0, but with an initial distribution
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_249-1
of concentration given by c = c0 for x < 0 and
c = 0 for x > 0, at time t = 0, solution of the
Fick’s second law in the one-dimensional case
(coordinate x) after several treatment steps and
substitutions gives a solution in the form (Jost
1960; Cranck 1975)
  
c0 x
c¼ 1  erf pffiffiffiffiffi (1)
2 2 Dt
where erf x is Gauss error function
ðerf ðxÞ ¼ erf ðxÞ; erf ð1Þ ¼ 1Þ and D is a
diffusion coefficient. Thus, with if we imagine
at t = 0 in cylinder (column) one solution with
diffusing species with its concentration c = c0
(at x < 0) and a second solution (pure solvent)
with c = 0 (at x > 0) given in contact (with sharp
interface at x = 0). If such system is kept at stable
conditions (constant temperature and no vibra-
tions from outside which could cause convec-
tion), at times t > 0 a former sharp interface
tends to vanish due to diffusion between both
solutions, and at long times (t = 1) concentra-
tion in the whole system became identical and is
equal to the half of the initial concentration
c = c0/2.
2 Free Diffusion

Free Diffusion,
Fig. 1 Schematic draw of
free diffusion with two
solutions: a change of
concentration profile in
time given by Eq. 1 from
time t = 0 (left) to t = 1
(right)

Cross-References References

▶ Brown Motion Cranck J (1975) The mathematics of diffusion. Clarendon

Press, Oxford
▶ Diffusion
Jost W (1960) Diffusion in solids, liquids, gases. Aca-
▶ Fick Second Law demic, New York
F
Free Volume Distribution
Shantarovich Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Size distribution of free volume in glassy mem-
brane materials is accessible to estimation by
computer simulations (molecular dynamics,
MD) and to experimental studies by the probe
methods. In low permeable and highly selective
conventional glassy polymers like polyimides,
size distribution of free volume elements
(microcavities), according to MD, is located
within the range of microcavity radius 1–5 Å
and can be represented by the Gauss function
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_250-2
(Heuchel et al. 2004) (see Fig. 1). For polymers
with greater gas permeability such as poly
(trimethylsilyl propyne) (PTMSP) or amorphous
Teflon AF, according to MD, it is much wider and
extends up to microcavity radius 10–12 Å
(Hofmann et al. 2003) (see Fig. 2). Positron anni-
hilation lifetime spectroscopy (PALS) also indi-
cates widely distributed sizes of free volume in
highly permeable polymers. However, there are
two interpretations of wide size distribution.
According to Shantarovich et al. (1993) and
Consolati et al. (1996), lifetime distribution can
be represented by bimodal size distribution
(Fig. 3), while Dlubek (2008) proposed to con-
sider monomodal size distribution with variable
dispersion. Both approaches are consistent with
the results of MD simulation.
2 Free Volume Distribution

Free Volume
Distribution, Fig. 1 Size
distribution (MD) of free 0.03
volume in 6FDA-3MPD
polyimide accessible for
o-positronium probe
(Adopted from Heuchel 0.02

FFV
et al. (2004))

0.01

0
0 1 2 3 4 5 6 7 8
R, Å

Free Volume
Distribution, Fig. 2 Size 0.04
distribution (MD) of free
volume in PTMSP
accessible for
o-positronium probe 0.03
(Adopted from Hofmann
et al. (2003))
FFV

0.02

0.01

0
0 2 4 6 8 10 12
R, Å
Free Volume Distribution 3

Free Volume 0.8

Distribution, Fig. 3 Size
distribution (PALS) of free
volume in PTMSP 0.6
(Adopted from Hofmann
et al. (2002))
0.4

f (R)
0.2

2 3 4 5 6 7 8
R, Å

References Hofmann D, Heuchel M, Yampolskii Y, Khotimskii V,

Shantarovich V (2002) Macromolecules
Consolati TG, Genco I, Pegoraro M, Zandeighi L (1996) 35:2129–2140
J Polym Sci: Part B: Polym Phys 34:357–367 Hofmann D, Entrialgo-Castano M, Lerbret A, Heuchel M,
Dlubek G (2008) Positron annihilation spectroscopy. In: Yampolskii Y (2003) Macromolecules 36:8528–8538
Seidel A (ed) Encyclopedia of polymer science and Yampolskii Y, Shantaovich V, Chernyakovskii F,
technology. Wiley, Hoboken Kornilov A, Plate N (1993) J Appl Polym Sci 47:85–92
Heuchel M, Hofmann D, Pullumbi P (2004) Macromole-
cules 37:201–214
F
Free Volume Element
Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Free volume element (FVE) (synonyms:
microcavity, hole) is a conditional notion used
for description of free volume in polymers
(mainly in glassy polymers). Thus, in the positron
annihilation lifetime spectroscopy (PALS)
(Shrader and Jean 1988; Bartos 2000), it is
defined as a sphere with the diameter
R estimated using the Tao-Eldrup equation (Tao
1972; Eldrup et al. 1981) via the o-positronium
lifetimes ti. In this approach it is conceived that
polymer can be considered as a continuous matrix
with uniformly distributed in it spheres with the
size 4/3(pR3). It was also assumed that cylindri-
cal shape of FVE is a more realistic representa-
tion, so corresponding equation for calculation of
the volume of FVE was proposed (Goworek
et al. 2000). The PALS method permits an esti-
mation of the mean concentration of FVE or hole
number density N (Dlubek et al. 2003). In all the
polymers, the N values are limited within rela-
tively narrow range of (2–8) 1020 cm 3 at the
glass transition temperature Tg (Dlubek
et al. 2003; Yampolsakii 2010). Computer
modeling of polymers indicates that the use of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_251-2
FVEs dispersed in dense continuous matrix is
only a convenient oversimplification. In reality
the nanostructure of polymers is better approxi-
mated as a more or less continuous form of free
volume, though the sizes of FVEs get within the
size distribution of free volume according to
molecular dynamics (Hofmann et al. 2003).
Reference
Bartos J (2000) Positron annihilation spectroscopy of
polymers and rubbers. In: Meyers RA (ed) Encyclope-
dia of analytical chemistry. Wiley, Chichester, p 7968
Dlubek G, Bondarenko V, Pionteck J, Supej M, Wutzler
A, Krause-Rehberg R (2003) Free volume in two dif-
ferently plasticized poly(vinyl chloride)s: a positron
lifetime and PVT study. Polymer 44:1921–1926
Eldrup M, Lightbody D, Sherwood JN (1981) The tem-
perature dependence of positron lifetimes in solid
pivalic acid. Chem Phys 63:51–58
Goworek T, Ciesielski K, Jasinska B, Wawzyszuk J
(2000) Temperature variations of average o-Ps life-
time in porous media. Radiat Phys Chem 58:719–722
Hofmann D, Entrialgo-Castano M, Lerbret A, Heuchel M,
Yampolskii Yu (2003) Molecular modeling investiga-
tion of free volume distributions in stiff chain poly-
mers with conventional and ultrahigh free volume:
comparison between molecular modeling and positron
lifetime studies. Macromolecules 36:8528–8538
Shrader DM, Jean YC (eds) (1988) Positron and positro-
nium chemistry. Elsevier, Amsterdam
Tao J (1972) Positron annihilation in molecular sub-
stances. J Chem Phys 56:5499–5510
Yampolskii Yu (2010) On estimation of concentration of
free volume elements in polymers. Macromolecules
43:10185–10187
F
Free Volume Estimation
Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Originally, free volume was interpreted (H. Fujita,
M.H. Cohen and D. Turnbull, J.S. Vrentas and J.L.
Duda) as an abstract parameter that fits the equation
of free volume model. The methods for quantitative
determination of free volume were proposed by
S. Sugden and later by A. Bondi (1968). According
to the latter, free volume Vf (cc/g) can be estimated
as the difference: Vf = Vsp – Vocc, where the
specific volume is defined as Vsp = 1/r (r is the
polymer density), while occupied volume Vocc can
be found as 1.3 Vw, where Vw is the van der Waals
volume of the repeat unit of the polymer. The Vw
value can be estimated from the increments tabu-
lated for various groups (Van Krevelen and te
Nijenhuis 2009). The factor 1.3 is taken from the
packing density of molecular crystal at 0 K
(accounting for inaccessible volume). Bondi’s for-
mula was criticized: the factor 1.3 might not be a
universal constant, applicable in all cases; Vw of
repeat units cannot be considered as the sum of
increments of the groups that form it. However,
Vf value found using this formula is a simple and
convenient measure of free volume in polymers
(especially glassy) and it found a wide use. Often,
it is more convenient to use a dimensionless value,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_252-2
fractional free volume FFV defined as Vf/Vsp. It is
widely used in many correlations. In most poly-
mers, FFV is in the range 0.1–0.25; however,
there are examples where it reaches the value of
0.35.
Since the 1990s, several experimental
methods (so-called probe methods) appeared
and started to be used for the direct estimation
of free volume in polymers (Yampolskii 2007).
Among these methods (inverse gas chromatogra-
phy, 129Xe-NMR, and others), the most accepted
and reliable one is the positron annihilation life-
time spectroscopy (PALS) (Dlubek 2008). It is
based on the measurement of annihilation life-
times of o-Ps (hydrogen-like atom formed by
electron and positron): the longer its lifetime,
the larger is the microcavity in the polymer
where it resides and annihilates. The method per-
mits estimation of discreet lifetimes or its distri-
bution (hence, size distribution of microcavities).
In conventional glassy and rubbery polymers, the
radius of microcavity R (it is assumed that it has
spherical geometry) is in the range 0.2–0.3 nm;
however, in highly permeable polymers, it can be
as large as 0.7 nm. In conventional polymers,
o-Ps lifetime distribution and free volume size
distribution is monomodal (Gauss-type distribu-
tion). In highly permeable polymers, it is, as a
rule, bimodal with prevailing larger
microcavities. By combining PALS and PVT
data, it is possible to estimate the concentration
of microcavities or hole number density N -
(Dlubek 2008). In all polymers, the N values are
2 Free Volume Estimation
in the range 1020–1021 cm 3. It is possible also to
calculate PALS-based FFV = N(4/3)pR3. Differ-
ent probe methods give the radii of microcavities
in rather good agreement (Yampolskii 2007).
References
Bondi A (1968) Physical properties of molecular crystals,
liquids and gases. Wiley, New York
Dlubek G (2008) Positron annihilation spectroscopy. In:
Seidel A (ed) Encyclopedia of polymer science and
technology. Wiley, Hoboken
Van Krevelen DW, te Nijenhuis K (2009) Properties of
polymers. Their correlation with chemical structure,
their numerical estimation and prediction from addi-
tive group contributions. Elsevier, Amsterdam
Yampolskii Y (2007) Methods for investigation of free
volume in polymers. Russ Chem Rev 76:59–78
F
Free Volume Model
Yuri Yampolskii
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
The concept of free volume is extensively used in
respect of various properties of condensed
phases. Regarding nonporous polymeric mem-
branes, it is quite useful in the description of
diffusion phenomena. The model proposed by
Cohen and Turnbull (1959) for transport in liq-
uids and amorphous glasses considers a matrix
consisting from hard molecules. It gives the fol-
lowing equation for the diffusion coefficient as a
function of average free volume per molecule
vf : D ¼ A expðgv =vf Þ , where A is the con-
stant, g is the constant that takes into account
possible overlapping of microcavities, and v is
the minimum required volume of microcavity
and often is considered as the size of the diffusing
molecule. A modified equation was proposed
later by Fujita (1961) where instead of vf, the
fractional free volume (FFV) was used:
D ¼ Ad RTexpðBd =FFVÞ. It is accepted that
the constants Ad and Bd depend on the nature
(size) of the diffusants. These equations are
valid only when the concentration of penetrants
is small and they do not exert perturbation on
polymer matrix (e.g., swelling). In transport of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_253-2
organic vapors, much more complicated equa-
tions were proposed and used (Vrentas
et al. 1977; Petropoulos 1994). It is important
that these equations include an activation term
exp(-Ej/RT), where Ej is the energy needed for
the diffusing molecule to jump into the next hole.
Free volume found using either of
abovementioned models usually shows good cor-
relations with the diffusion coefficients of gases
in polymers and often with the gas permeability
coefficients. The concept of free volume was
strongly enriched by the use of contemporary
simulation methods (molecular dynamics, molec-
ular mechanics, and Monte Carlo) and experi-
mental probe techniques. However, in many
cases (especially for highly permeable poly-
mers), it is important to supplement the consider-
ation with information on connectivity
(openness) of free volume (Willmore et al. 2006).
References
Cohen MH, Turnbull D (1959) J Phys Chem
31:1164–1169
Fujita H (1961) Fortshcr Hochpolym-Forsch 3:1–47
Petropoulos JH (1994) In: Paul DR, Yampolskii Yu
P (eds) Polymeric gas separation membranes. CRC
Press, Boca Raton, p 17
Vrentas JS, Duda JL (1977) J Polym Sci Polym Phys Ed
15:403–417; J Appl Polym Sci 21(1977):1715–1728
Willmore FT, Wang X, Sanchez IC (2006) J Polym Sci
B Polym Phys 44:1385–1393
F

Freundlich Isotherm Q ¼ K:Cn (2)

in which K and n are constants at a given

Bart Van der Bruggen
temperature.
Department of Chemical Engineering, Process
When the Freundlich equation is written in
Engineering for Sustainable Systems (ProcESS),
logarithmic form, a linear relation between log
KU Leuven, Leuven, Belgium
Q and log C is obtained:

logQ ¼ logK þ nlogC (3)

A Freundlich isotherm is a mathematical expres-
sion for the adsorption equilibrium between a
fluid (liquid or gas) and a solid material. The
Freundlich equation is an empirical expression
representing the isothermal variation of adsorp-
tion of a liquid or gas onto the surface of a solid
material, derived by Freundlich (1909) as an
empirical relation.
For adsorption of a gas as the adsorbate to a
solid adsorbent, the following equation repre-
sents a Freundlich isotherm:
x 1
¼ kPn (1)
m
In this equation, x is the adsorbed quantity, m is
the mass of the adsorbent, P is the partial pressure
of the adsorbate in the gas, and k and n are empir-
ical constants for each adsorbent-adsorbate pair
at a given temperature.
For adsorption of a liquid, the relation between
the adsorbed amount per gram of the solid at
equilibrium Q (mg/g) and the concentration C in
solution at the equilibrium (mg/l or mg/l) is given
by the following equation:
Freundlich isotherms are often used to describe
adsorption equilibria between a membrane and a
feed solution. This is essential for the description
of phenomena such as membrane fouling (Van
der Bruggen et al. 2002) and breakthrough effects
due to desorption (McCallum et al. 2008) in
aqueous solutions. Desorption of adsorbed
organic compounds to the permeate may result
in negative apparent rejections when the concen-
tration of the organic compound in the membrane
phase is larger than the equilibrium permeate
concentration given by the Freundlich isotherm.
The permeate concentration during this unsteady-
state filtration period is similar to breakthrough
curves encountered in the description of adsorp-
tion columns. Kimura et al. (2003) demonstrated
that adsorption of hydrophobic compounds,
which can be described by the Freundlich equa-
tion, might lead to underestimation of the perme-
ate concentration (or overestimation of rejection)
due to saturation of the membrane and subse-
quent desorption. This is very important in the
translation of experimental results to real scale

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_254-3
2 Freundlich Isotherm
applications. Thus, a fundamental understanding
of adsorption is a prerequisite.
Adsorption equilibria using the Freundlich
isotherm can also be used for membrane charac-
terization. Ge et al. (2006) demonstrated that the
variation in membrane thickness and pore size
can be predicted by studying Freundlich iso-
therms. They found that when the variations
were larger, the time of total saturation is
delayed, the loading capacity at the point of
breakthrough decreases, the solute recovery effi-
ciency and ligand utilization efficiency decrease,
and the thickness of unused membrane increases.
The Freundlich isotherm is often used because
of its simplicity and wide applicability. However,
other isotherms can also be used to describe
adsorption on membrane surfaces. The most
commonly applied are the Langmuir isotherm
and the BET equation. The Langmuir model
was derived theoretically by Irving Langmuir in
1916 as a mathematical expression for monolayer
adsorption onto a solid surface. Although this
model has a theoretical basis, its application is
limited to monolayers; in addition, the Langmuir
model does not work well for rough surfaces,
which is often the case for membranes. The Lang-
muir model was extended in 1938 by Stephen
Brunauer, Paul Emmett, and Edward Teller,
who developed a new theoretical model for mul-
tilayer adsorption that became known as the BET
model (as an acronym for Brunauer-Emmett-
Teller). Although more complex than the empir-
ical Freundlich equation, it has the advantage of a
strong fundamental basis, which goes beyond the
simple approximation in the Freundlich model.
References
Freundlich H (1909) Kapillarchemie: eine Darstellung der
Chemie der Kolloide und verwandter Gebiete.
Akademische Verlagsgesellschaf, Leipzig
Ge D, Shi W, Ren L, Zhang F, Zhang G, Zhang X, Zhang
Q (2006) Variation analysis of affinity-membrane
model based on Freundlich adsorption. J Chromatogr
A 1114:40–44
Kimura K, Amy G, Drewes J, Watanabe Y (2003) Adsorp-
tion of hydrophobic compounds onto NF/RO mem-
branes: an artifact leading to overestimation of
rejection. J Membr Sci 221:89–101
McCallum EA, Hyung H, Do TA, Huang CH, Kim JH
(2008) Adsorption, desorption, and steady-state
removal of 17b-estradiol by nanofiltration membranes.
J Membr Sci 319:38–43
Van der Bruggen B, Braeken L, Vandecasteele C (2002)
Flux decline in nanofiltration due to adsorption of
organic compounds. Sep Purif Technol 29(1):23–31
F
Fuel Cell Membrane
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
Low-temperature fuel cells can be equipped with
a proton or anion exchange membrane in alterna-
tive to liquid electrolytes (Aricò et al. 2001). The
core of a polymer electrolyte fuel cell (PEMFC)
is the ion exchange membrane. The electrodes
(anode and cathode) are in intimate contact with
the membrane faces. The membrane determines
the fuel cell resistance and the fuel permeation
rate, and it influences the reaction rate. It is well
known that the use of non-noble metal catalysts is
possible in the presence of alkaline electrolytes.
Proton-conducting electrolytes have been pre-
ferred to alkaline electrolytes for several decades
for practical reasons, e.g., to avoid carbonation.
The standard electrolyte membrane is usually a
perfluorosulfonic acid membrane such as Nafion.
Most of the electrolytes alternative to Nafion both
proton conducting and alkaline type, e.g., hydro-
carbon type, are significantly cheaper, and, in
some cases, they are also characterized by
smaller hydrogen and methanol crossover. How-
ever, lifetime characteristics similar to those
shown by Nafion-type membranes in fuel cells
have not yet been demonstrated for the alterna-
tive membranes. Concerning with the conductiv-
ity, only recently, membranes alternative to
Nafion type have shown similar levels of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_255-2
performance. One critical aspect is related to the
fact that the presence of water is a requirement of
low-temperature PEMFCs and DMFCs for the
occurrence of the electrochemical reactions and
for the promotion of ionic conductivity (water-
assisted conductivity mechanism). High ionic
conductivities are often associated to the pres-
ence of large water uptake by the membrane,
but this property often causes poor mechanical
characteristics such as large swelling and relevant
crossover (especially methanol). Phosphoric
acid-doped polybenzimidazole membranes use a
Grotthus mechanism of proton transport and do
not require water (Wang et al. 1995). These mem-
branes operate at about 180–200  C, whereas
composite perfluorosulfonic acid membranes or
sulfonated hydrocarbon membranes including
inorganic fillers such as silica rely on the water-
assisted mechanism, but they can operate up to
145  C, under particular conditions (3 bar abs
pressure), due to the enhanced water retention
of the filler (Aricò et al. 2003).
Composite recast Nafion® membranes
containing inorganic fillers have been employed
in high-temperature (~150  C) direct alcohol
(Aricò et al. 1998) and H2 air fuel cells
(Watanabe et al. 1996). These composite mem-
branes were originally developed for reduced
humidification operation in polymer electrolyte
fuel cells (Watanabe et al. 1996) due to the
enhanced water retention inside the membrane
by the effect of the inorganic filler (Aricò
et al. 1998). A further advantage of composite
2 Fuel Cell Membrane
membranes relies in the barrier effect given by
the inorganic filler for methanol crossover (Ren
et al. 1996).
References
Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998)
Comparison of ethanol and methanol oxidation in a
liquid-feed solid polymer electrolyte fuel cell at high
temperature. Electrochem Solid-State Lett 1:66–68
Arico AS, Srinivasan S, Antonucci V (2001) Fuel Cells
1:133
Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
Antonucci V (2003) Influence of the acid–base char-
acteristics of inorganic fillers on the high temperature
performance of composite membranes in direct meth-
anol fuel cells. Solid State Ionics 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells.
J Electrochem Soc 143:L12
Wang J, Wasmus S, Savinell RF (1995) Evaluation of
Ethanol, 1-Propanol, and 2-Propanol in a Direct Oxi-
dation Polymer-Electrolyte Fuel Cell. J Electrochem
Soc 142:4218
Watanabe M, Uchida H, Seki Y, Emori M, Stonehart
P (1996) Self-humidifying polymer electrolyte mem-
branes for fuel cells. J Electrochem Soc 143:3847
G
Gas Permeation Unit (GPU)
May-Britt Hägg
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Norway
The intrinsic permeation property of a gas
through a membrane is characterized by the per-
meability coefficient P of a gas A, PA. Barrer was
early introduced as a practical unit for this prop-
erty and made it easy to compare the suitability of
materials to be used for membrane gas separa-
tion. Barrer is also defined below.
Permeance is directly related to the thickness,
l, of the membrane and as such defined as
pressure-normalized steady-state flux, P/l. The
permeance will characterize the gas transport
through the membrane. Permeance is an
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_260-1
important parameter when comparing the separa-
tion suitability of membranes for mixed gases.
A practical unit often used is GPU (gas perme-
ation unit) (see below).
Permeability:
1Barrer ¼ 1010 cm3 ðSTPÞcmcm2 s1 cmHg1
¼ 1, 33  1014 m3 ðSTPÞmm2 s1 kPa1
¼ 2:99  1015 kmolmm2 s1 kPa1
Permeance:
1GPU ¼ 106 cm3 ðSTPÞcm2 s1 cmHg1
¼ 7:6  109 m3 ðSTPÞm2 s1 kPa1
¼ 3:35  103 kmolm2 s1 kPa1
(For conversions on membrane key parameters,
please refer to: Table according to Journal of
Membrane Science.)
G

Gas Separation (PSA) method. The separation occurs when the

gas mixture comes in contact with the sorbent/
Mariolino Carta solvent in a vessel which is then pressurized. The
School of Chemistry, The University of gas with the highest affinity for the adsorbent is
Edinburgh, Edinburgh, Scotland, UK “trapped,” whereas the others pass through the
system. The regeneration of the vessel is carried
out by returning it to atmospheric pressure or by
Gas separation is a widely used technique in increasing the temperature, with release of the
which the objective is the separation of one or “trapped” gas. The main advantage of this tech-
more gases from a mixture. It is becoming crucial nique is the high purity of the separated gas; the
for several industrial processes such as the treat- disadvantage consists in the high energy required
ment of fumes from coal-fired plants, in particu- for running the system, especially for the regen-
lar, aiming for the removal of CO2 to reduce the eration of the vessel (Fig. 1).
greenhouse effect. Growing interest is also given
to other applications such as the separation and
purification of commercially important gases
Separation by Cryogenic Distillation
such as H2, CH4, and O2 from natural gas. The
most common methods to perform gas separation
Cryogenic distillation is based on the fact that in a
are:
mixture of gases, they all have different boiling
points and they could be separated by increasing/
1. Separation with solvent/sorbents
decreasing the temperature and pressure of the
2. Separation by cryogenic distillation
system in which they are stored, so that they can
3. Separation with membranes
be divided into their single components. The gas
mixture is cooled down to a low temperature
(typically < 50  C). Once in the liquid form,
Separation with Solvent/Sorbents
the components of the gas can be directed in a
distillation column, and through a series of com-
The separation with solvent/sorbents is based on
pression, cooling, and expansion steps, they can
the affinity of the gas toward a specific sorbent
be distributed to different channels, depending on
such as zeolites, alumina, or activated carbon or a
their boiling points (Fig. 2).
solvent, for instance, MEA (methanolamine).
It is a widely used technique for streams that
The most illustrative example of this technology
already have a high concentration of desired gas
is represented by the pressure swing adsorption
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_261-1
2 Gas Separation

Gas Separation,
Fig. 1 Schematic
representation of pressure
swing adsorption method
(PSA)

Gas Separation,
Fig. 2 Schematic
representation of cryogenic
distillation method

(typically >90 %), but it is not very appropriate

for more dilute gas streams.
The main advantage of the cryogenic gas sep-
aration is that it enables direct production of
liquid gas, which is often very useful for certain
transport options, such as transport by ship.
A major disadvantage is connected with the
high amount of energy required for the refrigera-
tion especially for dilute gas streams.

Separation with Membranes

Separation of gases with membranes relies on the
different affinities of one or more gases toward
the membrane material, causing one gas to per-
meate faster (or slower) than others. It is one of
the fastest growing field for gas separation tech-
niques, especially due to the high variety of mate-
rials which the membrane could be composed of,
including microporous organic polymers,
Gas Separation, Fig. 3 Schematic representation of
membranes for gas separation
zeolites, ceramic, and metal-containing materials
(for a more in-depth reading, see Yampolskii and
Freeman (Yampolskii et al. 2010)).
The gas mixture is directed into a vessel and put
in contact to the membrane material which is at the
interface with another vessel (Fig. 3). The mixture
Gas Separation
Gas Separation,
Fig. 4 An example of
Robeson plot, in this case
O2/N2 (Carta et al. 2013).
The black line represents
the 1991 (Robeson 1991)
upper bound, whereas the
red line is the current
(2008) upper bound
(Robeson 2008)
is allowed to diffuse into the second vessel under a
pressure gradient which promotes the mass trans-
port through the membrane separating the retentate
(slower gas) from the permeate (faster gas).
The use of membranes for gas separation
offers several benefits, probably the most valu-
able is the high cost efficiency (both for the
mechanical simplicity of the system and for
low-energy regeneration). In fact, they do not
require thermal regeneration, a phase change, or
active moving parts in their operation.
Probably the greatest limitation of membranes
for gas separation is derived from their trade-off
relationship between permeability and selectivity
for a required gas component. This means that high
permeable membranes have low selectivity, requir-
ing several run for a good separation, and highly
selective membranes have low permeability,
meaning long operational times. This trade-off
was well addressed by Robeson in two well-
known articles (Robeson 1991, 2008) in which he
studied the gas separation performance of several
membrane-forming materials in terms of perme-
ability of a particular species (PA) and selectivity
toward one component of a gas pair (aA/B = PA/
PB), organizing the data in double logarithmic plots
for a series of commercially selected important gas
pairs such as H2/CH4, H2/CO2, and O2/N2. He
3
confirmed that highly selective membranes gener-
ally exhibit low permeability and vice versa. The
most important outcome of this study is
represented by the so-called Robeson upper
bound, an empirical line which is drawn for every
gas pair plot that is meant to define how good a
material for gas separation is. In Fig. 4, there is a
typical example (Carta et al. 2013) in which the red
line represents the 2008 upper bound for the gas
pair O2/N2. Supposedly, if we plot the selectivity
aA/B versus permeability PA for a new membrane
and the data point fall close or go over the upper
bound, it is widely accepted that the material has an
excellent compromise between P (rate of separa-
tion) and a (goodness of separation).
References
Carta M, Malpass-Evans R, Croad M, Rogan Y, Jansen
JC, Bernardo P, Bazzarelli F, McKeown NB (2013) An
efficient polymer molecular sieve for membrane gas
separations. Science 339(6117):303–307
Robeson LM (1991) Correlation of separation factor ver-
sus permeability for polymeric membranes. J Membr
Sci 62(2):165–185
Yampolskii Y, Freeman B (eds) (2010) Membrane gas
separation. Wiley, Chichester, UK, 370 pp
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320(1+2):390–400
G
Gas Separation by Membrane
Operations
Mariolino Carta1 and Paola Bernardo2
1
School of Chemistry, University of Edinburgh,
Edinburgh, UK
2
Research Institute on Membrane Technology,
ITM-CNR, Rende (CS), Italy
The separation of mixtures of gases and vapors is
required in manufacturing processes across vari-
ous industries. In the last years, membrane sys-
tems are gaining a larger acceptance in industry
for gas separation and are recognized as a cost-
efficient separation able to compete with consol-
idated processes such as pressure swing absorp-
tion and cryogenic distillation (Bernardo
et al. 2009; Sanders et al. 2013). Membrane pro-
cesses have several advantages over conventional
separation techniques (e.g., distillation, extrac-
tion, absorption, and adsorption), including mod-
ularity and compactness, operational flexibility,
and no need for energy-intensive phase changes
or potentially expensive adsorbents and/or diffi-
cult to handle solvents. The features of membrane
operations allow implementing the process inten-
sification strategy in different production cycles.
Their versatility represents a decisive factor to
impose membrane processes in most gas separa-
tion fields.
The first membrane units were installed in
ammonia plants for the separation of hydrogen
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_262-1
from nitrogen more than 30 years ago. Today, the
production of nitrogen from air is the largest
application of membrane systems, owing to the
demand for nitrogen to inert fuel tanks, also
aboard aircrafts, and for blanketing chemical
and liquefied gas shipments. Membrane systems
are also applied to enrich oxygen for medical
uses, for hydrogen recovery and purification in
refineries, for air and gas dehydration, and for
ratio adjustment of gas mixtures. Natural gas
processing represents an important emerging
application field (Baker and Lokhandwala
2008). The relatively low volume flow and the
relatively high inlet carbon dioxide content are
strong drivers for the implementation of the
membrane technology in the biogas upgrading
that it is at a developing stage (Makaruk
et al. 2010). The challenging olefin/paraffin sep-
aration, not yet commercial, is attracting a lot of
interest from the scientific community (Rungta
et al. 2013).
Membrane separation allows recovering and
recycling valuable compounds, such as hydrogen
and light hydrocarbons (ethylene, propylene, and
LPG), present in different off-gas streams (Baker
et al. 1998). Polymeric membranes, cheap and
with an easy processability, are typically used in
the commercially available membrane system for
gas separation (Yampolskii 2012). Commercial
modules employ composite membranes (Pinnau
et al. 1988), mainly in the form of compact hol-
low fibers. These membranes typically operate
the separation based on a solution-diffusion
2 Gas Separation by Membrane Operations
transport mechanism: sorption of the permeant
into the membrane, permeation by diffusion
through the membrane, and desorption at the
low-pressure side of the membrane.
The experimentally observed upper bound,
based on various polymeric membranes, was
reported by Robeson in 1991 and then updated
in 2008 (Robeson 1991, 2008), thanks to the
efforts to improve the gas separation performance
of ultrahigh free volume and perfluoropolymers.
Glassy polymers are chosen for their size-
selective behavior (e.g., in O2/N2 or H2 separa-
tions). However, when applied to mixtures and/or
at high gas activities, these materials are prone to
plasticization, which causes swelling of the poly-
mer matrix and results in a higher permeability
coupled with a loss of selectivity. Strategies to
overcome plasticization include thermal curing
and chemical cross-linking, which reduce the
polymer free volume (Wind et al. 2002). The
addition of nanofillers to a polymer matrix repre-
sents an interesting solution to overcome the
trade-off of the polymeric membranes and the
inherent brittleness issues of inorganic mem-
branes (Goh et al. 2011).
Rubbery polymers, instead, present a
solubility-controlled permeation and preferen-
tially allow the permeation of large gas or
vapor molecules in a gaseous mixture containing
also smaller molecules (Grinevich et al. 2011).
Their permeability, much higher than in conven-
tional glassy polymers, increases with the criti-
cal volume of the penetrant (Matteucci
et al. 2006). These materials are applied to the
separation of organic vapors from
non-condensable gases, treating petrochemical
vent and process streams to recover valuable
feedstocks (Baker 1999).
An interesting new concept is the use of water-
swollen thin film composite membranes for bio-
gas purification, taking advantage of the large
difference in solubility in water to become selec-
tive for CO2 (Kárászová et al. 2012).
Facilitated transport membranes contain car-
rier agents that can react reversibly with the target
gas component. Therefore, the reaction in the
membrane creates another transport mechanism,
in addition to the simple solution–diffusion
mechanism (Huang et al. 2008). However, carrier
poisoning and short life span of the polymeric
membranes are typically reported (Rungta
et al. 2013). Ionic liquids were considered as
additives for facilitated transport membranes.
Indeed, their negligible vapor pressure avoids
solvent losses by evaporation, providing stability
to the metallic cation dissolved inside, and acting
as a medium for facilitated transport with mobile
carrier (Fallanza et al. 2013). Ionic liquid gel
membranes based on conventional polymers
(Jansen et al. 2011) or on polymer ionic liquids
(Bara et al. 2008) were proposed to increase the
stability compared to supported liquid
membranes.
The key for new applications of membranes in
challenging and harsh environments (e.g., petro-
chemistry) is the development of new tough,
high-performance materials. In the field of inor-
ganic membranes, metal organic frameworks
were recently considered for preparing mem-
branes to be applied to the olefin/paraffin separa-
tion (Bux et al. 2011) or as additive to a polymer
matrix (Bushell et al. 2013).
High free volume polymers have been inves-
tigated as gas separation membranes, combining
their ease of processing and mechanical stability
with the potential to surpass the polymeric upper
bound for different gas pairs (Budd and
McKeown 2010). Novel PIMs, characterized by
a significant shape persistence, were developed,
showing interesting performance for the O2/N2
separation (Carta et al. 2013).
Properly designed hybrid processes, combin-
ing a membrane system with a conventional one
(e.g., PSA or absorption), represent technically
and economically viable solutions, able to reduce
energy consumption and total costs (Esteves and
Mota 2007).
References
Baker R (1999) Recent developments in membrane
vapour separation systems. Membr Technol
1999(114):9–12
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47:2109–2121
Gas Separation by Membrane Operations
Baker RW, Wijmans JG, Kaschemekat JH (1998) The
design of membrane vapour-gas separation systems.
J Membr Sci 151:55–62
Bara JE, Hatakeyama SE, Gin DL, Noble RD
(2008) Improving CO2 permeability in polymerized
room-temperature ionic liquid gas separation mem-
branes through the formation of a solid composite
with a room-temperature ionic liquid. Polym Adv
Technol 19:1415–1420
Bernardo P, Drioli E, Golemme G (2009) Membrane gas
separation. A review/state of the art. Ind Eng Chem
Res 48(10):4638–4663
Budd PM, McKeown NB (2010) Highly permeable poly-
mers for gas separation membranes. Polym Chem
1(1):63–68
Bushell AF, Attfield MP, Mason CR, Budd PM,
Yampolskii YP, Starannikova L, Rebrov A,
Bazzarelli F, Bernardo P, Jansen JC, Lanč M,
Friess K, Shantarovic V, Gustov V, Isaeva V (2013)
Gas permeation parameters of mixed matrix mem-
branes based on the polymer of intrinsic microporosity
PIM-1 and the zeolitic imidazolate framework ZIF-8.
J Membr Sci 427:48–62
Bux H, Chmelik C, Krishna R, Caro J (2011) Ethene/
ethane separation by the MOF membrane ZIF-8:
molecular correlation of permeation, adsorption, dif-
fusion. J Membr Sci 369:284–289
Carta M, Malpass-Evans R, Croad M, Rogan Y, Jansen
JC, Bernardo P, Bazzarelli F, McKeown NB (2013) An
efficient polymer-based molecular sieve membranes
for membrane gas separations. Science 339:303–307
Esteves IAAC, Mota JPB (2007) Gas separation by a
novel hybrid membrane/pressure swing adsorption
process. Ind Eng Chem Res 46(17):5723–5733
Fallanza M, Ortiz A, Gorri D, Ortiz I (2013)
Polymer–ionic liquid composite membranes for pro-
pane/propylene separation by facilitated transport.
J Membr Sci 444:164–172
Goh PS, Ismail AF, Sanip SM, Ng BC, Aziz M (2011)
Recent advances of inorganic fillers in mixed matrix
membrane for gas separation. Sep Purif Technol
81:243–264
Grinevich Yu, Starannikova L, Yampolskii Yu,
Gringolts M, Finkelshtein E (2011) Solubility
3
controlled permeation of hydrocarbons in novel highly
permeable polymers. J Membr Sci 378:250–256
Huang J, Zou J, Ho WSW (2008) Carbon dioxide capture
using a CO2-selective facilitated transport membrane.
Ind Eng Chem Res 47(4):1261–1267
Jansen JC, Friess K, Clarizia G, Schauer J, Izák P (2011)
High ionic liquid content polymeric gel membranes:
preparation and performance. Macromolecules
44:39–45
Kárászová M, Vejražka J, Veselý V, Friess K, Randová A,
Hejtmánek V, Brabec L, Izák P (2012) A water-
swollen thin film composite membrane for effective
upgrading of raw biogas by methane. Sep Purif
Technol 89:212–216
Makaruk A, Miltner M, Harasek M (2010) Membrane
biogas upgrading processes for the production of nat-
ural gas substitute. Sep Purif Technol 74:83–92
Matteucci S, Yampolskii Y, Freeman B, Pinnau I (2006)
Transport of gases and vapors in glassy and rubbery
polymers. In: Yampolskii Y, Pinnau I, Freeman
B (eds) Material science of membranes for gas and
vapor separation. Wiley, Chichester, pp 1–48
Pinnau I, Wijmans JG, Blume I, Kuroda T, Peinemann KV
(1988) Gas permeation through composite mem-
branes. J Membr Sci 37(1):81–88
Robeson LM (1991) Correlation of separation factor ver-
sus permeability for polymeric membranes. J Membr
Sci 62(2):165–185
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320(1–2):390–400
Rungta M, Zhang C, Koros WJ, Xu L (2013) Membrane-
based ethylene/ethane separation: the upper bound and
beyond. AIChE J 59(9):3475–3489
Sanders D, Smith ZP, Guo R, Robeson LM, McGrath JE,
Paul DR, Freeman BD (2013) Energy-efficient poly-
meric gas separation membranes for a sustainable
future: a review. Polymer 54(4):729–4761
Wind JD, Staudt-Bickel C, Paul DR, Koros WJ (2002) The
effects of crosslinking chemistry on CO2 plasticization
of polyimide gas separation membranes. Ind Eng
Chem Res 41(24):6139–6148
Yampolskii Y (2012) Polymeric gas separation mem-
branes. Macromolecules 45(8):3298–3311
G
Gas/Vapor Transport
Johannes Carolus Jansen1 and Marek Lanč2
1
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
2
University of Chemistry and Technology Prague,
Prague 6, Czech Republic
General Introduction
Transport of gases and vapors in membranes
depends first of all on their micro- and macro-
scopic structure. There is a fundamental differ-
ence between dense membranes, where transport
takes place through the material of the membrane
itself, and porous membranes, where the transport
takes place through the open space of the pores in
the membrane. In the latter, different transport
modes exist, depending on the size of the pores
and on the interaction of the gases and vapors with
the membrane material and with themselves. The
most representative examples of transport mech-
anisms are shown in Fig. 1.
(A) In large pores, convective or viscous flow
occurs. Such membranes find application as
filters to remove particulate matter from gas
and liquid streams, but they are not able to
separate gases, which move as a homoge-
neous mixture through the pores.
(B) If the average pore diameter is smaller than
the mean free path between the molecules in
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_263-1
the gas mixture at the given pressure,
so-called Knudsen diffusion takes place
(Knudsen 1909; Datta et al. 1992). In this
case, the transport rate is inversely propor-
tional to the square root of the molecular
weight of the gas species and the selectivity
is only a function of their molecular weight
ratios.
(C) For even smaller pores, where the size of the
pores is in the range of the size of the gas
molecules themselves, molecular sieving can
occur. Molecules that are larger than the pore
size are completely excluded, and only
smaller molecules may diffuse through the
pores of the membrane. Such membranes
can have very high selectivities, in the case
of very narrow pore size distributions. Typi-
cal examples are carbon membranes
(Vu et al. 2001) or zeolite membranes (Caro
and Noack 2008; Rangnekar et al. 2015).
Also dense polymer membranes, when they
have a combination of very high free volume
and high stiffness of the polymer chains, may
exhibit behavior that comes close to molecu-
lar sieving (Carta et al. 2013).
(D) In the case of strong interaction of the mem-
brane material with the permeating species or
in case of readily condensable species, the
latter condenses on the pore wall. In this
case, what is the most permeable species
depends on various factors, including the
molecular dimensions of the permeating spe-
cies of the mixture and on the remaining
2 Gas/Vapor Transport
Gas/Vapor Transport, Fig. 1 Schematic representation
of different transport mechanisms in porous and dense
membranes
aperture of the pores, as well as the mobility
of the condensed species on the pore surface.
(E) In the extreme situation of the previous, cap-
illary condensation takes place and the whole
pore is filled with the condensed liquid. The
selectivity of these membranes for gas mix-
tures may be completely different from the
ideal selectivity for single gases. Based on the
Kundsen diffusion mechanism, small mole-
cules would always be much more permeable
than larger molecules. However, if the larger
molecules condense inside the pore, the con-
densed phase obstructs the permeation of
smaller molecules. Thus, the mixed gas selec-
tivity may be opposite to the ideal selectivity.
(F) In dense membranes, the molecules move
through the bulk of the membrane material
itself, or more precisely through its free vol-
ume. The rest of this chapter will focus mostly
on the transport in dense membranes because
of their relevance for gas separation
applications.
Gas/Vapor Transport in Dense
Membranes
Fick’s Law of Diffusion
The penetrant flow, J, through a nonporous mem-
brane can be described by Fick’s first law of
diffusion (Fick 1855), derived analogically to
Fourier’s law for the description of heat transfer.
dci
J i ¼ Di (1)
dx
where D is the diffusion coefficient and dc/dx the
concentration gradient. The concentration in
nonstationary conditions depends not only on
the position in the continuous phase but also on
time. Assuming one-dimensional diffusion, the
transport behavior can be described by Fick’s
second law of diffusion:
@ci @ 2 ci
¼ Di 2 (2)
@t @x
Both equations assume that the diffusion coeffi-
cient is independent on concentration, which is
true at low penetrant activity. Figure 2 describes
the gas concentration profile at different times, for
a previously evacuated polymer membrane after
single-sided and double-sided exposure to a gas,
based on Eq. 2 (Crank 1975). These profiles cor-
respond to those in a typical permeation and sorp-
tion experiment, respectively.
The Solution-Diffusion Mechanism
The transport of gases and vapors in dense poly-
mer membranes is governed by the solution-
diffusion model (Wijmans and Baker 1995,
2006). The driving force of this process in dense
membranes is the partial pressure gradient of the
permeating species across the membrane, or more
correctly its chemical potential gradient. The pro-
cess consists of three steps: first, the gas is
absorbed by the membrane at the polymer/gas
interface on the feed side, then it diffuses across
the polymer bulk, and finally it desorbs from the
membrane at the permeate side. The permeability
coefficient, P, is the product of the diffusion coef-
ficient, D, and the solubility coefficient, S:
Gas/Vapor Transport
Gas/Vapor Transport, Fig. 2 Concentration profiles in a
flat sheet membrane (100 mm) calculated by Eq. 2, for D =
1012 m2 s-1 (Crank 1975) in the case of: (a) ideal time lag
permeation experiment (Relative feed
concentration = 1, permeate concentration = 0); (b) ideal
P¼DS (3)
where S is defined as the ratio of the equilibrium
gas concentration, C, and the gas pressure, p:
S ¼ C=p (4)
The selectivity aA/B of two species A and B is
defined as the ratio of the two individual perme-
ability coefficients and this can be decomposed
into a diffusion selectivity term and a solubility
selectivity term:
PA D A S A
aA=B ¼ ¼  (5)
PB D B S B
In ideal systems, such as for the transport of light
gases in rubbers, P, D, and S are constants, but this
is rather an exception and in many cases D and
S depend on the concentration of the permeating
species in the membrane and thus on the gas
pressure. Numerous correlations have been pro-
posed, relating the gas and vapor transport prop-
erties of polymeric membranes to the molecular
properties of the penetrating species and to the
chemical and physical properties of the polymer
3
sorption experiment (Relative feed concentration = 1)
Arrows represent the increasing time during the experi-
ment. Dashed lines represent the concentration profile in
time equal to permeation time lag (see below)
matrix, and they can be found in an excellent
review (Matteucci et al. 2006).
In phenomenological terms, the membrane
productivity is expressed by means of its
permeance, defined as an amount of permeate
per unit membrane area, time, and driving force.
A commonly used unit is the gas permeation unit,
GPU:
cm3STP
1 GPU ¼ 106
cm2  s  cm Hg
(6)
m3
¼ 2:70  109 2 STP
m  h  bar
The permeance is a property of the membrane and
depends on its effective thickness. The permeabil-
ity coefficient is an intrinsic property of the mate-
rial. The most commonly used unit to describe the
permeability coefficient is the Barrer:
cm3STP  cm
1 Barrer ¼ 1010 (7)
cm2  s  cm Hg
Diffusion is an activated process and solubility is
a thermodynamic property. The temperature
dependence of diffusivity and solubility can there-
fore be described by the following Arrhenius and
4 Gas/Vapor Transport
van’t Hoff relationships, respectively (Van
Amerongen 1946; Costello and Koros 1992).
D ¼ D0  eED =RT (8)
S ¼ S0  eDHs =RT (9)
where DHs is the enthalpy of sorption of the
penetrant in the polymer, ED activation energy of
diffusion, and D0 and S0 are the preexponential
factors.
Assuming solution-diffusion model (Eq. 3),
temperature dependency of permeability is:
P ¼ P0  eEP =RT (10)
where P0 is preexponential factor and EP activa-
tion energy of permeation which is equal to:
EP ¼ DH S þ ED (11)
As a temperature-activated process, diffusion usu-
ally accelerates with temperature. Dissolution of
the gas can be considered as a two-step process of
condensation of the gas phase, followed by
mixing with the polymer matrix. For light gases,
the solubility therefore increases with increasing
temperature, because the negative enthalpy of
condensation is negligible with respect to the pos-
itive enthalpy of mixing. On the other hand,
enthalpy of sorption of more condensable gases
and vapors is negative due to the high negative
enthalpy of condensation and the solubility
decreases with increasing temperature. Tempera-
ture dependency of diffusivity is usually stronger
than that of solubility, and therefore the perme-
ability usually increases with increasing tempera-
ture (Ghosal and Freeman 1994).
Gas/Gas, Gas/Vapor, and Vapor/Vapor
Separation
The most important industrial applications of gas
and vapor separations vary from (A) gas/gas sep-
arations to (B) gas/vapor separations, where the
membrane is in contact with highly condensable
species. In the extreme case of pervaporation (C),
the membrane is at one side in contact with a
liquid phase and at the downstream side it is in
contact with a gas phase. The type of separation
process dictates the possible operation conditions
and the choice of the membrane materials.
(A) For simple gas/gas separations, for instance,
O2/N2 separation from air for pure nitrogen
production or for O2 enrichment, in principle
many membrane materials can be safely used
(Baker and Low 2014). The choice depends
mainly on the need to achieve a high separa-
tion factor at relatively low flux or if a high
flux is needed and the separation factor is less
important.
(B) For gas/vapor separations, the transport prop-
erties of the different species vary widely.
Often the vapor consists of readily condens-
able large molecules, which have a high sol-
ubility in combination with a low diffusion
coefficient, in contrast to the light gas, with a
lower solubility and a high diffusion coeffi-
cient. In this case, the species in the mixture
are likely to influence each other, directly via
competitive sorption in the limited free vol-
ume available and indirectly via plasticiza-
tion of the polymer matrix by the
condensable species. The same situation
occurs in gas/gas separations, where one of
the two gases readily condenses at higher
pressure, for instance, CO2. Typical examples
are volatile organic compounds (VOC)
removal from air (Leemann et al. 1996), or
CO2 removal from natural gas (Adewole
et al. 2013) or biogas, air dehydration,
etc. For such separations, it may be conve-
nient to use rubbery membranes, which are
less prone to plasticization and which are
solubility selective rather than diffusivity
selective.
(C) Pervaporation is the extreme case of vapor/
vapor separation, with condensed vapors
(=liquid mixture) at the feed side of the mem-
brane and gaseous species at the permeate
side, either by application of a vacuum or by
the use of a sweeping gas (Mulder and Smol-
ders 1991). Pervaporation is particularly
Gas/Vapor Transport 5

advantageous in the case of azeotropic liq- 4

uid mixtures, where the membrane can
break the azeotrope. Typical examples of

Permeate pressure (mbar)

practical separations are the dehydration of 3
alcohol with hydrophilic membranes, etha-
nol recovery from hydroalcoholic solu-
tions, or VOC removal from wastewater 2

with hydrophobic membranes. In terms of

the transport properties, these membranes
1
are often strongly affected by the swelling
of the polymer by the permeating species. Θ
An exception is the alcohol dehydration
0
with glassy perfluoropolymer membranes 0 25 50 75 100 125
(Scholes et al. 2015a, b). A further compli- Time (s)
cation in pervaporation with respect to
gas/vapor separation is the existence of the Gas/Vapor Transport, Fig. 3 Typical permeation curve
for analysis of pure gas permeability by the time lag
Schroder’s paradox, according to which the method, with indication of time lag Y determined via the
membrane material often behaves differ- tangent method
ently in contact with a liquid phase or in
contact with the saturated vapor phase pt ¼ p0 þ ðdp=dtÞ0 
t 
(Vallieres et al. 2006). A curiosity is that RT  A  l Dt 1
þ  pf  S   ser
pervaporation membranes can be porous VP  Vm l2 6
and nonselective in the dry state and with

become dense and selective in contact 2 X ð1Þ
1 n
D  n2  p2  t
ser ¼ 2 exp 
with the feed mixture (Van Der Bruggen p n¼1 n2 l2
et al. 2004, 2006). (12)

in which pt is the permeate pressure at time t and

Methods for Analysis of the Transport
Parameters in Membranes
Time Lag Method for Pure Gases
The most common way to determine the basic gas
transport parameters is the so-called time lag
method (Crank 1975), in which the membrane is
fully evacuated inside a closed permeation cell,
and after exposure of the membrane to the gas at
the feed side, the pressure at the permeate side is
recorded as a function of time. For ideal systems,
the concentration profile in the early stage of the
experiment takes the form of Fig. 2a and the
resulting permeation curve takes the form of
Fig. 3, which is described by the following equa-
tion (Jansen et al. 2011):
p0 is the starting pressure, typically as close to
zero as the vacuum pump allows. In a leak-proof
instrument, the baseline slope (dp/dt)0 is usually
negligible for a defect-free and well-evacuated
membrane. R is the universal gas constant, T the
absolute temperature, A the exposed membrane
area, VP the permeate volume, Vm the molar vol-
ume of a gas at standard conditions (0  C and
1 atm), pf the feed pressure, and l the membrane
thickness. The permeability coefficient, P, is cal-
culated in the regime of quasi steady state perme-
ation, which is defined by the simplified Eq. 13,
describing the tangent to the linear part of the
permeation curve:
6 Gas/Vapor Transport
pt ¼ p0 þ ðdp=dtÞ0  t
(13)
RT  A pf  P
þ  ðt  Y Þ
VP  Vm l permeate flux, QPermeate, to the partial pressure
The last term is the so-called permeation time lag,
Y, which is usually determined from the intersec-
tion of the tangents before the onset of permeation
and after reaching the quasi steady state:
l2
Y¼ (14)
6D
For a membrane of known thickness, it allows the
determination of the diffusion coefficient of the
gas. The gas solubility coefficient, S, can then be
obtained indirectly as the ratio of the permeability
to the diffusion coefficient, using Eq. 3.
While the transport parameters P and D are
usually obtained by using the tangents to the per-
meation curve, the permeation curve can also be
fitted directly with Eq. 12, after expansion into a
sufficient number of terms (Scheichl et al. 2005;
Jansen et al. 2011). This yields the values of P, D,
and S directly. An inaccurate fit in the case of a
deviating curve shape is a direct indication of
nonideal behavior. This happens, for instance, in
the case of clustering or in the case of strong dual
mode sorption (DMS) behavior.
Constant Pressure: Variable Volume Method
In this method, the pure feed gas or the feed gas
mixture flows through the membrane cell in cross-
flow mode and the permeate is either collected as
such or it is transported by a sweeping gas to the
gas analyzer. The total permeation rate can be
determined directly, for instance, by a bubble
flow meter or electronic flow meters, measuring
the volumetric permeate flow rate, JPermeate. The
permeate flux, QPermeate, is the volumetric flow
rate per unit area:
J Permeate
QPermeate ¼ (15)
A
When using a sweeping gas, the permeate flux can
also be calculated from the known sweeping gas
flow rate and the gas concentration in the
permeate/sweeping gas mixture. The individual
gas permeance, P, of the ith species in a gas
mixture is obtained as the ratio of its volumetric
difference between the feed and permeate sides:
xi Permeate QPermeate
Pi ¼ (16)
Feed
xi p Feed  xi Permeate pPermeate
in which xi is the volume fraction or mole fraction
of the ith species, pFeed and pPermeate are the total
feed and permeate pressures, respectively. The
mixed gas selectivity of species A and B, aA/B, is
then calculated as the ratio of their individual
permeances:
PA
aA=B ¼ (17)
PB
Sorption Analysis
Direct sorption analysis is the most reliable way to
determine the solubility of the gas in the polymer
matrix. Sorption can be determined volumetri-
cally, gravimetrically, and with the pressure
decay method (Keller and Staudt 2005), or by
inverse gas chromatography (IGC) (Danner
et al. 1998). Equilibrium sorption in polymers is
one of the basic characteristics describing the
interaction between a penetrant and a polymer.
In all these methods, the polymer sample is placed
inside the test cell and exposed to a given pene-
trant pressure. In gravimetric measurements, the
mass uptake can be measured electromagnetically
(Mamaliga et al. 2004), by a quartz crystal micro-
balance (QCM) (Mikkilineni et al. 1995) or
McBain’s quartz spiral balance (Friess
et al. 2011; Vopička et al. 2013).
Since the sorption coefficient (solubility) is
usually a function of pressure or activity, knowl-
edge of the sorption isotherm shape is important.
There are many different types of sorption iso-
therms (Rouquerolt et al. 1994) depending on
the polymer structure and the relative difference
between penetrant/polymer and penetrant/pene-
trant interaction.
Sorption of light gases in rubbery polymers
increases linearly with pressure according to
Gas/Vapor Transport 7

Henry’s law. On the other hand, vapor’s sorption v m  h  p  p

can be described by numerous equations such as
Flory-Huggins theory (Flory 1953), Flory-Rehner
(Flory and Rehner 1943a; Flory and Rehner
Jr. 1943b; Izák et al. 2003), Koningsveld-
Kleintjens equations (Koningsveld and Kleintjens
1971), or the ENSIC model (Favre et al. 1996).
In the case of dense glassy polymeric mem-
branes, three models are the most often used.
Permanent gases behave almost linearly, at low
pressures following Henry’s law. Alternatively,
the dual-mode sorption model, Eq. 18, gives usu-
ally a satisfactory description of the behavior
(Barrer et al. 1958). This model is a combination
of Henry’s law and the Langmuir sorption iso-
therm, assuming monolayer sorption at existing
sorption sites.
ch  p  b
C ¼ CD þ C H ¼ k d  p þ
1þbp
where C is the gas concentration in the polymer,
CD and CH are the Henry and Langmuir concen-
tration contributions, respectively, kd is the linear
sorption parameter, ch is the monolayer capacity,
and b is the affinity parameter, reflecting the inter-
action strength between polymer and penetrant.
In the case of vapor sorption in glassy poly-
mers, the sorption curves often have a typical
S-shape and the DMS model cannot be used. In
such cases, the Guggenheim, Anderson, and de
Boer (GAB) model (Guggenheim 1966) gives a
better description:
v¼ (20)
ð p  pÞ ð h  p þ p  pÞ
where p* is a pressure independent constant
which has the meaning of a reference pressure.
When p* is equal to saturated vapor pressure, the
model is equivalent to the BET model (Brunauer
et al. 1938) (Fig. 4).
For samples with a well-defined geometry,
sorption kinetics measurements allow the deter-
mination of the diffusion coefficient by equations
based on Fick’s second law (Crank 1975). The
relative sorbed amount Qt/Q1 in a flat film with
thickness l is given as a function of time by the
following equation:
Qt 8X1
1 
Dð2nþ1Þ2 p2 t
¼1 2  e l2 (21)
Q1 p n¼0 ð2n þ 1Þ2
(18)
The corresponding concentration-time profile in a
flat membrane during a sorption experiment is
shown schematically in Fig. 2b. Under real con-
ditions, a finite time is needed to charge the gas in
the sorption apparatus and a correction for the
assumed step-pressure-increase is necessary
(Vopička et al. 2009). An example of a typical
sorption kinetics curve obtained with this model is
shown in Fig. 5.

vm  h  a  f
v¼ (19)
ð 1  f  aÞ ð 1  f  a þ h  f  aÞ

where v is the mass of adsorbed vapor per mass of

polymer adsorbent, vm is the capacity of the first
adsorption monolayer, h defines the ratio of the
adsorption strength in the first and the subsequent
layers, a is the vapor activity, and f is a constant
defining the deviation of the saturated vapor pres-
sure from a chosen reference pressure. For gases,
the following form of the GAB model was pro-
posed (Vopička and Friess 2014).
Gas/Vapor Transport, Fig. 4 Gravimetric sorption iso-
therm of CO2 in Amine-PIM-1 (Mason et al. 2014), extrap-
olated with GAB and DMS models
8 Gas/Vapor Transport
Gas/Vapor Transport, Fig. 5 Typical gravimetric sorp-
tion kinetics curve. CO2 sorption fitted with the model
proposed by Vopička (Vopička et al. 2009) in microporous
Tröger’s base polymer EA-TB-PIM (Carta et al. 2013) after
MeOH treatment
Modeling of Transport
With the increasing computational power of mod-
ern computers, modeling of structural (Heuchel
et al. 2008) and transport properties of gases
(Hofmann et al. 2000; Frentrup et al. 2015) and
vapors (Giacinti Baschetti and De Angelis 2015)
in polymeric membranes has gained a prominent
position in membrane research. Especially in the
description of the free volume distribution of
membrane materials, computational methods
offer a level of insight that no single experimental
method can give. The transport can be studied at
the atomistic level (Hofmann et al. 2000;
Theodorou 2006), showing, for instance, the
“hopping” mechanism of a gas molecule from
one free volume element to the next, confirming
the activated mechanism seen experimentally.
Although there is often a large discrepancy
between the calculated sorption and diffusion
coefficients and the experimental values, the
trends between different gas species are usually
reproduced well in the simulations (Macchione
et al. 2007; Jansen et al. 2010). Whereas molecu-
lar dynamics simulations work fairly well for
small molecules at low concentration, like in gas
separation, models to analyze and predict the mass
transport in pervaporation require different
approaches (Lipnizki and Tr€agårdh 2001), such
as the UNIQUAC model (Heintz and Stephan
1994).
Transport in Heterogeneous
and Homogeneous Mixtures
The description of the transport in polymers with
homogeneously or heterogeneously dispersed
additives or in polymer blends is much more
complex than that in neat polymers. Mixed matrix
membranes are currently receiving much attention
(Aroon and Ismail 2010; Rezakazemi et al. 2014)
because they have the potential to combine the
high permeability and selectivity of inorganic
(e.g., zeolites (Miller et al. 2007)), carbonaceous
(Vu et al. 2003), and organometallic filler particles
(metal organic frameworks, MOFs (Bushell
et al. 2013; Zornoza et al. 2013; Adatoz
et al. 2015)) with the good mechanical properties
of polymers. There is a large number of predictive
models to describe the performance of MMMs
(Vinh-Thang and Kaliaguine 2013). One of the
simplest and most commonly used models to
describe the transport in MMMs is the Maxwell
model (Shimekit et al. 2011), valid for a low
concentration of spherical particles dispersed in
the continuous phase:
Pd þ 2Pc  2fd ðPd  Pc Þ
Peff ¼ (22)
Pd þ 2Pc þ 2fd ðPd  Pc Þ
where the Peff is the effective permeability of the
mixed matrix membrane, Pc and Pd represent the
gas permeabilities in the continuous and dispersed
phase, respectively, and fd is the volume fraction
of the dispersed phase. Generally, the permeabil-
ity of the gases through the dispersed phase
depends on the overall void volume, its distribu-
tion in the filler particles, and on the channel size,
which affect the free volume of the overall system.
More sophisticated models take into account also
the particle shape of the dispersed phase (Cussler
1990). Such particles may have a pronounced
Gas/Vapor Transport
effect in the case of high aspect ratios (Rodenas
et al. 2014) due to the strong effect on the diffu-
sion path length (Falla et al. 1996). Interestingly,
also impermeable fumed silica (Merkel
et al. 2002) or graphene (Althumayri et al. 2016)
filler particles, with intrinsic barrier properties,
can have a positive effect on the permeability of
the membranes, when additional free volume is
created at the polymer-particle interface.
When the dispersed phase is another polymer,
in the case of immiscible polymer blends, the
transport can be described by fundamentally the
same equations as the mixed matrix materials
(e.g., Eq. 22). Instead, for miscible polymer
blends, the permeability, Pb, is reported to obey
the following equation (Robeson 2010):
lnPb ¼ f1 lnP1 þ f2 lnP2 (23)
in which f1 and f2 are the volume fractions of the
two polymers, respectively, and P1 and P2 are
their permeabilities. It shows a linear trend when
the permeabilities are plotted on a logarithmic
scale and deviates from linearity in the case of
(partial) immiscibility of the two polymers
(Jansen et al. 2013).
Overall Performance
Robeson Trade-Off Behavior
Although membrane separations may have many
advantages compared to traditional separation
processes such as distillation or pressure swing
adsorption, a limitation is the trade-off behavior
between selectivity and permeability. This trend
was firstly discussed by Robeson in 1991, who
suggested a linear so-called upper bound for many
relevant gas pairs (Fig. 6) (Robeson 1991), which
were subsequently updated and extended
(Robeson et al. 1994; Robeson 2008). In 2015, a
new upper bound was set for O2/N2, H2/N2, and
H2/CH4, based on mostly the development of
polymers of intrinsic microporosity (Swaidan
et al. 2015). Freeman discussed the basis of the
upper bound (Freeman 1999) and concluded that a
combination of high free volume and extreme
rigidity of the polymer chains is needed to exceed
9
Gas/Vapor Transport, Fig. 6 O2/N2 1991 and 2008
upper bound curves for the selectivity versus permeability
trade-off relation (Robeson 1991, 2008) with the latest
upper bound suggested by Swaidan et al. (2015). The
oval represents the approximate cloud of experimental data
the current upper bound (Robeson et al. 2009).
This was confirmed by McKeown et al. with a
novel polymer of intrinsic microporosity based on
Troger’s base and ethanoanthracene (Carta
et al. 2013) or benzotriptycene units (Rose
et al. 2015). Alentiev presented a similar approach
for the trade-off in diffusion coefficient and diffu-
sion selectivity (Alentiev and Yampolskii 2013).
Effect of Physical Aging on the Transport
Properties
The global nonequilibrium state of glassy poly-
meric membranes tends to relax over time. This
process, where no chemical changes occur, is
called physical aging (Struik 1978) and affects
different properties of a polymer. One of these is
the free volume distribution, which, in turn, is
reflected in the gas transport properties of the
membrane. Physical aging therefore has a strong
impact on the performance of amorphous glassy
gas separation membranes (Pfromm 2006), and
gas diffusion is a very sensitive method to probe
changes in the free volume of a polymer mem-
brane (Jansen et al. 2009). Different aging mech-
anisms have been proposed. Harms claims that
free volume elements diffuse towards the surface
10
of the polymer (Harms et al. 2012). However, due
to the very low expected diffusion coefficient of
this process, it is significant only in the case of thin
layers. McCaig et al. proposed that the aging
consists of two distinct processes (McCaig and
Paul 2000): (i) thickness independent lattice con-
traction and (ii) thickness dependent diffusion of
free volume. Usually, the polymer chains pack
more efficiently during physical aging and the
polymer becomes denser, resulting in a decrease
in permeability and an increase in selectivity.
Many approaches have been used to overcome
physical aging and to prepare time-stable mate-
rial, such as crosslinking and addition of fillers.
Lau et al. showed that addition of an ultraporous
additive can prevent the effect of aging on the
transport properties of super glassy polymer mem-
branes (Lau et al. 2014).
Anomalous Transport
As already anticipated, Fick’s first and second
laws give a rather simplified representation of
diffusion in polymers, which usually applies
only to permanent gases at low pressures. In the
majority of cases, the diffusion coefficient is not a
constant, because of mutual interactions between
the permeating species, giving rise to clustering
(Jansen et al. 2011) and interaction between the
polymer and the permeating species,
“immobilizing” the latter (Mason et al. 2014) or
plasticizing the polymer (Lo et al. 2010) and
favoring diffusion. The solubility of gases and
vapors in the polymer matrix is usually only con-
stant at very low gas pressure or vapor activity. As
a result, the simple expression for the solution
diffusion model in Eq. 3 becomes concentration
dependent:
Pð c Þ ¼ D ð c Þ  S ð c Þ (24)
This anomalous behavior becomes even more
complex in the case of mixed gas or vapor perme-
ation, where there may also exist a coupling effect
between the different species in the mixture.
Gas/Vapor Transport
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G
Gas–Liquid Membrane Contactor
Denis Roizard
Laboratoire Réactions et Génie des Procédés,
CNRS- Université de Lorraine, Nancy, France
Synonym
Gas–liquid exchangers using membrane as inter-
face; Nondispersive gas–liquid contactor
History
Gas–liquid contactors are devices which are
designed to promote mass transfer between a
gas phase and a liquid phase, thanks to gas–liquid
contact. Among the various types of existing
contactors, e.g., valve trays, random or structured
packing, demister, vacuum towers, etc., and
membranes, one can clearly distinct two catego-
ries: firstly, contactors requiring a straight mixing
between the gas and the liquid phases and,
secondly, contactors where the direct physical
contact between the two phases does not exist,
i.e., a contactor which does not need dispersion of
one phase into the other one to be efficient (Fig. 1).
Up to now, membrane contactors are the only
example of the second category, i.e., systems
which are simultaneously able to avoid phase
mixing while promoting mass transfer. Obvi-
ously the higher the membrane permeability, the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_265-1
better is mass transfer efficacy. Currently, most of
the industrial applications are using microporous
membrane contactors (Liqui-Cell ® 2014).
Like with other gas/liquid contactors, the mass
transfer obtained by means of contactors can be
directed to carry out either separation and purifi-
cation operations of a gas mixture by the selective
removal of a given gas component or, conversely,
absorption of gas (e.g., N2, O2, O3, etc.) in the
liquid phase. The driving force is the gas partial
pressure according to the Henry law: pi = Hxi
with p the partial pressure, x the concentration
of gas at equilibrium, and H the Henry law coef-
ficient. Note also that the driving force of the
mass transfer can also be due to a chemical reac-
tion between the gas species and the liquid phase.
Phenomenon
In the 1980s, Qi and Cussler (1985) achieved
pioneering work devoted to the understanding
of mass transfer in gas–liquid membrane
contactors. Within this specific type of
contactors, the membrane is primarily a physical
barrier between a gas phase and a liquid phase. So
to get an efficient device, a proper choice of
membrane and operating conditions must be
done to ensure a high level of mass transfer. For
the membrane selection, it turned out that a
microporous structure looked to be the best one
to gather appropriate mechanical properties and
high mass transfer coefficient. Most of the time,
2 Gas–Liquid Membrane Contactor
Gas–Liquid Membrane Contactor, Fig. 1 Schematic
representation of a G/L membrane contactor
Gas–Liquid Membrane Contactor,
Fig. 2 Microporous polypropylene
the liquid phase used is an aqueous phase; hence,
it logically orientated the selection of membranes
to hydrophobic rigid polymers, i.e., glassy or
semicrystalline structures, like polypropylene
(PP) (Fig. 2), polyvinyl difluoride (PVDF), or
Teflon. Thus the aqueous phase cannot enter
spontaneously the small pores (
0.1–1.106 m)
of the membrane structure, as predicted by the
Young–Laplace equation given below. Neverthe-
less, the main concern with a microporous mem-
brane contactor is to avoid pore wetting by the
liquid phase, because pore wetting would induce
a detrimental decrease of the overall mass trans-
fer coefficient (Fig. 3a, b). In case of pore
flooding, the mass transfer coefficient can drop
by a factor 1,000–10,000.
Hence there is a breakthrough pressure to be
respected; this limiting pressure (Dp) difference
between the two phases can be calculated by the
Young–Laplace equation (Kim and Harriott
1987):
Dp ¼ 4gL : cos y=dmax (1)
with gL the surface tension of water, y the contact
angle, and dmax the diameter of the biggest
micropores.
As a guide, using pure water

(gL = 72.8 mN/m at 20 C) and PP (with pore
dmax = 1 mm and y = 115 ), the breakthrough
pressure is 1.23 bar. However in reality, the mea-
sured breakthrough pressure is often much lower
due to the presence of impurities or organic sol-
utes in the water; any alteration of the polymer
surface properties can also lower this value. On
the other hand, to avoid any gas bubbling in the
liquid phase, a slight overpressure is usually
applied at the membrane liquid interface.
Mass Transfer Theory
As one can expect, the mass transfer extent is
closely related to the operating parameters, i.e.,
mainly gas partial pressure in each phase, tem-
perature, gas and liquid flow rates, hydrodynamic
conditions, and the specific transfer area. To
achieve a given purification target, the mecha-
nism of the gas/liquid transfer must be known
and used to model the mass transfer and thus to
predict adequate operating parameters.
The performance of the mass transfer can be
related to the variation of gas composition either
between the inlet and the outlet of the gas phase
or between the inlet-dissolved gas and the outlet-
dissolved gas of the liquid phase. For a fast reac-
tion with a steady gas phase velocity, the same
basic equations, which are used to predict trans-
ferring gas in conventional columns, also apply
for membrane contactors as recalled below:
CGout
¼ ek:a:L=ug (2)
CGin
where CGout and CGin are respectively the outlet
and inlet gas concentrations, k is the overall mass
transfer coefficient, L is length of the contactor, a
is the contact area between the two phases, and ug
the gas phase velocity.
Gas–Liquid Membrane Contactor
a Gas phase Æ Æ Liquid phase
Cgas Cgas-Mb CMb-Liquid
Cliquid
1/kov = 1/kgas + 1/kmembrane + H/kliquid
Gas–Liquid Membrane Contactor, Fig. 3 (a) In a nonwetted porous membrane, the membrane transport occurs in
gas-filled pore. (b) In a wetted porous membrane, the membrane transport in liquid-filled pore is much slower
Noting one can define the gas transfer effi-
ciency Z = (CGin–CGout)/CGin, thus one can
write:
CGout
¼ 1  Z ¼ ek:a:L=ug
CGin
It is worth noting that modeling the mass transfer
properties of a membrane contactor is even easier
than with conventional contactors because the
gas/liquid contact area is well known and remains
constant whatever the gas or liquid flow rates.
As shown in Fig. 3, the overall mass transfer
resistance is due to the successive resistances of
the gas phase, of the membrane, and of the liquid
phase. Clearly the analogy can be made with
electrical resistances, and the reciprocal of the
overall mass transfer coefficient (kov) can be
written as the sum of the individual mass transfer
coefficients:
1=kov ¼ 1=kgas þ 1=kmembrane þ H=kliquid
H being the Henry law constant between the gas
and liquid phases.
Pros and Cons
Compared to conventional gas/liquid contactors
(tower, packed columns, mixer settler), mem-
brane contactors are known to avoid a number
3
b Gas phase Æ Æ Liquid phase
of drawbacks due to phase dispersion such as
solvent loss, foaming, unknown specified area,
and column flooding. It is worth also to underline
that as polymer is the core of membrane
contactors, one can get a strong reduction in
(3)
weight of the equipment compared to conven-
tional ones. At last one can note as well that a
membrane contactor can be installed horizontally
or vertically without problems and that its effi-
ciency is not dependent of roll and pitch marine.
Note that liquid–liquid extraction can also be
achieved using membrane contactors, hence
avoiding any hazard of emulsion formation.
All these advantages are linked to the mixing
nondispersive feature of a membrane contactor.
On the other side, drawbacks can come from
the facts that the pores of a membrane do not have
the same size, that pore fouling can occur and
block the transfer, and that the hydrophobic prop-
erties of the surface can be altered inducing a
dramatic decrease of the breakthrough pressure.
(4)
Intensification Potential of Mass
Transfer
As with any membrane modules, the membrane
contactors can be prepared with different geom-
etries, going from plate and frame modules, spiral
modules, or hollow fiber modules. The last type
has received the most attention because it allows
the creation of very large interfacial areas, up to
4 Gas–Liquid Membrane Contactor
10,000 m2/m3 that is up to 20-fold the interfacial
area of a structured packed column (Gabelman
and Hwang 1999; http://docnum.univ-lorraine.fr/
public/INPL/2011_NGUYEN_P_T.pdf6). Thus
the factor k.a., which is one of the key parameters
predicting the mass transfer efficiency (Eq. 3),
indicates clearly that for a constant value of k, a
strong intensification of the transfer can be
reached with membrane contactors.
This high value of area will be obtained with
fibers having very low inner diameter, typically
in the 50–100 mm range. Hence, a limit of the
transfer with membrane contactor can now be
foreseen: the increase of the specific area shall
correspond to an increase of the pressure drop in
the fibers of smaller diameter. This drawback will
be amplified by using fluid of high viscosity.
Thus the potential of intensification is also
strongly linked to the hydrodynamic conditions
prevailing in the contactor. This shall depend
merely on the nature of the fluid circulating in
the lumen of the fibers.
Applications
As example of separations, acid impurities of flue
gases like SOx, NOx, or even CO2 can be
removed by contacting the gas feed flow with a
liquid properly chosen to trap the acidic species.
The gas removal can be due to a physical chem-
ical dissolution of the acid gas into the liquid or to
a chemical reaction with the liquid; in this case,
the liquid must be endowed of basic properties or
contains a solute which is itself a base. When the
principle of gas removal is linked to physical
chemical affinities, it is wise to operate under
pressure to promote higher solubility of the gas
into the liquid. On the other case, if a chemical
reaction is involved between the gas and the
liquid, pressure is not a key parameter.
As example of gas dissolution, one can cite
nitrogenation in the beverage industry or blood
oxygenation. It is worth to note that blood oxy-
genation has been one of the very first examples
of using membrane contactors in 1975 (Esato and
Eiseman 1975); currently the total annual market
is above €500 million.
Some examples of use of membrane
contactors are listed here:
– Liquid degassing: O2, CO2, and N2 removal
from liquids, used for carbonation (food and
beverage industry), nitrogenation
(microelectronics), deoxygenation, etc.
– Bubble-free gas/liquid mass transfer primarily
for ozonation of semiconductor cleaning
water
– Dehydration
– Blood oxygenator (health sector)
Cross-References
▶ Gas Stripping
▶ Henry Law
References
Liqui-Cell ® web site (visited Apr 2014). http://www.
liquicel.com/
Esato K, Eiseman B (1975) Experimental evaluation of
Gore-Tex, membrane oxygenator. J Thorac Cardiovas-
cular Surg 69(5):690–697
Gabelman A, Hwang S-T (1999) Hollow fiber membrane
contactors. JMS 159:61–106
Kim B, Harriott P (1987) Critical entry pressure for liquids
in hydrophobic membranes. J Colloid Interface Sci
115(1):1–8
Qi Z, Cussler EL (1985) Microporous hollow fibers for gas
absorption. I, II. Mass transfer in the liquid. J Membr
Sci 23(3):321–332, and ibid 23(3):333–345
G
Glass Transition Temperature (Tg)
Johannes Carolus Jansen
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
General Introduction
At the macroscopic scale, the glass transition tem-
perature, Tg, represents the temperature above
which a material changes from a stiff glass into a
viscous fluid or a rubbery material. Besides poly-
mers, which are the most common materials with
a glass transition temperature, also various amor-
phous solids, organic liquids, alloys, or inorganic
glasses may exhibit a glass transition.
At the molecular scale, the Tg of a polymer is
the temperature above which large segmental
motions of the polymer chains become possible
within the time scale of the experiment. The glass
transition temperature depends on the molecular
architecture. Substituents that restrict the back-
bone rotation of a very simple polymer, such as
polyethylene, will increase its Tg, and the pres-
ence of polar groups will have an even stronger
effect (Table 1). Besides the substituents on a
flexible polymer backbone, the chemical structure
of the backbone itself obviously has a major
impact on the glass transition temperature. The
presence of sterically hindered groups, conjugated
bonds, fused rings, etc., increases the glass transi-
tion temperature significantly. In the extreme case,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_267-1
the mobility is so much restricted that a Tg is no
longer observed. For instance, polymers of intrin-
sic microporosity (PIMs), a novel class of poly-
mers with growing interest for their high gas
permeability (McKeown and Budd 2010), consist
of ladder structures with such a high rigidity that
large-scale motions are impossible and they do
not exhibit a glass transition below their degrada-
tion temperature.
The glass transition temperature of polymer
blends depends on their miscibility. In the rare
case of miscibility at the molecular level, the
glass transition of the blend has a value between
those of the neat polymers. Different equations
describe the behavior of polymer blends more or
less satisfactorily.
In the Fox equation, the Tg of the blend
depends exclusively on its composition:
1 w1 w2
¼ þ (1)
T g T g ,1 T g ,2
where w1 and w2 are the weight fractions and Tg,1
and Tg,2 are the glass transition temperatures of
pure polymer 1 and polymer 2, respectively.
The Gordon-Taylor equation is able to describe
slightly asymmetric dependencies of the Tg on the
blend composition, by means of an adjustable
parameter, KGT:
2 Glass Transition Temperature (Tg)

Glass Transition Temperature (Tg), Table 1 Glass transition temperature of polymers -[-CH2CH(R)-]n- with the same
backbone and different substituents R (Brandrup et al. 1999)
Polymer R Tg
Polyethylene H 155
Polypropylene CH3 258–270
Poly(vinyl fluoride) F 314
Poly(vinyl chloride) Cl 354
Poly(vinyl alcohol) OH 358
Polystyrene C6H5 373
Poly(vinyl acetate) CH3COO 305

Glass Transition Temperature Analysis

Besides a change in the mechanical properties, the

Tg is also accompanied by a fairly abrupt change
in the specific heat of the sample (Fig. 1). Various
other properties undergo more or less pronounced
changes at the Tg, such as the density, the specific
heat, the elasticity coefficient or Young’s modu-
lus, the rate of diffusion of gases or liquids
through the polymer, the thermal expansion coef-
ficient, etc.
There is a clear correlation between the glass
transition temperature and the transport properties
in dense membranes (Matteucci et al. 2006). The
gas and vapor permeability is much higher in the
Glass Transition Temperature (Tg), Fig. 1 Schematic rubbery state than in the glassy state, and the
representation of a DSC trace (bottom) and of the specific
volume (top) of an amorphous polymer
selectivity is usually lower. Therefore, the value
of the Tg is one of the main parameters influencing
the membrane performance. For most other mem-
w1 T g,1 þ K GT w2 T g,2
Tg ¼ (2) brane applications, also those using porous mem-
w1 þ K GT w2 branes, the glass transition temperature is of large
interest too. Since porous membranes may col-
The Kwei equation introduces a binary parameter,
lapse upon softening, it is of fundamental impor-
q, which represents the interaction between the
tance that they are operated at a temperature
two polymers, and can be used to describe even
sufficiently far below the Tg.
more asymmetric Tg versus composition profiles
(ElMiloudi et al. 2009):
References
w1 T g,1 þ K Kwei w2 T g,2
Tg ¼ þ qw1 w2 (3)
w1 þ K Kwei w2 Andrews RJ, Grulke EA (1999) Glass Transition Temper-
atures of Polymers. In: Brandrup J, Immergut EH,
Grulke EA (eds) Polymer handbook, 4th edn. Wiley,
Hoboken
ElMiloudi K, Djadoun S, Sbirrazzuoli N, Geribaldi S
(2009) Miscibility and phase behaviour of binary and
ternary homoblends of poly(styrene-Co-Acrylic acid),
poly(styrene-Co-N, N-Dimethylacrylamide) and Poly
Glass Transition Temperature (Tg)
(styrene-co-4-Vinylpyridine). Thermochim Acta
483(1–2):49–54
Matteucci S, Yampolskii Y, Freeman BD, Pinnau I (2006),
Transport of gases and vapors in glassy and rubbery
polymers, In: Yampolskii Y, Pinnau I, Freeman BD
(eds.) Materials science of membranes for gas and
3
vapor separation, John Wiley & Sons, Ltd, Chichester,
UK. doi: 10.1002/047002903X.ch1
McKeown NB, Budd PM (2010) Exploitation of intrinsic
microporosity in polymer-based materials. Macromol-
ecules 43(12):5163–5176
G
Glass Transition Temperature
Depression
Johannes Carolus Jansen
Institute on Membrane Technology ITM-CNR,
Consiglio Nazionale delle Ricerche, Rende (CS),
Italy
Glass transition temperature depression is the phe-
nomenon which describes the reduction of the
glass transition temperature by external factors,
usually by the presence of solvent molecules or
of other additives in the polymer matrix. Such
additives have the capacity to enhance the mobil-
ity of the polymer chains, thus enabling long
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_268-1
range motions at lower temperature than in the
neat polymer. Although this often goes hand in
hand with the phenomenon of plasticization, a
reduction of the elastic modulus at room temper-
ature, the two concepts should not be confused.
Plasticization strictly refers to the mechanical
properties of the polymer and the molecules,
which reduce the elastic modulus of a polymer
by an increase of the chain mobility generally also
reduce their glass transition temperature. The
opposite is not necessarily the case and it may
happen that an additive, which lowers the Tg, at
low concentration increases the elastic or Young’s
modulus at room temperature. This is then
referred to as anti-plasticization.
G
Glassy Membranes
John Jansen
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rande(CS), Italy
Glassy membranes are membranes consisting of
amorphous polymers which are in their glassy
state at room temperature or under the normal
operation conditions, i.e., their glass transition
temperature is above room temperature or the
operating temperature. The high stiffness of the
glassy polymer provides sufficient mechanical
strength to the membranes to exist also as porous
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_269-1
or dense integrally skinned flat films or hollow
fibers.
The polymer stiffness is an essential aspect in
the membrane formation process by non-solvent
induced phase inversion, where at a certain point
of the process solidification of the polymer is
required to consolidate the morphology of the
membrane. In glassy polymers, this is typically
by vitrification of the polymer when diffusion of
the solvent from the polymer rich phase into the
coagulation bath leads to a gradual increase of the
glass transition temperature until this exceeds the
coagulation bath temperature.
G
Glassy Polymer
Johannes Carolus Jansen
Institute on Membrane Technology ITM-CNR,
Consiglio Nazionale delle Ricerche, Rende (CS),
Italy
Strictly, any amorphous polymer is glassy at tem-
peratures below its Tg, but in practice a glassy
polymer refers to those polymers which are in
their glassy state at room temperature, thus to
amorphous polymers with a glass transition tem-
perature above room temperature, in contrast to
rubbery polymers, which have a Tg below room
temperature, and (semi-)crystalline polymers with
a melting point above room temperature. Under
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_270-1
particular circumstances also semi-crystalline
polymers can become glassy after quenching, if
the crystallization kinetics and the crystal nucle-
ation rate are sufficiently slow to prevent crystal-
lization upon rapid cooling. A typical example of
such polymer is poly(ethylene
terephthalate), PET.
Glassy polymers are characterized by their
high stiffness and amorphous non-crystalline
structure. These properties make them size selec-
tive in their dense form and also mechanically
sufficiently resistant to exist as porous flat film
or hollow fibre membranes. Examples of the most
commonly used polymers in commercial mem-
branes are cellulose acetate, polysulfone, poly
(ether sulfone), polyimide, and polycarbonate.
G
Gold Recovery by Supported Liquid
Membranes
Argurio Pietro
Department of Environmental and Chemical
Engineering, University of Calabria, Arcavacata
di Rende (CS), Italy
Gold is the chemical element which symbol is Au
(from Latin aurum) and the atomic number is 79.
The oxidation states in its compounds range from

1 to +5, and Au(III) is the most common. Typ-
ical Au(I) complex is Au(CN)2
(in cyanide
media) which is the soluble form of gold encoun-
tered in mining, while in chloride media Au(III)
complexes (Au2Cl6) are the typical ones.
Gold production by means of its extraction
from mining can represent an important contri-
bution to environmental pollution. Metal ores,
which generally contain less than 1 ppm of
gold, are ground and mixed with sodium or potas-
sium cyanide for gold chemical extraction. Pre-
cious metal and heavy metal impurities such as
cadmium, lead, zinc, copper, nickel, and arsenic
are usually present in an anionic form (i.e., cya-
nide salts) after their extraction from metal ores.
These salts are toxic to the liver and kidneys
because of both cyanide and metal content.
Thus, it would be desirable to be able to selec-
tively remove these complexes for the recovery
of precious metals.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_272-6
Gold, over its use in jewelry, also has a wide
use in various industries, thanks to its physical
and chemical properties. Thus, the recovery of
this metal from the different wastewater gener-
ated by these industries is also of growing interest
(Alguacil 2004).
Gold can be recovered from different aqueous
solutions by various physicochemical separation
techniques as precipitation, ion exchange, carbon
adsorption, cementation, solvent extraction,
etc. In the case of convectional solvent extrac-
tion, metal ion-containing solution is placed in
contact with a large amount of an appropriate
organic phase (Kargari et al. 2004). This extrac-
tion step is followed by a stripping one. The main
drawback of solvent extraction is the large
amount of solvent required when dilute solutions
were processed, making this process not very
cheap and safe, since the used solvents are often
chlorinated and sometimes carcinogenic.
Liquid membrane (LM)-based processes have
become an attractive alternative to conventional
techniques for selective separation and concen-
tration of both organic and inorganic compounds
from dilute aqueous solutions since they combine
extraction and stripping into a single process,
thus reducing the solvent inventory requirement
and then cost significantly (Molinari and Argurio
2011). They also allow the use of expensive and
highly selective extractants, which otherwise
would be uneconomic in solvent extractions.
LM systems include nonsupported liquid
membranes (bulk liquid membrane (BLM) and
2 Gold Recovery by Supported Liquid Membranes
emulsion liquid membrane (ELM)) and
supported liquid membrane (SLM). SLMs con-
sist of an organic LM phase impregnated in a thin
hydrophobic microfiltration membrane. This LM
phase generally contains an extractant (carrier)
which binds very selectively the target compo-
nent in the donor phase (feed), transporting it into
the acceptor phase (strip), resulting in the
so-called facilitated transport (Molinari
et al. 2009a, b).
Referring to gold transport, SLM systems
have been tested in the separation of this precious
metal mainly from cyanide (Au(I)) or chloride
(Au(III)) media. Highly acidic conditions are
required for the extraction and transport of Au
(III) because of its easily reducible nature.
Various carriers for Au transport across a SLM
were reported in literature. Among them, the
commercially available extractant Cyanex ®
921 has been applied in the carrier-facilitated
transport of both gold(I) and gold(III) recovery
from cyanide and chloride media, respectively
(Alguacil et al. 2005). Gold(I) is transported
from alkaline pH values (6–11). Gold
(I) extraction takes place in that pH range by the
following equilibrium reaction:
Mþ þ AuðCNÞ2aq
þ 3 Lorg
, Mþ AuðCNÞ2
 3Lorg
where the subscripts aq and org denote the spe-
cies contained in the aqueous and organic phase,
respectively, and L represents the extractant.
In the case of gold(III), the extraction is
governed by the following pH-dependent equi-
librium reaction:
Hþ aq þ AuCl4
þ nLorg , Hþ AuCl4
nLorg
where n = 1, 2.
References
Alguacil FJ (2004) Carrier-mediated gold transport in the
system Cyanex 921–HCl–Au(III). Hydrometallurgy
71:363–369
Alguacil FJ, Alonso M, Sastre AM (2005) Facilitated
supported liquid membrane transport of gold (I) and
gold (III) using Cyanex ® 921. J Membr Sci
252:237–244
Kargari A, Kaghazchi T, Soleimani M (2004) Role of
emulsifier in the extraction of gold (III) ions from
aqueous solutions using the emulsion liquid membrane
technique. Desalination 162:237–247
Molinari R, Argurio P (2011) Recent progress in
supported liquid membrane technology: stabilization
and feasible applications. Membr Water Treat
2(4):207–223
Molinari R, Argurio P, Poerio T (2009a) Studies of various
solid membrane supports to prepare stable sandwich
liquid membranes and testing copper(II) removal from
aqueous media. Sep Purif Technol 70:166–172
Molinari R, Argurio P, Poerio T (2009b) Flux enhance-
ment of stagnant sandwich compared to supported
liquid membrane systems in the removal of Gemfibro-
zil from waters. J Membr Sci 340:26–34
G
Graft Polymerization
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Pakistan
Graft polymerization is a process in which mono-
mers are covalently bonded and polymerized as
side chains onto the main polymer chain (the
backbone).
Grafting is an attractive approach to impart a
variety of functional groups to a polymer. Graft
polymers are also known as graft copolymer
since it contains at least two different kinds of
monomer units such as the grafted side chains
that are structurally distinct from the main
chain. The monomer to be grafted may be of
one or more than one type; thus, the graft chains
in grafted copolymer may be homo-polymers or
copolymers as illustrated in Fig. 1 (A, B, and
C are representing different types of monomers).
Grafting can be accomplished by either
“grafting to” or “grafting from” approaches. In
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_274-2
“grafting to” approaches, functionalized mono-
mers react with the backbone polymer to form the
grafted one. On the other hand, “grafting from” is
achieved by treating a substrate with some
method to generate immobilized initiators
followed by polymerization. High grafting den-
sity polymer also can be accomplished using this
technique (Bhattacharya et al. 2009).
Graft copolymerization can be initiated by
various methods including chemical treatment,
photochemical treatment, ionizing radiation
(such as gamma radiation, electron beam radia-
tion, etc.), photo-irradiation, plasma-induced
techniques and enzymatic grafting, etc. Grafted
polymers can be very useful as they can be tai-
lored to the requirements of particular applica-
tions by appropriate selection of backbone and
monomers to be grafted.
Grafted polymers have wide range of applica-
tion such as in the field of biomedical, textiles,
automobiles, cable technology, separation and
purification, electrolyte membranes, coatings,
adhesives, laminates, commodity plastics, etc.
2 Graft Polymerization

graft homo-polymer graft copolymer

B
B B
B C C C
B B C
B C
base polmer C C
C
A A A B C
A A A A A A A A
A A A A A A A C
A A A A A A A A A
B A A A A
C C B
B C
B C B
B B
B C C
B B
B C graft homo-polymer B
B
graft copolymer B
B

Graft Polymerization, Fig. 1 Structural representation of graft copolymer

References

Bhattacharya A, Rawlins JW, Ray P (2009) Polymer

grafting and crosslinking. John Wiley & Sons, Inc.,
Hoboken, New Jersey
H
Hexavalent Chromium Separation by 0.05 mg/L. Usually Cr(VI) concentrations in
Supported Liquid Membranes industrial wastewaters range from 0.5 to
Argurio Pietro
Department of Environmental and Chemical
Engineering, University of Calabria, Arcavacata
di Rende (CS), Italy
The removal and/or recovery of heavy metals
from industrial wastewater is a major topic of
research. Chromium is a unique, toxic heavy
metal released in aqueous environment in both
+3 and +6 oxidation states. Hexavalent chromium
(Cr(VI)) receives particular attention because of
its muta-, terato- and carcinogenic properties. Cr
(VI) exists as anionic species, such as HCrO4
,
Cr2O72
, and CrO42
, which are highly mobile on
subsurface environment (Kumbasar 2008). These
anionic species are bioaccumulative, and their
oxidizing potentials make them highly toxic to
biological systems. The major industries that con-
tribute to water pollution by chromium are mining,
leather tanning, textile dyeing, electroplating,
metal finishing, and corrosion inhibition
(Rajasimman and Karthic 2010).
The World Health Organization recommends
the toxic limits of Cr(VI) in wastewaters at the
level of 0.005 mg/L. Many countries have regu-
lations of the maximum permissible concentra-
tion of Cr(VI) in natural or drinking water which
typical tolerance limit for discharge into inland
surface waters is 0.1 mg/L and in potable water is
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_276-9
270,000 mg/L. Then chromium-bearing waste-
waters must be discharged into aquatic environ-
ments or onto land after appropriate treatments to
drastically reduce Cr(VI) content.
The methodologies for Cr(VI) recovery, from
industrial wastewater, range from ion exchange
to solvent extraction, non-dispersive solvent
extraction, precipitation, and adsorption. Solvent
extraction has been widely used for the removal
and/or recovery of chromium in hydrometallurgy
since this technique allows the Cr ions recovery,
but it involves high capital and operating costs
due to large inventory of solvent, especially in the
case of dilute solutions. Conventionally the treat-
ment chromium-bearing wastewaters consists of
the reduction of Cr(VI) to Cr(III) with an ade-
quate chemical-reducing agent. Cr(III) is then
easily precipitated by the addition of an alkali
compound (generally calcium hydroxide) to the
liquid effluent. The main drawback of this
method is the production of a large amount of
sludge-containing chromium often in high con-
centration, which disposal/treatment is a very
costly affair and it is not eco-friendly.
Supported liquid membrane (SLM) process
offers a technology with a low solvent/extractant
consumption since it involves in a single stage the
extraction and stripping processes, which are
generally performed in two separate steps in con-
ventional solvent extraction. SLM consists of a
LM phase, impregnated in the pores of a thin
2 Hexavalent Chromium Separation by Supported Liquid Membranes
Feed Liquid membrane Strip
HCrO4− H2CrO4 TOPO HCrO4−
H+ TOPO H+
HCrO4− HCrO4−
H+ H+
Hexavalent Chromium Separation by Supported
Liquid Membranes, Fig. 1
hydrophobic microfiltration membrane, kept
there by capillary forces. It combines the typical
advantages of liquid membrane with the mechan-
ical resistance of solid membranes. The transport
across a SLM is mediated by a mobile extractant
(carrier) which binds very selectively the target
component in the donor phase (feed),
transporting it into the acceptor phase (strip),
resulting in the so-called facilitated transport
(Molinari et al. 2009a, b). The selection of an
appropriate carrier provides higher selectivity
and enrichment factor as compared to the other
separation methodologies.
Despite of their advantages with respect to the
traditional separation techniques, SLM is not
widely applied in treatment of chromium-bearing
wastewaters. Cr(VI) compounds could be
removed from dilute aqueous solutions by using
trioctylphosphine oxide (TOPO), Alamine
336, tri-n-octylamine (TOA), and tributyl phos-
phate (TBP) as ionic carrier.
The extraction of HCrO4
with TOPO from
acidic solutions could be expressed by the fol-
lowing equation (Kumbasar 2009; Hasan
et al. 2009):
HCrO4
ðaqÞ þ Hþ ðaqÞ þ TOPOðorgÞ
, H2 CrO4 TOPOðorgÞ
The so-formed complex diffuses through the
membrane toward the stripping basic solution
where the de-complexation reaction takes place
and HCrO4
and H+ ions are released. The
so-regenerated carrier molecule diffuses back to
the feed and the transport cycle begins again
(Fig. 1). This transport mechanism is the
so-called facilitated coupled co-transport, typical
when a basic carrier like amines or phosphates is
used to transport negatively charged species
(in this case HCrO4
) and usually H+ as counter-
ion across the membrane in the same direction
(Fig. 1).
Cr(VI) complexes can be efficiently removed
from acidic chloride aqueous solutions by facili-
tated transport with TOA into a basic (NaOH
0.1 M) acceptor phase (Kozlowski and
Walkowiak 2002). In agreement with the trans-
port mechanism that is similar to that one previ-
ously reported for TOPO, the permeability
coefficient and then initial flux values decrease
linearly by increasing the feed pH. Cr
(VI) concentration can be successfully reduced
in the feed phase from 1.0 to 0.0028 mg/L, thus
respecting the World Health Organization’s
recommendations.
References
Hasan MA, Selim YT, Mohamed KM (2009) Removal of
chromium from aqueous waste solution using liquid
emulsion membrane. J Hazard Mater 168:1537–1541
Kozlowski CA, Walkowiak W (2002) Removal of chro-
mium (VI) from aqueous solutions by polymer inclu-
sion membranes. Water Res 36:4870–4876
Kumbasar RA (2008) Studies on extraction of chromium
(VI) from acidic solutions containing various metal
ions by emulsion liquid membrane using Alamine
336 as extractant. J Membr Sci 325:460–466
Kumbasar RA (2009) Extraction of chromium (VI) from
multicomponent acidic solutions by emulsion liquid
membranes using TOPO as extractant. J Hazard
Mater 167:1141–1147
Molinari R, Argurio P, Poerio T (2009a) Studies of various
solid membrane supports to prepare stable sandwich
liquid membranes and testing copper(II) removal from
aqueous media. Sep Purif Technol 70:166–172
Molinari R, Argurio P, Poerio T (2009b) Flux enhance-
ment of stagnant sandwich compared to supported
liquid membrane systems in the removal of Gemfibro-
zil from waters. J Membr Sci 340:26–34
Rajasimman M, Karthic P (2010) Application of response
surface methodology for the extraction of chromium
(VI) by emulsion liquid membrane. J Taiwan Inst
Chem Eng 41:105–110
H
Heterogeneous Ion-Exchange
Membranes
Mitsuru Higa
Graduate School of Science and Engineering,
Yamaguchi University, Ube, Yamaguchi, Japan
Heterogeneous ion-exchange membrane consists
of finely powdered ion exchanger and a binder
polymer, and, in many cases, the membrane is
reinforced by woven cloth or net to improve its
mechanical properties. In general, heterogeneous
ion-exchange membranes (IEMs) are prepared by
the following method (Sata 2004): finely pow-
dered organic and/or inorganic ion exchanger is
homogeneously mixed and heated with a thermo-
plastic polymer such as poly(vinyl chloride),
polyethylene, polypropylene, or other engineer-
ing plastics, and then the mixture is formed into
the membrane by pressing and/or heating. Het-
erogeneous IEMs have slightly lower electro-
chemical properties: lower permselectivity for
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_278-1
counterions and/or higher membrane resistance
than homogeneous ion-exchange membrane.
However, heterogeneous IEMs are easily pre-
pared and have high mechanical strength. More-
over, the IEMs of various kinds of shapes can be
easily prepared by pressing and/or heating as
shown in Fig. 1: (a) commercial flat-sheet IEMs
such as Ralex CMH and AMH (Mega a.s., Czech
Republic), (b) profiled IEM for reverse electro-
lyte applications (Vermaas et al. 2011),
(c) hollow fiber-type IEMs (Kiyono et al. 2004),
and (d) commercial tubular-type IEMs
(EDCORE, Astom. Co., Ltd., Japan). EDCORE
is a membrane electrode apparatus, with smooth-
surfaced seamless and tubular IEMs (Fig. 2), and
is used in industries such as electro-deposition
painting of automobile, building materials,
house appliance, and other applications due to
their high mechanical strength and ease of
handling.
2 Heterogeneous Ion-Exchange Membranes

Heterogeneous Ion-Exchange Membranes, Fig. 1 Schematic diagram of heterogeneous IEMs with various kinds
of shapes

References

http://www.astom-corp.jp/en/en-main2-edcore.html
Kiyono R, Koops GH, Wessling M, Strathmann H (2004)
Mixed matrix microporous hollow fibers with
ion-exchange functionality, J Membr Sci 231:
109–115
Sata T (2004) Ion exchangemembrane. The Royal Society
of Chemistry, Cambridge
Vermaas DA, Saakes M, Nijmeijer K (2011) Power
generation using profiled membranes in reverse elec-
trodialysis, J Membr Sci 385-386. 234-242
Heterogeneous Ion-Exchange Membranes,
Fig. 2 Tubular-type heterogeneous IEM, EDCORE
H
High Free Volume Polymer
Peter M. Budd
Organic Materials Innovation Centre, School of
Chemistry, University of Manchester,
Manchester, UK
Free volume is the unoccupied space between
molecules. The concept of free volume is used
to explain molecular motion in liquids and solids.
In a liquid or rubber, free volume increases with
increasing temperature. A flexible polymer will
flow or behave as a rubber at temperatures at
which there is sufficient free volume for large-
scale movements of polymer segments but will
behave as a glass when the temperature is
reduced to the point where there is not enough
free volume for such movements.
Different assumptions may be made about
what constitutes “occupied” and what constitutes
“free” volume in a material. Thus, in different
contexts, different values may be quoted for the
amount of free volume in a polymer. In mem-
brane science, it is common to define fractional
free volume as
V  1:3V w
fv ¼
V found in polymers of intrinsic microporosity,
where V is the specific volume (reciprocal of
density) and Vw is the specific van der Waals
volume, which for many polymers may be
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_279-5
estimated using group contribution methods.
The factor 1.3 takes account of the fact that mol-
ecules cannot completely fill space even in a
perfectly ordered crystal at absolute zero and is
an average value for crystalline materials. By this
definition, most glassy polymers have fv < 0.2.
Some glassy polymers, however, have much
higher fractional free volumes and consequently
exhibit high permeabilities to gases and vapors
(Budd and McKeown 2010; Yampolskii 2012;
Pinnau and Toy 1996; Starannikova et al. 2008;
Thomas et al. 2009). The structures of some poly-
mers with exceptionally high free volume are
shown in Fig. 1.
A common feature of high free volume poly-
mers is that they have relatively inflexible,
twisted backbones, which cannot change confor-
mation in order to fill space efficiently. In
substituted polyacetylenes such as PTMSP, the
bulky side group inhibits rotation about single
bonds in the backbone and forces the backbone
into a twisted shape. In perfluoropolymers such as
Teflon AF2400, neighboring dioxolane rings can-
not easily rotate past each other. In substituted
polynorbornenes prepared by addition polymeri-
zation, such as PTMSN, ring structures and bulky
side groups restrict rotation about backbone
bonds. The ultimate extension of this idea is
such as PIM-1, which have no single bonds in
the backbone about which rotation can occur but
which incorporate sites of contortion (the spiro
2 High Free Volume Polymer
High Free Volume Polymer, Fig. 1 Molecular struc-
tures and fractional free volumes of poly(1-trimethylsilyl-1-
propyne) (PTMSP), a copolymer of 2,2-bistrifluoromethyl-
4,5-difluoro-1,3-dioxole and tetrafluoroethylene (Teflon
AF2400), addition-type poly(trimethylsilyl norbornene)
centers in PIM-1) to force the backbone to twist
and turn.
The polymers shown in Fig. 1 are soluble and
can readily be processed from solution to form
membranes. However, there are other high free
volume polymers which cannot be prepared in
soluble form. Sometimes, it is possible to form a
membrane from a soluble precursor and subse-
quently convert it to the desired structure through
chemical or thermal treatment. For example,
polybenzoxazole structures can be prepared by
thermal rearrangement from aromatic hydroxyl-
containing polyimides (Park et al. 2007).
The permeation of gases and vapors through a
polymer depends not only on the amount of free
(PTMSN), and a polymer of intrinsic microporosity
prepared from 5,50 ,6,60 -tetrahydroxy-3,3,30 ,30 -tetramethyl-
1, 10 -spirobisindane and 1,4-dicyanotetrafluorobenzene
(PIM-1)
volume but also on the size, distribution, and
connectivity of free volume elements. Computer
simulation is useful for visualizing the free vol-
ume distribution in amorphous polymers
(Hofmann et al. 2002). A number of experimental
techniques, notably positron annihilation lifetime
spectroscopy (PALS), have been employed to
obtain information about the size and distribution
of free volume elements. In a high free volume
polymer, there may be sufficient connectivity
between free volume elements for the polymer
to behave like a molecular sieve or microporous
material (pore size <2 nm) (Rutherford 2001), in
which case the apparent micropore distribution
High Free Volume Polymer
can be determined from gas adsorption studies
(McKeown and Budd 2010).
References
Budd PM, McKeown NB (2010) Highly permeable poly-
mers for gas separation membranes. Polym Chem
1:63–68
Hofmann D, Heuchel M, Yampolskii Y, Khotimskii V,
Shantarovich V (2002) Free volume distributions in
ultrahigh and lower free volume polymers: compari-
son between molecular modeling and positron lifetime
studies. Macromolecules 35:2129–2140
McKeown NB, Budd PM (2010) Exploitation of intrinsic
microporosity in polymer-based materials. Macromol-
ecules 43:5163–5176
Park HB, Jung CH, Lee YM, Hill AJ, Pas SJ, Mudie ST,
Van Wagner E, Freeman BD, Cookson DJ (2007) Poly-
mers with cavities tuned for fast selective transport of
small molecules and ions. Science 318:254–258
3
Pinnau I, Toy LG (1996) Gas and vapour transport prop-
erties of amorphous perfluorinated copolymer mem-
branes based on 2,2-bistrifluoromethyl-4,5-difluoro-
1,3-dioxole/tetrafluoroethylene. J Membr Sci
109:125–133
Rutherford SW (2001) Mechanism of sorption and diffu-
sion in a high free volume polymer. Ind Eng Chem Res
40:1370–1376
Starannikova L, Pilipenko M, Belov N, Yampolskii Y,
Gringolts M, Finkelshtein E (2008) Addition-type
polynorbornene with Si(CH3)3 side groups: detailed
study of gas permeation and thermodynamic proper-
ties. J Membr Sci 323:134–143
Thomas S, Pinnau I, Du N, Guiver MD (2009) Pure and
mixed-gas permeation properties of a microporous
spirobisindane-based ladder polymer (PIM-1).
J Membr Sci 333:125–131
Yampolskii Y (2012) Polymeric gas separation mem-
branes. Macromolecules 45:3298–3311
H

Higher (C3+) Hydrocarbon Removal
Arnaud Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
very profitable for the recovery of high-value
monomer in petrochemical plants’ purge gases
(Table 1). In the case of large polymerization
facilities, the value of purge monomers can
reach amounts up to two million USD/year.

Rubbery polymer membrane materials have the

ability to permeate preferentially condensable
vapors. Rubbery membranes were found to be

# Springer-Verlag Berlin Heidelberg 2012

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_280-1
2 Higher (C3+) Hydrocarbon Removal

Higher (C3+) Hydrocarbon Removal, Table 1 Membrane-based olefin recovery from polymer resin degassing vent
(MTR Inc. membrane modules) Baker and Jacobs 1996; Baker et al. 2000
Application Feed composition Olefin flow rate recovered (recovery yield)
LLDPE/HDPE reactor purge Butene 36 % C2 = 145 kg/h (88 %)
Ethylene 41 % nC4 = 142 kg/h (98 %)
Ethane 1 %
Nitrogen 21 %
Hydrogen 1 %
HDPE resin degassing 1-butene 57 % iC4 = 1160 kg/h (97 %)
CO2/O2 2 %
Nitrogen 40 %
Water 1 %
Polypropylene resin degassing Propylene 14 % C3 = 500 kg/h (91 %)
Propane 0.3 %
Nitrogen 84.4 %
Hydrogen 1 %
Water 0.3 %

References Baker RW, Lokhandwala KA, Jacobs ML, Gottschlich DE

(2000) Recover feedstock and product from reactor
Baker RW, Jacobs M (1996) Improve monomer recovery vent streams. Chem Eng Progr 96:51–57
from polyolefin resin degassing. Hydrocarbon Proc
75:49–51
H
High-Throughput Membrane
Technology
Sanne Hermans and Ivo Vankelecom
Centre for Surface Chemistry and Catalysis,
Department of M2S, Faculty Bioscience
Engineering, KU Leuven, Leuven, Belgium
The term “high-throughput” (HT) refers to the
creation of a large output, i.e., a large amount of
data that is obtained from simultaneous, parallel
experiments. In general, HT methodologies are
used to speed up the formulation and discovery of
new materials or the optimization of processes.
They include a variety of advanced tools which
allow fast parallel experiments, leading to higher
productivities and shorter “time to market” times.
While “HT” thus refers to the number of experi-
ments, “combinatorial” strategies are related with
the experimental design.
Besides automation (to whatever desired
degree), a faster screening and more rapid opti-
mization due to simultaneous testing, other
advantages of HT technologies are the miniatur-
ization (leading to smaller sample sizes and
reductions in costs and waste streams) and the
reproducible conditions between samples
(as parallel tests are performed under identical
experimental conditions, e.g., pressure,
temperature).
Membrane technology can gain from the
implementation of HT technologies on several
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_281-1
levels. As membrane performance is influenced
by a variety of parameters, an efficient HT
screening of multiple variables can lead to the
rapid development of new membranes and mem-
brane applications.
HT devices can be implemented during the
membrane preparation, the membrane screen-
ing, and the optimization of the membrane pro-
cess parameters. The former relates to automated
devices developed for weighing powders, dis-
pensing liquids, homogenizing solutions, casting
these polymer solutions, dip coating, etc. More
details can be found on www.html-membrane.
beand, www.porometer.com.
HT devices for membrane screening are
commercially available for pressure-driven liq-
uid separation systems with a variable number of
membranes and different membrane areas per
equipment (Vandezande et al. 2005; Cano-
Odena et al. 2011; Van Doorslaer et al. 2010;
www.porometer.com 2014). Commercially
available HT devices also exist for gas separa-
tions, which were successfully applied to perform
quality control tests at industrial-scale production
and to quickly analyze membrane performance in
diverse studies (Khan et al. 2010, 2013; Basu
et al. 2011). The development of an HT mem-
brane bioreactor (MBR) was also reported to
simultaneously study the performance and foul-
ing properties of multiple membranes in one aer-
ated MBR (Bilad et al. 2011). In addition, an HT
cross flow filtration system was adapted into an
online fouling monitoring system, allowing
2 High-Throughput Membrane Technology
fouling studies of multiple membranes with high-
quality imaging and a high reproducibility
(Vanysacker et al. 2013). Filter plate HT plat-
forms were also applied together with photoin-
duced graft polymerization or atmospheric
pressure plasma-induced graft polymerization to
synthesize and screen antifouling membranes
(Zhou et al. 2009; Gu et al. 2013). An HT ionic
conductivity apparatus and an HT mechanical
testing apparatus for thin membranes were also
reported (Zapata et al. 2009, 2010).
When new HT devices are developed, their
performance should be evaluated based on
their reproducibility (of the same sample), inter-
changeability (of sample positions), and scalabil-
ity of the setup (compared to conventional
methods) (Bilad et al. 2011).
Together with the application of HT technol-
ogy, the design of experiments (DoE) has
become increasingly important. As membranes
can now be quickly synthesized and screened,
the implementation of appropriate experimental
design is crucial to obtain membranes with opti-
mal performances. The aim is then to quickly
eliminate experimental areas in which limited
successes are expected so combined experimen-
tation can be focused on potentially promising
areas. An efficient search strategy combined
with HT technology can rapidly lead to an opti-
mum in a large parameter space, in contrast to the
slower and less effective traditional parameter-
by-parameter approach. Two important aspects
are the certainty of finding an optimum and a
rapid progression of convergence toward the
optimal membrane performance.
Several experimental design types were
already applied in membrane technology.
Among them are artificial neural networks
(ANNs) to predict membrane fouling and separa-
tion performances in both liquid and gaseous
environments (Soleimani et al. 2013; Shokrian
et al. 2010). Genetic algorithms (GAs) were
applied to obtain an optimum in membrane com-
position, separation modules and operating con-
ditions, gas separation systems, and desalination
units (Bulut et al. 2006; Vandezande et al. 2009;
Yuen et al. 2000; Chang and Hou 2006; Guria
et al. 2005). Genetic programming, Plackett-
Burman design, Taguchi’s method, response sur-
face methodology, and fractional factorial design
are other DoE types already employed in mem-
brane technology.
The combination of HT technology with
appropriate DoE clearly leads to the acceleration
of acquiring output, hence, to a better understand-
ing of the effects of parameters and the properties
of new membrane materials and formulations. It
can thus generate a significant decrease in cost
and increase in efficiency during the discovery
and optimization stages of membrane design and
development processes.
Cross-References/Related Terms
▶ Combinatorial Strategies
▶ Design of Experiments
▶ Optimization
References
Basu S, Cano-Odena A, Vankelecom IFJ (2011) -
MOF-containing mixed-matrix membranes for CO2/
CH4 and CO2/N2 binary gas mixture separations. Sep
Purif Technol 81:31–40
Bilad MR, Declerck P, Piasecka A, Vanysacker L, Yan X,
Vankelecom IFJ (2011) Development and validation
of a high-throughput membrane bioreactor
(HT-MBR). J Membr Sci 379:146–153
Bulut M, Gevers LEM, Paul JS, Vankelecom IFJ, Jacobs
PA (2006) Directed development of high-performance
membranes via high-throughput and combinatorial
strategies. J Comb Chem 8:168–173
Cano-Odena A, Spilliers M, Dedroog T, De Grave K,
Ramon J, Vankelecom IFJ (2011) Optimization of
cellulose acetate nanofiltration membranes for
micropollutant removal via genetic algorithms and
high throughput experimentation. J Membr Sci
366:25–32
Chang H, Hou W-C (2006) Optimization of membrane gas
separation systems using genetic algorithm. Chem Eng
Sci 61:5355–5368
Gu M, Vegas AJ, Anderson DG, Langer RS, Kilduff JE,
Belfort G (2013) Combinatorial synthesis with high
throughput discovery of protein-resistant membrane
surfaces. Biomaterials 34:6133–6138
Guria C, Bhattacharya PK, Gupta SK (2005) Multi-
objective optimization of reverse osmosis desalination
units using different adaptations of the non-dominated
sorting genetic algorithm (NSGA). Comput Chem Eng
29:1977–1995
High-Throughput Membrane Technology
Khan AL, Basu S, Cano-Odena A, Vankelecom IFJ
(2010) Novel high throughput equipment for
membrane-based gas separations. J Membr Sci
354:32–39
Khan AL, Klaysom C, Gahlaut A, Khan AU, Vankelecom
IFJ (2013) Mixed matrix membranes comprising of
Matrimid and -SO3H functionalized mesoporous
MCM-41 for gas separation. J Membr Sci 447:73–79
Shokrian M, Sadrzadeh M, Mohammadi T (2010) C3H8
separation from CH4 and H2 using a synthesized
PDMS membrane: Experimental and neural network
modeling. J Membr Sci 346:59–70
Soleimani R, Shoushtari NA, Mirza B, Salahi A (2013)
Experimental investigation, modeling and optimiza-
tion of membrane separation using artificial neural
network and multi-objective optimization using
genetic algorithm. Chem Eng Res Des 91:883–903
Van Doorslaer C, Glas D, Peeters A, Cano Odena A,
Vankelecom I, Binnemans K, Mertens P, De Vos
D (2010) Product recovery from ionic liquids by
solvent-resistant nanofiltration: application to ozona-
tion of acetals and methyl oleate. Green Chem
12:1726–1733
Vandezande P, Gevers LEM, Paul JS, Vankelecom IFJ,
Jacobs PA (2005) High throughput screening for rapid
3
development of membranes and membrane processes.
J Membr Sci 250:305–310
Vandezande P, Gevers LEM, Weyens N, Vankelecom IFJ
(2009) Compositional optimization of polyimide-
based SEPPI membranes using a genetic algorithm
and high-throughput techniques. J Comb Chem
11:243–251
Vanysacker L, Declerck P, Vankelecom I (2013) Devel-
opment of a high throughput cross-flow filtration sys-
tem for detailed investigation of fouling processes.
J Membr Sci 442:168–176
Yuen CC, Aatmeeyata, Gupta SK, Ray AK (2000) Multi-
objective optimization of membrane separation mod-
ules using genetic algorithm. J Membr Sci
176:177–196
Zapata P, Basak P, Carson Meredith J (2009) High-
throughput screening of ionic conductivity in polymer
membranes. Electrochim Acta 54:3899–3909
Zapata P, Mountz D, Meredith JC (2010) High-throughput
characterization of novel PVDF/acrylic polyelectro-
lyte semi-interpenetrated network proton exchange
membranes. Macromolecules 43:7625–7636
Zhou M, Liu H, Kilduff JE, Langer R, Anderson DG,
Belfort G (2009) High-throughput membrane surface
modification to control NOM fouling. Environ Sci
Technol 43:3865–3871
H
Hollow Fiber Liquid Membrane
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Hollow fiber (HF) supported liquid membrane is
a three-phase liquid membrane system in which
the membrane phase (liquid) is held by capillary
forces in the pores of microporous polymeric or
inorganic hollow fibers. The design of the hollow
fiber SLM module consists of a certain number of
thin fibers, placed along the length of the shell.
The feed phase is pumped through the fibers; the
pores in the fibers are filled with the LM solution,
and the receiving (strip) phase is forced out
through the sides of the shell. HF SLMs are
schematically presented in the Figs. 1, 2, and 3.
Compact and modular hollow fiber devices can
be used with exceptionally high mass transfer
area per unit equipment volume. Very often
such HF systems are termed as contactor devices.
Contactor devices are used as construction units
in many of the SLM, HFCLM, and BLM systems.
The theory of the HFLM transport was developed
by Sirkar et al. (see in Sirkar 1996) and Schlosser
et al. (see in Schlosser and Sabolova 2002).
Different hollow fiber modules can be classi-
fied into several groups. One, termed as a “hollow
fiber contained liquid membrane (HFCLM)”
(Majumdar and Sirkar 1992) configuration, is
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_283-2
shown in Fig. 1a. The process is achieved by
packing thousands of microporous hollow fibers
in a permeator shell filled with stationary liquid
membrane solution. The fibers are present in feed
and strip sets very close to each other but with the
ends of each set being separated. If the fibers are
hydrophilic, the aqueous feed and strip flow
through the lumen side of the fibers and fill the
pores of the fiber; if fibers are hydrophobic, they
are wetted by organic LM phase (Fig. 1b). So,
reader can see that this is a hybrid system with
combination of modified SLM and BLM
configurations.
Hollow fibers in tube pertractor (Schlosser
2000) is another type of HF module (see Fig. 2)
“with parallel flow consisting of one or two
intermixed U-shaped bundles of microporous
polypropylene fibers, inserted into polysulfon
(or glass) tubes”. Pulsation of the LM phase
along the fibers is used for better mixing.
One more type of the HF modules is presented
schematically in Fig. 3. A crossflow with pulsa-
tion perpendicularly to fibers was used here.
Some plate and frame HF modules were pro-
posed. The module with “fiber in fiber” units
and crossflow of one phase is described in Ref.
Schlosser and Sabolova (2002).
A capillary membrane module was developed
(Teramoto et al. 2003) for gas separation. The
concept of a capillary membrane apparatus is
shown in Fig. 4. Both a feed gas and a LM
solution are supplied to the lumen side (high-
pressure feed side) of the capillary ultrafiltration
2 Hollow Fiber Liquid Membrane

b Sweep out
a

F F F

S S S
S Feed Feed
out in
F F F
Pressure
source
S S
LM -
reservoir
Sweep in

Hollow Fiber Liquid Membrane, Fig. 1 Hollow fiber contained liquid membrane (HFCLM): (a) configuration of
permeator shell and (b) side view of the permeator

Hollow Fiber Liquid RO R MO

M
Membrane, F FO
Fig. 2 Scheme of the
hollow fiber contactor with
parallel flow of phases
distributed U-shaped
bundles of fibers with 1
separated inlet and outlet
end chambers. [F feed
(donor) phase, M liquid 3
membrane phase,
A A'
R stripping solution,
1 hollow fiber for the feed, 2 Cross-section AA':
2 glass tubulet, 3 glass R
1
tempering jacket of the
contactor] (From Schlosser
M
and Sabolova 2002)

2 F
3

membrane module and flow upward. The LM
solution, which contains dissolved solute gas
(CO2), flows to the permeate side (low-pressure
shell side), where the solution liberates dissolved
gas to become a lean solution. The lean solution
is returned to the lumen of the capillary module
by a pump. In the shell side, dissolved gas is
stripped from the liquid flowing down on the
outer surface of the capillary and discharged
from a vacuum pump through a liquid reservoir.
One more example of hollow fiber LM sepa-
ration system is described as affinity dialysis
(Devis et al. 1988) Water-soluble polymer
(WSP) solutions as LM were immobilized into
the pores of hollow fiber units (fibers of 5,000
molecular weight cutoff from Spectra/Por were
used). Selective separation and concentration of
both cations (Ca/Na, Cu/Zn) and anions
(potassium chromate/sodium chloride) were
tested. 2.5 % w/v aqueous solution of poly
Hollow Fiber Liquid Membrane
Hollow Fiber Liquid
Membrane,
Fig. 3 Scheme of the
hollow fiber contactor of
three phases with crossflow
of LM phase: (1) body of
A 1
element, (2, 3) hollow fiber
in downstream and
upstream part, (4, 5) inlet 7
and outlet chamber, (6,7)
inlet and outlet tube, (8)
5
flowing head, (9) central
baffle; F feed, E LM phase, 9
R strip solution (From
Schlosser 2000) 3
A'
(2-acrylamido-2-methyl-1-propanesulfonic acid)
(poly-AMPS) for cation separations and 5 % w/v
solution of poly(ethylenimine) (PEI) for anion
separations were used as LM. High concentration
factor (50–75) and selectivity (30–40) were
obtained.
Hollow fiber membrane catalytic reactors
(HFMCR) and bioreactors (HFMBR) are rela-
tively new developments of SLM techniques.
The SLM reactors can be used to shift the equi-
librium conversion (e.g., esterification reaction),
to remove selectively products and by-products
from the reaction mixture, and to supply selec-
tively the reagents (e.g., oxygen for partial oxi-
dation reactions) (Li et al. 2003). Application of
SLM reactors appears of particular interest in
hydrogen production and oxidation reactions.
Applications of biocatalytic membrane reactors
(Cussler and Ding 1995) provide an ideal support
for catalyst immobilization due to their wide
3
R RO
6
FO F
B B'
SO 4
2
E 2
5
Section AA:
3
Section BB:
1 3 9 2
available surface area per unit volume and
include production of new or better foodstuffs,
novel pharmaceutical products with well-defined
enantiomeric compositions, conversion of lactose
into glucose and galactose, the isomerization of
glucose into fructose, and the separation of chiral
isomers of acylated racemic amino acids and
wastewater treatment.
The regeneration of degraded hollow fiber liq-
uid membranes could be done by pumping the
fresh LM at the lumen side of the support for a
few minutes instead of the aqueous solution.
Continuous impregnation of the membrane
pores is possible as it is in the HFCLM devices
or by adding membrane phase as an emulsion to
the strip aqueous phases. It is termed the
pseudoemulsion-based hollow fiber strip disper-
sion (PEHFSD) technique. The main drawback is
pollution of the product with the membrane
liquid.
4 Hollow Fiber Liquid Membrane

a b
exhaust gas exhaust gas
capillary
membrane
to pressure 30mm
gauge permeable
stripped gas section capillary
(165mm) membrane
to vacuum
liquid
pump
permeation capillary
enriched capillary membrane
impermeable
CO2 membrane coated with
section
opoxy (265mm) adhesive
adhesive to vacuum
capilarty mem exhaust gas pump distributor
vacuum module
absorbent feed gas absorbent feed gas
pump
CO2/N2 tee tee
carrier feed gas
solution (a) Module A (b) Module B

Hollow Fiber Liquid Membrane, Fig. 4 Schematic dioxide: (a) experimental capillary membrane apparatus
diagrams of facilitated transport of gas using capillary and (b) capillary membrane modules with permeation of
membrane module for removal and enrichment of carbon carrier solution (From Teramoto et al. 2003)

References Schlosser S (2000) Pertraction through liquid and poly-

Cussler EL, Ding H (1995) Bioseparations, especially
using hollow fibers. In: Singh RK, Rizvi SSH (eds)
Bioseparation processes in foods. Marcel Dekker, New
York, pp 1–15
Devis JC, Valus RJ, Lawrence EG (1988) Affinity
dialysis-a method of continuous, rapid metal ion sep-
aration using dialysis membranes and selective water-
soluble polymers as extractants. Sep Sci Technol
23(10–11):1039–1066
Li N, Giorno L, Drioli E (2003) Effect of immobilization
site and membrane materials on multiphasic
enantiocatalytic enzyme membrane reactors. Ann NY
Acad Sci 984:436–452
Majumdar S, Sirkar KK (1992) Hollow-fiber contained
liquid membrane. In: Ho WSW, Sirkar KK (eds) Mem-
brane handbook. Van Nostrand Reinhold, New York,
pp 764–808
meric membranes. In: Belafi-Bako K, Gubicza L,
Mulder M, (eds) Integration of membrane processes
into bioconversions. In: Proceedings of the 16th Euro-
pean Membrane Society Annual Summer School,
Veszprem, Aug 1999. Kluwer/Plenum, New York,
pp 73–100
Schlosser S, Sabolova E (2002) Three-phase contactor
with distributed U-shaped bundles of hollow-fibers
for pertraction. J Membr Sci 210:331–347
Sirkar KK (1996) Hollow fiber-contained liquid mem-
branes for separations: an overview. In: Bartsch RA,
Way JD. (eds) Chemical separations with liquid mem-
branes. American Chemical Society, Symposium
Series 642, pp 222–238
Teramoto M, Ohnishi N, Takeuchi N, Kitada S,
Matsuyama H, Mano H (2003) Separation and enrich-
ment of carbon dioxide by capillary membrane module
with permeation of carrier solution. Sep Purif Technol
30:215–227
H
Homogeneous Anion-Exchange
Membranes
Mitsuru Higa
Graduate School of Science and Engineering,
Yamaguchi University, Ube, Yamaguchi, Japan
Anion-exchange membranes (AEMs) are classi-
fied into two types by their microstructure: het-
erogeneous and homogeneous. Homogeneous
AEMs consist of a uniform membrane matrix
with anion-exchange groups (positively charged
groups) and, in many cases, reinforcing materials
such as woven cloth or net. Various methods have
been reported for preparing homogeneous
AEMs; however, almost commercial homoge-
neous AEMs are copolymer membranes
composed of styrene and divinylbenzene (DVB)
with benzyl trimethylammonium groups. Figure 1
shows a schematic diagram of a typical prepara-
tion method (paste method) of the AEMs
(Sata 2004). A monomer mixture consisting of
chloromethylstyrene (CMS)/DVB, acrylonitrile-
butadiene rubber, and benzoyl peroxide to initiate
polymerization was used to prepare the paste.
A reinforcing material such as woven poly
(vinyl chloride) cloth, reserved to roll 1, was
dipped in the paste reservoir 4. A separating
film such as poly(ethylene terephthalate) was
fed from roll 2. The reinforcing material coated
with the paste was wound on roll 3 in layers with
the separating film. In this way, the paste (the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_285-1
monomer mixture) was continuously coated on
the reinforcing material and covered on both
sides with the separating film. A precursor mem-
brane was obtained by heating the resultant com-
posite at 80
C for 10 h under a nitrogen
atmosphere to polymerize the monomers. An
ion-exchange group was introduced by
quaternization by immersing the precursor mem-
brane in an aqueous solution of 1.0 mol/dm3
trimethylamine at 30
C for 20 h. The cross-linker
content (CLC) in the mixture was changed to
control the network structure of the membranes.
The CLC was defined as follows:
 
CDVB
CLC ¼ (1)
CCMS þ CDVB
where CDVB and CCMS are the content of DVB
and CMS in the mixture. The value of CLC is
controlled to optimize the fundamental physico-
chemical properties, transport number of anions
and electrical resistance, to their applications. In
general, the transport number and electrical resis-
tance of AEMs increase with increasing CLC.
Other preparation methods of homogeneous
AEMs have been reported such as:
(a) modification of aromatic polymer. An aro-
matic polymer such as poly(ether-ether-ketone)
is chloromethylated using chloromethyl ether in
the presence of a catalyst, and then the
chloromethylated polymer is quaternized using
triethylamine. The quaternized polymer solution
2 Homogeneous Anion-Exchange Membranes

porous film (e.g., porous polyethylene) with a

+ mixture of vinylbenzene-based monomers, a
+ + +
cross-linking agent, and an initiator. Then, ther-
2 + 5 6
1 mal cross-linking polymerization is performed.
3
7 Finally, quaternary ammonium groups are intro-
+ + duced. (c) Electron-beam-induced graft polymer-
ization. A polymer film such as high-density
5 7 polyethylene is grafted by electron-beam-
induced graft polymerization with CMS and DV-
4
B. The quaternary ammonium groups are intro-
duced by treating the grafted film with
Homogeneous Anion-Exchange Membranes, trimethylamine.
Fig. 1 A typical preparation method of AEMs (paste
method). 1 Reserve roll of reinforcing fabric, 2 reserve
roll of separating film, 3 receiving role, 4 paste (mixture of
vinyl monomers, inert polymers, initiator, additives, etc.) References
reservoir, 5 expand roll, 6 press roll, 7 guide roll
Sata T (2004) Ion exchange membrane. The Royal Society
is cast to form an AEM. (b) Pore-filling method. of Chemistry, Cambridge
AEMs are prepared by filling the pores of a
N
Natural Organic Matter (NOM)
Tony Fane
UNSW, School of Chemical Engineering, The
University of New South Wales, Sydney, NSW,
Australia
Natural organic matter (NOM) is an organic
material from environmental origin and produced
by biodegradation of organic substances (plants,
etc.). NOM gives surface waters a brownish color
and is a problem in drinking water supply, not
because of its toxicity but because some of its
components can react with chlorine used as dis-
infectant. The reaction by-products include tri-
halomethane, haloacetic acids, chlorophenols,
etc. which are potentially carcinogenic. The
NOM components are known as trihalomethane
precursors (THMPs), and it is recognized that
their removal prior to disinfection is important
for public health. Membrane technology is fre-
quently used for treatment to remove NOM from
surface waters (see ▶ NOM Removal and
Fouling).
Natural organic matter (NOM) has a broad
spectrum of molecular weights and size distribu-
tions, functional groups, and substructures. The
term NOM covers the particulate colloids (POM),
“dissolved” colloids, and macrosolutes or
dissolved organic matter (DOM) and the humics.
Since NOM is from environmental origin, its
composition is highly variable both spatially
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_286-1
and temporally. One of the major groups in
NOM is humic substances (HS), which include
a complex mixture of organic compounds such as
humic acids (HA), fulvic acids (FA), and other
hydrophilic compounds. Typically, humic sub-
stances have molecular weights from a few hun-
dreds to approximately 100,000 Da. They contain
both aromatic and aliphatic components with car-
boxylic and phenolic groups attached to the aro-
matic rings. As a result, humic substances can be
negatively charged as well as having hydropho-
bic and hydrophilic components. The humic frac-
tion also has neutral components. The charge
character is important as it influences interactions
with other pollutant species and the treatment
process equipment (such as membrane surfaces).
The complexity of NOM makes characteriza-
tion difficult. A review of methods can be found
in Leenheer and Croue 2003. Recently NOM
characterization has involved size exclusion
chromatography, combined with UV and online
DOC and organic nitrogen detection, in a system
called “liquid chromatography-organic carbon
detection-organic nitrogen detection”
(LC-OCD-OND) (Huber 2014). This instrument
provides a molecular weight distribution and also
identifies components (in descending size) as bio-
polymers, humics, building blocks, low MWt
acids and humics, and neutrals. This measure-
ment technique is now widely used in membrane
applications to water and wastewater.
2 Natural Organic Matter (NOM)

References Further Reading

Fane AG, Wei X, Wang R (2006) Membrane filtration
Huber S (2014) www.doc-labor.de/Basics.html processes and fouling. In: Newcombe G, Dixon
Leenheer JA, Croue J-P (2003) Characterizing dissolved D (eds) Interface science in drinking water treatment:
organic matter. Environ Sci Technol 37(1):18A–26A fundamentals and applications. Academic, New York,
Chapter 10
N
Natural Organic Matter, Removal
and Fouling of
Tony Fane
School of Chemical Engineering, UNSW, The
University of New South Wales, Sydney, NSW,
Australia
Natural organic matter (NOM) is present in sur-
face waters and its removal prior to disinfection is
important to avoid formation of potentially car-
cinogenic trihalomethanes (see “▶ Natural
Organic Matter”). With a size range from colloi-
dal to a few hundred Daltons the NOM species
are well suited to removal by membranes, includ-
ing removal of trihalomethane precursors
(THMPs). However, some of the components of
NOM are potential membrane foulants, as
discussed below.
Most typically, NOM removal involves
microporous membranes (micro- or ultrafiltra-
tion), often in combination with a coagulant
(ferricsalts, polyaluminium chloride, etc). The
hybrid processes, combining membranes with
chemical addition, give improved removals as
seen in Table 1. The hybrid processes also pro-
vide better control of membrane fouling (see
below). The disadvantage is the disposal of the
waste sludge solids. Nanofiltration (NF), with
pores in the 5–2 nm size range, is capable of
high removals of NOM and is used extensively
in Norway and Scotland, particularly in remote
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_287-1
areas where chemical dosing would be trouble-
some. This advantage of NF may be offset by
higher pressures and energy costs in some
applications.
NOM fouling of membranes is complex with
many influencing factors, including the variable
nature of the raw water. It should be noted that no
one single component of NOM has been identi-
fied as the major cause for membrane fouling and
there are conflicting views in the literature. How-
ever, some components are clearly implicated.
The mechanisms of UF membrane fouling have
been shown to be cake formation, pore restriction
by adsorption, and pore plugging (see “▶ Irre-
versible Fouling”). Both reversible and irrevers-
ible fouling have been found in the membrane
treatment of surface waters. Thus, a fraction of
NOM with molecular sizes smaller than the mem-
brane pores may adsorb and reduce the pore
cross-sectional area for permeation and larger
fractions may plug pore entrances or contribute
to cake formation.
The hydrophobicity/hydrophilicity of NOM
has been found to be a factor influencing mem-
brane fouling in natural water treatment. There is
evidence that the hydrophobic components in
NOM tend to be responsible for the fouling of
hydrophobic membranes due to hydrophobic
interactions. However, there are contrary views.
In an Australian study, NOM was isolated into
four fractions: hydrophilic neutral, hydrophobic
acids, transphilic acids, and hydrophilic charged.
The order of the fouling potential of the individual
2 Natural Organic Matter, Removal and Fouling of
Natural Organic Matter, Removal and Fouling of, Table 1 Typical removals of NOM by membranes
TOC/DOC
Process Removal (%)
Microfiltration 10–40
MF + chemical ~80
Ultrafiltration ~50
UF+ chemical ~90
Nanofiltration 90–99
components during MF with PVDF membranes
was hydrophilic neutral > hydrophobic acids >
transphilic acids > hydrophilic charged. How-
ever, it may be that the hydrophilic neutral frac-
tion exhibited the greatest fouling potential
because of its size (>30 kD) relative to the mem-
brane pore size. The components of NOM can also
be fractionated into the following four fractions by
pyrolysis-GC/MS: polysaccharides, proteins,
polyhydroxy-aromatics, and amino sugars. It has
been found that the fouling potential could be
ranked in the order of polyhydroxy-aromatics
> proteins > polysaccharides and amino sugars.
The polyhydroxy aromatics were thought to be the
main foulants for negatively charged NF mem-
brane surfaces, and are probably hydrophobic
acids with phenolic groups, exhibiting no negative
charge at a neutral pH. However, this could
change in the presence of calcium, and similar
divalent cations, that appear to exacerbate NF
fouling by NOM due to binding between the neg-
ative membranes and negative components of
the NOM.
Controlling NOM fouling can significantly
reduce the cost of membrane water treatment,
extend membrane life, and reduce energy
demand. Techniques developed to minimize
NOM fouling include hybrid membrane pro-
cesses, pretreatment to reduce the NOM in the
raw water, optimization of hydrodynamic param-
eters, careful membrane selection, and cleaning
of the membrane system.
Hybrid membrane processes involve the com-
bination of coagulation/flocculation, or sorbents,
such as powdered activated carbon (PAC), heated
iron oxide particles (HIOPs), or an ion-exchange
resin (such as MIEX ®) with membrane
THMP
Removal (%)
15–20
~60
~40
~80
90–99
processes. MIEX ® is an anion-exchange resin
capable of removing relatively low molecular
weight negative organics from NOM. It has
been shown that using MIEX ® to remove
organics leads to very low fouling of a UF mem-
brane which is hydrophilic and positively
charged. The performance was particularly
enhanced when calcium was removed.
Pretreatment strategies include biologically acti-
vated carbon, where a bed of granular carbon
with developed biofilms treats the feed water
and reduces the biodegradable components
of NOM.
Hydrophilic membranes have been found to
be less prone to fouling than hydrophobic mem-
branes when treating natural water containing
NOM. Unfortunately, most commercially avail-
able UF and MF membranes are relatively hydro-
phobic materials with low surface energies such
as polypropylene, polysulfone, polyethersulfone,
and polyvinylidene fluoride. Some membranes
(such as PVDF) can be rendered more hydro-
philic by blending or surface treatment. A recent
development involves the use of ceramic UF
membranes with ozone pretreatment to oxidize
NOM components. This method appears to limit
fouling, even at relatively high fluxes.
References
Fane AG, Wei Xi, Wang R (2006) Membrane filtration
processes and fouling, chapter 10. In: Newcombe G,
Dixon D (eds) Interface science in drinking water
treatment: fundamentals and applications. Academic
Mallevialle J, Odendaal PE, Wiesner MR (eds)
(1996) Water treatment membrane processes.
McGraw-Hill, New York
H
Hybrid Membranes
Mario Aparicio
Instituto de Ceramica y Vidrio (CSIC), Madrid,
Spain
The term “hybrid membrane” more commonly
refers to a membrane formed by at least two
components of different chemical nature
(considering chemical-bond modes) from the
groups of metals, organic materials and their
polymers, and inorganic materials.
Hybrid membranes can be classified into two
main types, depending on the nature of the inter-
action between components: (1) systems where
there are no covalent or iono-covalent bonds
between components, only Van der Waals,
hydrogen bonding, or electrostatic forces, and
(2) systems where at least parts of the compo-
nents are linked through strong covalent or iono-
covalent bonds (Sanchez and Gómez-Romero
2004). The first type can also be named as
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_292-3
composites, or nanocomposites, where at least
one of the components’ domains has a dimension
ranging from a few angstroms to several
nanometers.
The main objective in the synthesis of hybrid
membranes is the performance improvement of
the material for different applications. It is obvi-
ous that the properties of these membranes are
not only the sum of the individual contributions
of both components, and interfaces can play a
significant role.
The high number of parameters involves in the
design and preparation of hybrid membranes: the
number of components, composition, compo-
nents ratio, size, shape, and kind of interaction
between components results in an almost infinite
number of combinations.
References
Sanchez C, Gómez-Romero P (2004) Functional hybrid
materials. Wiley VCH, Weinheim
H
Hybrid Organic-Inorganic
Nanostructured Membranes
Mario Aparicio
Instituto de Ceramica y Vidrio (CSIC), Madrid,
Spain
A hybrid organic-inorganic nanostructured mem-
brane is a specific kind of hybrid membrane
formed by at least two components from organic
materials and their polymers and inorganic mate-
rials. The components of this kind of hybrid
membranes have dimensions up to several nano-
meters, and components are linked through cova-
lent or iono-covalent bonds.
Improved and also new properties are
expected in this specific kind of hybrid mem-
branes because of the combination of two very
different materials and their chemical interac-
tions. For example, it is possible to obtain mem-
branes with a high flexibility and processability,
such as a polymer, but with the improved thermal
and chemical stability, and mechanical strength
of inorganic materials (Sanchez et al. 2005).
The possible applications of these hybrid
membranes are increasing continuously. For
example, an antimicrobial drug (substituted
1,3,4-oxadiazole) with functionalized silica was
successfully incorporated into an organic phase
by sol-gel to achieve a highly stable and anti-
biofouling membrane for water treatment (Singh
et al. 2012). Hybrid organic-inorganic
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_293-3
nanostructured membranes have also found
applications in the medical field for advanced
separation of heavy metals from blood or other
physiological liquids, such as new polymeric-
carbon nanotube composite membranes based
on polysulfone with different types of nanotubes
(Nechifor et al. 2009). Another important area
where these hybrid membranes may have a sig-
nificant relevance is the energy sector, especially
as new membranes for proton exchange mem-
brane fuel cells (PEMFC) and solid-state Li-ion
batteries. There membranes share several com-
mon characteristics, such as high ion conductiv-
ity (proton and lithium ion, respectively), low
electronic conductivity, high thermal stability,
and high chemical/electrochemical stability.
Decreasing the membrane thickness but preserv-
ing the properties described above would
improve the performance of the systems. Hybrid
organic-inorganic nanostructured membranes
can be designed to incorporate all these proper-
ties (Mosa and Aparicio 2012).
References
Mosa J, Aparicio M (2012) Hybrid materials for high ionic
conductivity. In: Aparicio M, Jitianu A, Klein LC (eds)
Sol–gel processing for conventional and alternative
energy, 1st edn. Springer, New York, pp 99–122
Nechifor G, Voicu SI, Nechifor AC, Garea S (2009) Nano-
structured hybrid membrane polysulfone-carbon
nanotubes for hemodialysis. Desalination
241:342–348
2 Hybrid Organic-Inorganic Nanostructured Membranes

Sanchez C, Julian B, Belleville P, Popall M (2005) Appli- Singh AK, Singh P, Mishrab S, Shahi VK (2012) Anti-
cations of hybrid organic–inorganic nanocomposites. biofouling organic–inorganic hybrid membrane for
J Mater Chem 15:3559–3592 water treatment. J Mater Chem 22:1834–1844
H
Hydrocarbon Branching
A. Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
For more than 20 years now, regulations have
imposed increasingly tight limitations on the con-
tent in gasoline of aromatic octane number
boosters produced by the reforming of straight-
run gasoline (alkanes). Among the available
alternative technologies designed to enhance the
octane number of straight-run gasoline,
hydroisomerization is a catalytic technology
that upgrades low-octane-number linear paraffins
into higher-octane-number branched paraffins.
Since the rate of conversion of linear paraffins
in the isomerization units is limited by a thermo-
dynamic equilibrium, an option for increasing the
production yield of dibranched paraffins consists
of separating the linear and monobranched par-
affins from the isomerization unit effluent and
recycling them in the input of the isomerization
reactor. The more conventional solution consists
of fractionating the output stream from the isom-
erization reactor through a continuous distillation
column (a deisohexanizer or DIH) into three
effluents:
– A sidestream, mainly containing unconverted
normal hexane and the monobranched
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_296-2
paraffins with six carbon atoms. This stream
is recycled to the isomerization unit.
– The bottom stream, containing the heaviest
alkanes (paraffins) with six carbon atoms and
naphthenes (cyclic paraffins) with six carbon
atoms, with an RON of 82, is sent directly to
the gasoline pool.
– At the top of the column, a head stream rich in
dibranched paraffins with six carbon atoms,
isopentane, and normal pentane. This stream,
which corresponds to 90 % by weight of the
fresh feed, has an RON (research octane num-
ber) of 87 though it contains about 16 % by
weight of normal pentane, which has a low
RON of 61.
With current distillation processes, it is not
economically feasible to separate normal pentane
from the other components in the top stream of
the deisohexanizer since their respective boiling
points are very close. This type of separation,
however, can be achieved with molecular sieves,
such as zeolites, implemented in cyclic adsorp-
tion processes such as a “simulated moving bed”
(UOP Molex process) or “cycled pressurization/
depressurization” (IFP IPSORB process or
ExxonMobil ISOSIEVE process). With such pro-
cesses, normal paraffins are preferentially
adsorbed inside the microporosity of the zeolites
and therefore separated from their branched iso-
mers. Though offering excellent separation per-
formance, this type of technology exhibits
2 Hydrocarbon Branching
several drawbacks: high investment costs,
sophisticated sequential operation (adsorption-
desorption cycle), the use of large quantities of
solvents (desorbants), and lack of modularity.
Since the beginning of the 1990s, much atten-
tion has been paid to overcoming the drawbacks
of conventional zeolite adsorbents through the
development of zeolite membranes that combine
the technical advantages of membranes
(modularity, continuous operation) with the high
separation performances of zeolites (due to their
sieving properties). Most of the published R&D
work on that topic was carried out at lab scale
mainly by academic laboratories, though a few
companies, like ExxonMobil or NGK Insulators,
have also published results on that topic. One of
the most studied topics in this research field was
the separation of normal short (C4–C6) paraffins
from their branched isomers through MFI-type
zeolite membranes (Arruebo et al. 2006; Bakker
et al. 1996; Coronas et al. 1998). Indeed, MFI
zeolites are crystalline aluminosilicates with a
microporous structure that is composed of two
intricate micropore networks: elliptical straight
channels with openings of 0.51  0.55 nm and
zigzag channels that are almost cylindrical with a
diameter of 0.53  0.56 nm, as measured by
X-ray diffraction at ambient temperature
(Flanigen et al. 1978). In such a confined porous
system wherein the diameter of the micropores
and the kinetic diameter of the diffusing mole-
cules are close, the higher the kinetic diameter of
a permeating molecule, the higher the friction of
the molecule alongside the micropore wall and
therefore the lower its diffusion coefficient inside
the microporosity of the MFI zeolite. Therefore,
the diffusion coefficient of normal alkanes in MFI
zeolites is higher (Courthial et al. 2008) than the
diffusion coefficient of their monobranched iso-
mers. Moreover, these materials prove to be
hardly permeable to dibranched paraffins. As an
illustration, it was shown experimentally that a
MFI zeolite membrane operated under close to
industrial operating conditions (2–4 bar feed pres-
sure, membrane temperature between 200  C and
400  C) was able to produce a permeate composed
of 95 % normal pentane and 5 % isopentane
from a vapor feed composed of 20 %
2,2-dimethylbutane, 55 % isopentane, and only
25 % normal pentane (Baudot and Bournay 2009).
References
Arruebo M, Falconer JL, Noble RD (2006) Separation of
binary C-5 and C-6 hydrocarbon mixtures through
MF1 zeolite membranes. J Membr Sci 269:171–176
Bakker WJW, Kapteijn F, Poppe J, Moulijn JA (1996) Per-
meation characteristics of a metal-supported silicalite-
1 zeolite membrane. J Membr Sci 117:57–78
Baudot A, Bournay L (2009) Integration of MFI zeolite
membranes in the light gasoline isomerisation process.
Oil Gas Sci Technol 64:759–771
Coronas J, Noble RD, Falconer JL (1998) Separations of
C-4 and C-6 isomers in ZSM-5 tubular membranes.
Ind Eng Chem Res 37:166–176
Courthial L, Baudot A, Tayakout-Fayolle M, Jallut C
(2008) A transient permeation-based method for com-
posite zeolite membrane characterization. AIChE J
54:2527–2538
Flanigen EM, Bennett JM, Grose RW, Cohen JP, Patton
RL, Kirchner RM, Smith JV (1978) Silicalite, a new
hydrophobic crystalline silica molecular-sieve. Nature
271:512–516
H
Hydrogen from Bioethanol
Jose M. Sousa
Chemistry Department, School of Life &
Environment Sciences, University of Tras-os-
Montes e Alto Douro, Vila Real Codex, Portugal
LEPABE - Laboratory for Process Engineering,
Environment, Biotechnology and Energy
Chemical Engineering Department Faculty of
Engineering, University of Porto Rua Roberto
Frias, Porto, Portugal
The production of hydrogen from bioethanol has
been considered an attractive way for exploring
sustainable renewable energy sources, from an
environmentally friendly point of view.
Bioethanol consists of an aqueous solution
containing 8–12 wt.% of ethanol, besides other
by-products such as glycerol, acetaldehyde,
diethyl ether, methanol, etc. (Ni et al. 2007;
Iulianelli and Basile 2011).
Hydrogen production from ethanol is essen-
tially carried out by steam reforming, according
to the main reaction described by C2 H5 OH þ 3H2
O ! 6H2 þ 2CO2 , DH ð298 KÞ ¼ 348 kJ  mol1 .
Ethanol steam reforming is a very attractive
way to locally produce hydrogen, comparatively
to other fuels such as methanol, glycerol, acetic
acid, diethyl ether, etc. For example, ethanol is
easily obtained by fermentation from renewable
sources such as sugars and starches (e.g.,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_297-3
sugarcane and corn – first-generation bioethanol)
and from lignocelluloses (agricultural, industrial,
and forest residues – second-generation
bioethanol), among other sources; ethanol is
easy to transport and store, it is biodegradable
and shows low toxicity; ethanol is relatively
easy to dehydrogenate by steam reforming, and
it does not contain catalyst poison such as sulfur
(Ni et al. 2007).
Steam reforming of ethanol is a highly endo-
thermic reaction, which limits its industrial appli-
cation for hydrogen production. The oxidative
reforming, oxidation of a fraction of ethanol to
provide part of the energetic needs, is a possible
way to minimize such impact. If the amount of
oxygen is sufficient for balancing the reforming
enthalpy needs, the process is named autothermal
reforming (Song 2012). Other ways to produce
hydrogen from ethanol are fermentation pro-
cesses using metabolically engineered microor-
ganisms, solar photocatalytic processes using
suitable semiconductors, CO2 dry reforming,
plasma reforming, partial oxidation, and aqueous
phase reforming (Song 2012).
Concerning the catalysts for the hydrogen pro-
duction from (bio)ethanol, current state of the art
includes the noble metal-based (Pt, Pd, Ru, Rh)
and non-noble metal-based (Cu, Co, Zn, Ni) ones
(Iulianelli and Basile 2011). The ethanol conver-
sion and hydrogen yield and selectivity are
strongly dependent on the catalyst type, its sup-
port (e.g., ZnO, MgO, Al2O3, SiO2, La2O3,
 2

CH3CH2OH H2O CO2 CO2

O O O O O O O O O O
O O O O Co O O
Co Co
e O O
ac Support (metal oxide) Support (metal oxide) Support (metal oxide)
urf
cs scheme 1 scheme 9 scheme 13
idi
Ac
H2 O O O O O
C C CO2
H

CH3CH2O
C2H4 2 H2O H
O O OH OH O O O O O O O O
O O O O Co O O
Co Co
H H H H
Co O Support (metal oxide) O
Support (metal oxide) Support (metal oxide)
scheme 3 scheme 8 scheme 12
Support (metal oxide)
scheme 2 CH CHO
3
Route 1
CH4CHO CH3COCH3
H2 O O
HC

CH3CH2O
H H
Route 2

CH3CH O
OH OH OH OH OH + O O O O O
O O O O O Co O O
Co CH4 CO H2
Deactivation O O Support (metal oxide) O
Cx Cx C Support (metal oxide)
Cx

OC
x scheme 4 OH H3C OH + OH scheme 11
x
OH OH OH O O

x
Cx
O Co

C C
O
Co
H2 CO
Support (metal oxide) O H2
Support (metal oxide) O

H3CC
H2 scheme 7 O
scheme 6 H H-CHx
OC

OH O O OH OH OH OH OH + OH
O O O O O Co O O
Deficient oxygen Co
or Co site accessiblity Sufficient oxygen accessiblity
Support (metal oxide) O Support (metal oxide) O
scheme 5 scheme 10

Hydrogen from Bioethanol, Fig. 1 Proposed reaction mechanism for ethanol steam reforming over supported Co catalysts (Song 2012)
Hydrogen from Bioethanol
Hydrogen from Bioethanol
Water
Feed
FBR HT WGS LT WGS
Cooler
Hydrogen from Bioethanol, Fig. 2 High-purity hydrogen production in a conventional multistage system
Hydrogen from
Bioethanol, Fig. 3 High-
purity hydrogen production
in a membrane reactor with
a Pd-based membrane
CeO2), and the reaction conditions (Costa-Serra
et al. 2010; Song 2012).
Besides the ethanol steam reforming main
reaction referred above, the process follows a
complex reaction system with several possible
consecutive parallel reactions, such as partial
reforming to CO, water gas shift, methanation,
coke formation from intermediate products,
Boudouard reaction, CO reduction, methane
cracking, dehydration/hydrogenation, and dehy-
drogenation. In addition to H2 and CO2, refor-
mate stream may contain also CO, methane,
aldehydes, ketones, ethylene, ethane, and high
alcohols, among others (Vizcaíno et al. 2007;
Song 2012) (Fig. 1).
The main drawback of using bioethanol to
produce hydrogen via steam reforming is the
high cost associated to the downstream distilla-
tion and purification steps of the crude ethanol
obtained from fermentation. Feeding directly the
crude bioethanol to the reformer would reduce
drastically the costs of the produced hydrogen.
Besides the unnecessary expensive distillation
process for water and other compounds elimina-
tion, the reforming of other oxygenated hydro-
carbons contained in the fermentation broth could
contribute to generate extra hydrogen. The main
challenge for the implementation of this
approach at an industrial level remains in the
tolerance and stability of the catalyst to the
3
Air
H2
CO PROX H2Purification
(PSA)
Cooler Cooler
impurities present in the crude ethanol solution,
especially high linear and branched alcohols
(Le Valant et al. 2011; Song 2012).
In the viewpoint of hydrogen production for
supplying polymer electrolyte membrane fuel
cells (PEMFCs), the reformate stream, which
comprises a complex mixture of compounds,
needs a separation/purification, especially due to
the maximum allowed CO concentration
(0.2 ppm). A conventional steam reformer system
is composed by the reformer (fixed bed reactor
(FBR)), two water gas shift reactors (high- and
low-temperature WGS), a CO partial oxidation
reactor (PROX), and pressure swing adsorption
(PSA) units (Fig. 2).
This complex process may be replaced by a
much simpler membrane reactor (MR) holding
hydrogen permselective membranes. This new
reactor is able to perform both the steam
reforming of bioethanol and the separation/puri-
fication of the produced hydrogen in the same
device (Fig. 3).
Moreover, this kind of MR makes possible the
in situ removal of hydrogen from the reaction side,
allowing the conversion to overcome the thermo-
dynamic equilibrium value (which is not possible
in the FBR). Furthermore, if Pd or Pd-based mem-
branes are used, a pure hydrogen stream is col-
lected in the permeate side, suitable for direct
PEMFC supplying (Iulianelli and Basile 2011).
4 Hydrogen from Bioethanol
References
Costa-Serra JF, Guil-López R, Chica A (2010) Co/ZnO
and Ni/ZnO catalysts for hydrogen production by
bioethanol steam reforming. Influence of ZnO support
morphology on the catalytic properties of Co and Ni
active phases. Int J Hydrog Energy 35:6709–6716
Iulianelli A, Basile A (2011) Hydrogen production from
ethanol via inorganic membrane reactors technology: a
review. Catal Sci Technol 1:366–379
Le Valant A, Garron A, Bion N, Duprez D, Epron F (2011)
Effect of higher alcohols on the performances of a 1 %
Rh/MgAl2O4/Al2O3 catalyst for hydrogen production
by crude bioethanol steam reforming. Int J Hydrog
Energy 36:311–318
Ni M, Leung DYC, Leung MKH (2007) A review on
reforming bio-ethanol for hydrogen production. Int
J Hydrog Energy 32:3238–3247
Song H (2012) Catalytic hydrogen production from
bioethanol. In: Lima MAP, Natalense APP (eds)
Bioethanol. InTech Publishing, Janeza Trdine 9,
Rijeka, Croatia
Vizcaíno AJ, Carrero A, Calles JA (2007) Hydrogen pro-
duction by ethanol steam reforming over Cu–Ni
supported catalysts. Int J Hydrog Energy
32:1450–1461
Further Reading
Curcio S (2011) Membranes for advanced biofuels pro-
duction. In: Basile A, Nunes S (eds) Advanced mem-
brane science and technology for sustainable energy
and environmental applications. Woodhead Publish-
ing Limited, Cambridge, UK
H
Hydroprocessor Purge Gases
A. Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
The demand for hydrogen is constantly increas-
ing in refineries due to more and more stringent
sulfur content specifications for fuels (leading to
an increasing hydrogen consumption in
hydrodesulfurization processes) and a growing
heavy crude consumption, which results in a
higher worldwide demand for highly hydrogen-
consuming upgrading processes, such as hydro-
cracking. In this changing landscape, permeation
membranes constitute an elegant option for the
recovery of hydrogen that is nowadays wasted in
an array of refinery off-gases, such as fuel gas,
PSA tail gas, FCC gas, catalytic reformer
off-gases, or hydrocracker/hydrotreater
off-gases.
Nowadays, three main membrane providers
offer hydrogen purification permeators:
– Air Products with the Prism ® silicon-coated
polysulfone membranes (issued from
Monsanto). Air Products claims that the life-
time of the Prism ® modules can be more than
15 years.
– Ube Industries with polyimide hollow fiber
membranes.
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_298-1
– Air Liquide with the MEDAL polyimide and
high selectivity polyaramide membranes.
All those membranes are based on glassy
polymers and offer a diffusion-based hydrogen
selectivity. Today’s membranes have high H2/
CH4 selectivities (from 35 to 200 at 80  C
(Roman et al. 2001)). For instance, Air Products
claims that a single-stage array of Prism ® mod-
ules is able to raise the concentration of gases
from 10–30 % up to 70–90 % (Air Products
website), while MEDAL membranes are able to
raise the concentration of a gas at 51 bar from
86 % in hydrogen up to 98 % with a permeate
pressure at 30 bar and a residue containing 52 %
of hydrogen at 50 bar (Medal website).
In 2003, it was reported that more than
400 hydrogen permeators were installed world-
wide (Monereau 2003) while approximately
100 were operated in refineries (Baker 2002).
As there are more than 500 refineries in the
world, it is clear that the potential market for
this type of membrane applications is far from
saturated. Nevertheless, three main limits still
hinder the wide acceptance of permeation-based
hydrogen purification in the refining industry:
– The purified hydrogen is recovered at low
pressure in the permeate side and requires
compression in order to feed it back to reac-
tors. As such, PSA (pressure swing adsorp-
tion) is a more attractive process, as the
2 Hydroprocessor Purge Gases
Hydroprocessor Purge Gases, Table 1 Ube Industries membrane material compatibility against contaminants (Ube
Industries website)
Contaminants
Water vapor
H2S
NH3 and amines
Methanol
Methyl ether
Benzene
Toluene
C5+ hydrocarbons
produced purified hydrogen is delivered
directly at high pressure.
– The sensitivity of membrane to contaminants,
such as water vapor, higher hydrocarbons, or
acid gases. The installation of permeators gen-
erally requires at first a very detailed analysis
of the contaminants present in the feed, even at
traces level, in order to design pretreatment
operations. A wide array of solutions can be
used in order to remove poisonous com-
pounds: coalescing filters in order to remove
aerosols, sorbent beds, or even complete PSA
(pressure swing adsorption) or TSA
(temperature swing adsorption) units
(Monereau 2003). This can lead to a signifi-
cant increase of investment and operating
costs. It should be reminded here that recent
hydrogen purification membranes are still rel-
atively tolerant to contaminants (Table 1).
This is particularly true if membrane modules
are operated at higher temperatures (from
80  C to 110  C), which results in lowering
of the sorption of contaminants.
– The membrane’s mechanical integrity can be
damaged in transient operating conditions,
especially in the case of an emergency blow-
Maximum allowable content
Up to saturation
3 % vol
100 ppm vol
5 % vol
5 % vol
1 % vol
2000 ppm vol
Up to saturation
down of the membrane-based process. In cer-
tain cases, the membrane module can be sub-
mitted to pressures differences larger than its
mechanical tolerance. Solution is nowadays
proposed by membrane providers in order to
monitor automatically the pressure balance
between the feed and the permeate compart-
ment when operating condition limits are
reached (Monereau 2003).
References
Air Products website. http://www. airproducts.
com/Products/Equipment/PRISMMembranes/page08.
htm
Baker RW (2002) Future directions of membrane gas
separation technology. Ind Eng Chem Res
41:1393–1411
Medal Internet website. www.medal.airliquide.com
Monereau C (2003) Perméation hydrogène: de la
périphérie des procédé vers le coeur des procédés.
Intégration des membranes dans les procédés
2:89:275–282
Roman IC, Ubersax RW, Fleming GK (2001) New direc-
tions in membrane for gas separation. Chim Industria
83:1–3
Ube Industries website. http://www.ube.com/content.
php?pageid=45
H
Hyperbranched Polyimides
Ryohei Shindo, Shinji Kanehashi and Kazukiyo
Nagai
Department of Applied Chemistry, Meiji
University, Tama-ku, Kawasaki, Japan
Hyperbranched polyimides are formed by
repeated division of branches of comb
polyimides. Hyperbranched polymers are synthe-
sized by polymerization of AB2-type monomers
and consist of branched structures and mixed
straight chains (Fig. 1). Rigorous structural anal-
ysis cannot be performed because branching does
not regularly occur. However, hyperbranched
polymers show properties differing from a nor-
mal linear polymer because entanglement of the
intermolecular chains is difficult. Flory (1952)
showed that gelation of polymerization of ABx-
type monomer cannot be statistically performed.
Kricheldorf et al. (1982) reported the use of AB2-
type monomer as one component in copolymers,
but their results lacked research attention.
Hyperbranched polymers containing various
repeating units have been reported since the syn-
thesis of hyperbranched polyphenylene by
one-step polymerization of AB2-type monomer
was reported as a simple synthesis method of
polymers, which were similar in structure to
dendrimers by Kim and Webster (1990) of Du
Pont. However, dendrimers as structurally-
controlled polymers have been actively studied
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_300-1
in the field of medicine and for use in catalytic
reaction and photoreaction. Hyperbranched poly-
mers have an obvious advantage in synthesis com-
pared with dendrimers. Thus, these polymers can
be used as an alternative to dendrimers and a
low-viscosity polymer in a wide range of areas.
Polyimide is a condensation polymer synthesized
from dicarboxylic anhydride and primary diamine.
Aromatic heterocyclic polyimides show good
mechanical property and superior thermal and oxi-
dation stability. These polyimides are widely used
in place of metal and glass. They are also used for
high-functional application in electrical engineer-
ing, electronic engineering, automobiles, aircraft,
and packaging industry. Linear aromatic
polyimides are known as polymers, which have
poor workability because they are insoluble and
infusible in the rigidity of the main chain structure.
However, solubility for organic solvent can
remarkably improve by the introduction of a mul-
tiple branching structure. Hyperbranched
polyimides with 4-methylphthalimide as end
groups show low dielectric constant, birefrin-
gence, and high optical transparency. These qual-
ities result from the improvement in isotropy of
molecular chains by the introduction of a multiple
branching structure and inhibition of the formation
of charge-transfer complex, causing coloration on
linear polyimides. For aromatic amine to react
easily with acid anhydride at room temperature,
isolation of ABx-type monomer with these func-
tional groups in a molecule is difficult because of
their instability. Poly(amic acid ester) is
2 Hyperbranched Polyimides
Hyperbranched
Polyimides,
Fig. 1 Architecture of
polymers
synthesized by AB2-type monomer, which has a
carboxylic acid ester and two amino groups in a
molecule and a condensation agent.
Hyperbranched polyimides are synthesized by
chemical imidization of poly(amic acid ester)
(Yamanaka et al. 2000). Hyperbranched
polyimides can be synthesized by self-
polycondensation of ABx-type monomers with
imide ring in the monomer framework. Thompson
et al. (1999) reported that hyperbranched
polyetherimides are synthesized by thermal poly-
condensation of AB2-type monomers with fluorine
(A functional group) and silylated phenolic
hydroxyl group (B functional group), which can
be detached in a molecule. When A2- and B3-type
monomers are used as starting materials in poly-
merization, AB2-type monomers need not be syn-
thesized. Various hyperbranched polyimides are
synthesized because they can be obtained by poly-
merization using a commercial A2-type monomer
and synthesized B3-type monomer.
Hyperbranched polyimides have attracted atten-
tion as materials for gas separation membranes
since the early 2000s, and most of them are syn-
thesized by A2- and B3-type monomers. The gas
permeability of hyperbranched polyimides is
almost equal to or higher than that of other glassy
polymers such as polysulfone or polycarbonate.
References
Flory PJ (1952) Molecular size distribution in three-
dimensional polymers. VI. Branched polymer
containing A-R-Bf-1-type units. J Am Chem Soc
74:2718–2723
Kim YH, Webster OW (1990) Water soluble
hyperbranched polyphenylene: “a unimolecular
micelle”. J Am Chem Soc 112:4592–4593
Kricheldorf HR, Zang QZ, Schwarz G (1982) New poly-
mer syntheses. 6. Linear and branched poly
(3-hydroxybenzoates). Polymer 23:1821–1829
Thompson DS, Markoski LJ, Moore JS (1999) Rapid syn-
thesis of hyperbranched aromatic polyetherimides.
Macromolecules 32:4764–4768
Yamanaka K, Jikei M, Kakimoto M (2000) Synthesis of
hyperbranched aromatic polyimides via polyamic acid
methyl ester precursor. Macromolecules
33:1111–1114
I
Ideal Gas Selectivity
Johannes Carolus Jansen
Institute on Membrane Technology ITM-CNR,
Consiglio Nazionale delle Ricerche, Rende (CS),
Italy
The ideal gas selectivity of a membrane, aij, is
defined as the ratio of the permeability of two pure
gases, measured separately under the same
conditions:
Pi
aij ¼
Pj
where Pi and Pj are the permeability (or the
permeance) of the two pure gases, respectively,
with i being the most permeable gas. Rarely the
real selectivity is equal to the ideal gas selectivity.
Most commonly the ideal selectivity of a mem-
brane is lower than the real selectivity, especially
when the more permeable gas species plasticizes
the polymer matrix, making it relatively more
permeable for the slower species. In some cases,
in particular in high free-volume polymers, strong
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_301-1
sorption of the more permeable species may
obstruct the transport of the less permeable spe-
cies, making the mixed gas selectivity higher than
the ideal selectivity.
In dense membranes, where transport occurs
by the solution-diffusion mechanism, the perme-
ability is the product of the diffusivity and the
solubility:
P ¼ D  S (2)
where D is the diffusion coefficient and S is the
solubility coefficient. Similarly, the selectivity can
be expressed in a diffusion term and a solubility
(1)
term:
D i Si
aij ¼  (3)
D j Sj
The ideal gas selectivity is an intrinsic property,
specific for the membrane material and the partic-
ular gas pair. However, it is not a constant but it
depends on the operation conditions temperature
and pressure because both D and S depend on the
temperature and on the operating pressure.
I
Ideal Separation Factor
Johannes Carolus Jansen
Institute on Membrane Technology ITM-CNR,
Consiglio Nazionale delle Ricerche, Rende (CS),
Italy
The separation factor, SF, is a measure of the
efficiency of the separation process and is deter-
mined from the ratio of the concentrations of the
more permeable gas species i and the less perme-
able gas species j in the permeate divided by the
ratio of the same gases i and j in the feed stream:
xi, p =xj, p
SF ¼
xi, f =xj, f
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_302-1
where xi,p and xj,p are the fractions of components
i and j in the permeate and xi,f and xj,f are the
fractions of components i and j in the feed. The
separation factor is not a material property, but it
also depends on the conditions of the separation
process. It depends both on the membrane prop-
erties and on the driving force, which in turn
depends on the pressure and on, for instance, the
presence of concentration polarization phenom-
ena, nonideal behaviour such as plasticization,
coupling effect, etc.
Analogously, the ideal separation factor is the
separation factor under ideal conditions. It can be
calculated from the pure gas permeabilities.
(1)
I
IgG Purification
Nilay Bereli, Deniz T€
urkmen, Handan Yavuz and
Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Owing to their use in the treatment of various
diseases, such as primary and secondary immune
deficiencies, infections, and inflammatory and
autoimmune diseases, large number of immuno-
globulin G (IgG) products is under clinical devel-
opment. This requires certain protocols for
purification and standardization. Affinity chro-
matography is the most popular technique to
reach these requirements (Low et al. 2007).
Staphylococcal protein A is one of the first affin-
ity ligands with a very high specificity for IgG
purification. It interacts with IgG through hydro-
phobic interactions and some hydrogen bonds
and electrostatic interactions. Main disadvan-
tages of protein A-containing carriers are the
possible ligand leakage that contaminates the
therapeutic product, and also they are expensive
and difficult to handle, sterilize, and preserve
(F€uglistaller 1989). Pseudo-specific ligands,
such as histidine, tryptophan, phenylalanine,
etc., can be used for the IgG purification. They
are small molecules with high physical and
chemical stability and low cost (Altıntaş and
Denizli 2009; T€ urkmen et al. 2008). The interac-
tion of histidine with IgG has been shown to be
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_303-1
water mediated involving the combined electro-
static, hydrophobic, and charge-transfer interac-
tions between histidine and the specific amino
acid residues available on the protein surface
(Bhattacharyya et al. 2003). In immobilized
metal ion affinity chromatography (IMAC), the
separation is based on the interaction of a Lewis
acid (electron pair acceptor), i.e., a chelated metal
ion, with electron donor atoms (N, O, and S) on
the side groups of the surface histidine, trypto-
phan, and cysteine of the protein. Histidine-rich
sequence-containing IgGs show an innate affinity
for metal ions, and IMAC allows one-step sepa-
ration of IgG (Altıntaş et al. 2007). Textile dyes
bind proteins in a selective and reversible manner
and can be used for antibody purification (Denizli
and Pişkin 2001). Dye ligands can engage in
ionic, hydrophobic, charge-transfer, and hydro-
gen bonding with proteins. In the thiophilic
adsorption of proteins, electron donor-acceptor
interactions between both functional groups pre-
sent in the ligand structure and the adjacent sul-
fone group are the driving force for selective
recognition (Bakhspour et al. 2014). In general,
specificity, rapid processing, mild operation con-
ditions, conventional equipment, and reusability
determine which technique to be used for IgG
purification. The use of membranes has become
indispensible for chromatographic applications
in both research and industry area for the last
few decades due to their relatively wide configu-
ration for the size-, charge-, and affinity-based
protein separation and purification. The pressure
2 IgG Purification
drop across the membranes is very low due to the
large pore size. Owing to the continuous pore
structure, mass transport occurs by convection
rather than by diffusion. Chromatographic mem-
branes are generally cost effective, and their
scale-up is easier than the packed-bed chroma-
tography (Charcosset 1998). Membrane opera-
tions including ultrafiltration (Mohanty and
Ghosh 2008; Rosenberg et al. 2009), dialysis
(Bruce et al. 2002), and affinity membrane chro-
matography (Boi et al. 2009) have been demon-
strated for their potential for IgG purification.
References
Altıntaş EB, Denizli A (2009) Monosize magnetic hydro-
phobic beads for lysozyme purification under mag-
netic field. Mater Sci Eng C 29:1627
Altıntaş EB, T€uzmen N, Uzun L, Denizli A (2007)
Immobilized metal affinity adsorption for antibody
depletion from human serum with monosize beads.
Ind Eng Chem Res 46:7802
Bakhspour M, Bereli N, Şenel S (2014) Preparation and
characterization of thiophilic cryogels with 2-
mercaptoethanol as the ligand for IgG purification.
Colloid Surf B 113:261
Bhattacharyya R, Saha RP, Samana U, Chakrabarti
P (2003) Geometry of interaction of the histidine ring
with other planar and basic residues. J Proteome Res
2:255
Boi C, Busini V, Salvalaglio M, Cavallotti C, Sarti GC
(2009) Understanding ligand-protein interactions in
affinity membrane chromatography for antibody puri-
fication. J Chromatogr A 1216:8687–8696
Bruce MP, Boyd V, Duch C, White JR (2002) Dialysis-
based bioreactor systems for the production of mono-
clonal antibodies-alternatives to ascites production in
mice. J Immunol Methods 264:59–68
Charcosset C (1998) Purification of proteins by membrane
chromatography. J Chem Technol Biotechnol 71:95
Denizli A, Pişkin E (2001) Dye-ligand affinity systems.
J Biochem Biophys Methods 49:391
F€
uglistaller P (1989) Comparison of immunoglobulin
binding capacities and ligand leakage using eight dif-
ferent protein A affinity matrices. J Immunol Methods
124:171
Low D, O’Leary R, Pujar NS (2007) Future of antibody
purification. J Chromatogr B 848:48
Mohanty K, Ghosh R (2008) Novel tangential-flow coun-
tercurrent cascade ultrafiltration configuration for con-
tinuous purification of humanized monoclonal
antibody. J Membr Sci 307:117–125
Rosenberg E, Hepbildikler S, Kuhne W, Winter G (2009)
Ultrafiltration concentration of monoclonal antibody
solutions: development of an optimized method mini-
mizing aggregation. J Membr Sci 342:50–59
T€
urkmen D, Özt€ urk N, Elkak A, Akgöl S, Denizli
A (2008) Phenylalanine containing hydrophobic
nanospheres for antibody purification. Biotechnol
Prog 24:1297
I
Immunoaffinity Membranes
Nilay Bereli, Handan Yavuz and Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Immunoaffinity chromatography is a process in
which the specific binding of an antigen to its
specific antibody is utilized (Subramanian
2002). The specificity of the binding makes this
technique a very useful tool for the applications
in which selective and strong antigen-antibody
binding is advantageous. Immunoadsorption, in
general, can be used for the purpose of therapy as
well as preparative chromatography. Normally,
the human immune system works to recognize,
respond, and destroy pathogenic substances.
When the ability of the immune systems to rec-
ognize foreign antigens versus healthy cells or
tissues is failed, arising immune complexes,
so-called autoantibodies, cause many kinds of
autoimmune diseases (Massey and McPherson
2007). For example, myasthenia gravis, autoim-
mune hemolytic anemia and immune thrombocy-
topenic purpura, rheumatoid arthritis, systemic
lupus erythematosus, thyroiditis, and insulin-
dependent diabetes mellitus are such diseases.
The immunoadsorption columns have been used
for the treatment of immune diseases since the
mid-1970s, in a study performed for the removal
of DNA antibodies (Terman et al. 1974). Since
then immunoadsorption therapy with affinity
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_305-1
adsorbents using target specific antibodies has
been increasingly utilized to remove pathogenic
autoantibodies from patients’ plasma (Uzun
et al. 2010). Besides their use in the treatment of
autoimmune diseases, immunoaffinity mem-
branes can be used for the purification of anti-
bodies or antigens with a high purity and also
used for the selective and specific removal of
toxic substances from human plasma (Denizli
2002). In such applications, membrane-based
columns have advantages over traditional col-
umns in terms of compressibility of the particles,
the fouling and slow flow rate through the col-
umn. Especially in contact with blood, stacked
membrane system is desirable because of high
convective transport rates without cell damage.
The other desirable properties of affinity mem-
branes are high porosity; large internal surface
area; high chemical, biological, and mechanical
stabilities; hydrophilicity; low nonspecific
adsorption of blood proteins; and the presence
of functional groups for derivatization (Denizli
2011).
References
Denizli A (2002) Preparation of immuno-affinity mem-
branes for cholesterol removal from human plasma.
J Chromatogr B 772:357
Denizli A (2011) Autoimmune diseases and immunoad-
sorption therapy. Hacettepe J Biol Chem 39(3):213
Massey HD, McPherson RA (2007) Human leukocyte
antigen: the major histocompatibility complex of
2 Immunoaffinity Membranes

man. In: Henry’s clinical diagnosis and management
by laboratory methods. 21st edn, McPherson RA,
Pincus AR (eds); Saunders-Elsevier publishes, Phila-
delphia pp. 876-893
Subramanian A (2002) Immunoaffinity chromatography.
Mol Biotechnol 20:41
Terman DS, Stewart I, Hofmann A, Carr R, Harbeck
R (1974) Specific removal of DNA antibody with an
immunoadsorbent. Experientia 30:1493
Uzun L, Yavuz H, Osman B, Çelik H, Denizli A (2010)
PHEMA based affinity membranes for in-vitro
removal of anti-dsDNA antibodies from SLE plasma.
Int J Biol Macromol 47:44
I
Imprinted Polysulfone-Aldehyde
Derivatized Nanofiber Membranes
Masakazu Yoshikawa
Department of Biomolecular Engineering, Kyoto
Institute of Technology, Kyoto, Japan
The functionalization of aromatic polysulfones
for tailoring properties in membrane applications
is of great interest. Polysulfone has overall ther-
mal and chemical stability combined with good
mechanical and membrane-making qualities.
Polysulfone is a stable platform for functional
group attachment and a good candidate poly-
meric material for membranes with tailored func-
tionalities (Guiver et al. 1999). To this end,
modified polysulfones have been intensively
studied in connection with chiral separation
(Yoshikawa et al. 1998, 2005, 2006, 2007;
Mizushima et al. 2011; Sueyoshi et al. 2012),
pervaporation separation (Yoshikawa
et al. 1992a, b, 1999), and selective separation
of CO2 (Yoshikawa et al. 2000).
In membrane separation, both flux and
permselectivity are important factors. The
enhancement of permselectivity would be rela-
tively easily attained by application of molecular
imprinting so that molecular recognition sites,
which specifically incorporate target substrate
into the membrane, can be introduced into a
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_306-1
given membrane. However, the enhancement of
flux without a concurrent reduction in
permselectivity is perceived to be an unsolved
problem or an unsolvable problem in membrane
separation. In other words, flux and
permselectivity often show a trade-off relation-
ship. Membranes with high surface area and high
porosity would be expected to break such a trade-
off relationship between flux and
permselectivity. Nanofiber membranes are
expected to simultaneously give both high flux
and high permselectivity. To this end, nanofiber
membranes with molecular recognition sites,
which are called molecularly imprinted nanofiber
membranes, were fabricated by simultaneously
applying an alternative molecular imprinting
and an electrospray deposition (Sueyoshi
et al. 2010; Yoshikawa et al. 2007). Those studies
revealed that molecularly imprinted nanofiber
membranes gave high flux without a concurrent
reduction in permselectivity. A breakthrough in
membrane separation was attained; in other
words, membrane morphology in the form of
molecularly imprinted nanofiber fabric was one
of the suitable membrane forms to solve a trade-
off relationship in membrane separation. Molec-
ularly imprinted nanofiber membranes and usual
molecularly imprinted membranes were fabri-
cated from polysulfone with aldehyde group
(PSf-CHO) and print molecules, and their
membrane performances, such as adsorption
2 Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes

Imprinted Polysulfone-
Aldehyde Derivatized
Nanofiber Membranes,
Fig. 1 Chemical structures
of polysulfone with
aldehyde group (PSf-CHO)
and print molecule
(Z-D-Glu or Z-L-Glu) (Cited
from Sueyoshi et al. 2012
with permission. Copyright
2012 Elsevier Inc)

Imprinted Polysulfone-
Aldehyde Derivatized
Nanofiber Membranes,
Fig. 2 Schematic
illustration for the
fabrication of molecularly
imprinted nanofiber
membranes, where
PSf-CHO and Z-Glu were
simultaneously
electrosprayed

selectivity, permselectivity, and flux, were stud-
ied (Sueyoshi et al. 2012).
PSf-CHO with degree of substitution of 0.50
and 1.00 were adopted as candidate materials,
and the derivative of D- or L-glutamic acid was
applied as a print molecule to obtain molecularly
imprinted nanofiber membranes and usual molec-
ularly imprinted membranes for optical resolu-
tion (Figs. 1 and 2).
Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes
Imprinted Polysulfone-Aldehyde Derivatized
Nanofiber Membranes, Fig. 3 Adsorption isotherm of
D-Glu and L-Glu in the nanofiber membrane molecularly
imprinted by Z-D-Glu. (PSf-CHO-10 was adopted as a
candidate material) (Cited from Sueyoshi et al. 2012
with permission. Copyright 2012 Elsevier Inc)
The membranes molecularly imprinted by
Z-D-Glu incorporated the D-isomer of glutamic
acid (Glu) in preference to the corresponding
L-isomer and vice versa. In other words, the mem-
brane imprinted by the L-isomer selectively
adsorbed the L-isomer.
Figure 3 shows the adsorption isotherms of
D-Glu and L-Glu for the Z-D-Glu molecularly
imprinted nanofiber membrane as an example of
adsorption isotherms. The adsorption isotherm of
D-Glu, which was preferentially adsorbed in the
membrane, shows a dual adsorption isotherm. It
consists of nonspecific adsorption and specific
adsorption on the specific recognition site,
which was constructed by the presence of a
print molecule during the membrane preparation
process. Contrary to this, L-Glu, which was
nonspecifically adsorbed in the membrane,
gives a straight line passing through the origin.
Time-transport curves of racemic Glu through
the D-isomer molecularly imprinted nanofiber
membrane are shown in Fig. 4. As often
observed, the transport of the enantiomer
3
2.0
D-Glu
L-Glu
105 Δ[Glu]R / mol dm−3
1.5 NaN3 NaN3
L R
membrane
1.0
a L/D = 1.20
0.5
D-Glu
L-Glu
0
0 2.0 4.0 6.0 8.0 10.0
Time / h
Imprinted Polysulfone-Aldehyde Derivatized
Nanofiber Membranes, Fig. 4 Time-transport curves
of racemic Glus through the nanofiber membrane molec-
ularly imprinted by Z-D-Glu (PSf-CHO-10 was adopted as
a candidate material) (Cited from Sueyoshi et al. 2012
with permission. Copyright 2012 Elsevier Inc)
preferentially incorporated into the membrane
was retarded by a relatively strong interaction
between the enantiomer and the membrane. As
a result, the antipode was selectively transported.
Such discrepancy between adsorption selectivity
and permselectivity is often observed in chiral
separation.
Table 1 summarizes membrane performances
for two types of molecularly imprinted mem-
brane. As can be seen, the fluxes through the
molecularly imprinted nanofiber membranes
gave one to two orders of magnitude higher than
those of usual molecularly imprinted membranes
without depression of permselectivity.
As proved in the previous studies (Sueyoshi
et al. 2010; Yoshikawa et al. 2007), the present
study revealed that molecularly imprinted
nanofiber membranes gave high flux without
depression of permselectivity. The emergence
of molecularly imprinted nanofiber membrane
would solve a trade-off relationship in membrane
separation (Yoshikawa et al. 2011).
4 Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes

Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes, Table 1 Results of chiral separation with
molecularly imprinted nanofiber (MINFM’s) and molecularly imprinted (MIPM’s) membranes
Z-D-Glu imprinted membrane Z-L-Glu imprinted membrane
Mmebrane aL/D u0 aD/L u0
MINFM-10a 1.24 1.15  10 9 (28) 1.20 1.67  10 9 (41)
MIPM-10a 1.20 4.20  10 11 (1) 1.20 4.10  10 11 (1)
MINFM-05b 1.12 7.00  10 9 (231) 1.20 2.20  10 9 (72)
MIPM-05b 1.25 6.64  10 11 (2.2) 1.16 3.05  10 11 (1)
a
Figures in parentheses are the relative values; the U Value for MIPM-10 imprinted by Z-L-Glu being set as unity
b
Figures in parentheses are the relative values; the U Value for MIPM-05 imprinted by Z-L-Glu being set as unity
c
U = (–J/C)/(dm/dx) [{(mol cm cm-2 h-1)/(mol cm-3)}/(J mol-1 cm-1) = mol cm cm-2 J-1 h-1].
(Cited from ref. Sueyoshi et al. 2012 with permission. Copyright 2012 Elsevier lnc.)

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hydroxyl groups. Polym J 24:1049–1055
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Robertson GP (1998) Carboxylated polysulfone
by an alternative molecular imprinting technique.
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(1999) Modified polysulfone membranes. III.
Pervaporation separation of benzene-cyclohexane
mixtures through carboxylated polysulfone mem-
branes. J Appl Polym Sci 74:407–412
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Modified polysulfone membranes. IV. Gas separation
with aminated polysulfone membranes. Sen’i
Gakkaishi 56:272–281
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(2005) Chiral separation of racemic amino acids
through membranes derived from modified
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group. Membrane 30:219–225
Yoshikawa M, Murakoshi K, Kogita T, Hanaoka K,
Guiver MD, Robertson GP (2006) Chiral separation
membranes from modified polysulfone having
myrtenal-derived terpenoid side groups. Eur Polym J
42:2532–2539
Yoshikawa M, Nakai K, Matsumoto H, Tanioka A, Guiver
MD, Robertson GP (2007) Molecularly imprinted
nanofiber membranes from carboxylated polysulfone
by electrospray deposition. Macromol Rapid Commun
28:2100–2105
Yoshikawa M, Tanioka A, Matsumoto H (2011) Molecu-
larly imprinted nanofiber membranes. Curr Opin
Chem Eng 1:18–26
I
Inert Membrane
Rune Bredesen
Sustainable Energy Technology, SINTEF
Materials and Chemistry, Oslo, Norway
The term inert membrane denotes that no change
in chemical reaction occurs due to contact
between the membrane material and the sur-
rounding constituents. A reaction occurring
between constituents A and B to form C and
D can be used as an example:
AþB¼CþD
If the membrane is catalytically inactive with
respect to the reaction, the term inert membrane
is used to describe the membrane. The presence
of a catalyst, deemed not to be part of the mem-
brane material, may yield a change in reaction 1,
and the integration of such a combination of
membrane and catalyst is referred to as an
▶ inert membrane reactor (IMR). The term inert
membrane is therefore commonly used in con-
nection with membrane reactors (Koros
et al. 1996) to distinguish the membrane proper-
ties from those of a catalytic membrane, the latter
being catalytically active. In such reactors, the
inert membrane may be used for selectively sep-
arating reaction products from the reaction for
which the catalyst serves to activate. Alterna-
tively, the inert membrane may be employed as
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_309-1
a distributor of reactants to ensure controlled
delivery to the catalytic reaction site. Classifica-
tion of a membrane as inert may also depend on
the operation conditions and surface properties
since the actual catalytic activity depends on
parameters such as temperature, surface area,
and surrounding chemical composition. Thus
the same membrane may, or may not, be an
inert membrane depending on the conditions
under which it is operated.
The interactions between an inert membrane
and its surroundings typically involve surface
adsorption/desorption reactions, which may be
followed by other reactions necessary for trans-
(1) port of matter within the membrane. For exam-
ple, in the case of dense polymeric membranes,
incorporation of the permeant gas molecule is
required on the feed side, while the reverse pro-
cess is required on the permeate side (Mulder
1996). Dense inorganic membranes, in addition,
require transformation of the adsorbed molecule
to atomic (in the case of metal membranes (Ward
and Dao 1999)) or ionic and electronic (in the
case of ceramic membranes (Sirman 2006) spe-
cies at the feed side, which are then able to diffuse
through the bulk membrane phase. At the perme-
ate side, the recombination of species to the same
molecular form as on the feed side takes place
before desorption to the gas phase. To enhance
the transformation of adsorbed gas molecules to
diffusing species within the membrane and, thus,
contribute to higher fluxes, catalytic surface
properties are usually required. Nevertheless,
2 Inert Membrane
such membranes which although they incorpo-
rate catalytic surface reactions, they are regarded
as inert membranes since the reaction is present
solely as a means of sustaining transport of the
gas molecule from one membrane side to the
other. Another example is inert membranes for
liquid separation applications, where surface
hydrophilicity and hydrophobicity may
completely determine the membrane transport
properties. The term inert membrane is rarely
used for conventional membrane separation pro-
cesses; however, one may find the term inert
membrane used in such phrases as “chemically
inert membrane” or “bio-inert membrane.” These
expressions refer to a specific property of the
membrane such as chemical stability or compat-
ibility in the case of chemical inertness or biolog-
ical inactivity in the case of bio-inertness. In these
cases the term inert membrane has a somewhat
different meaning than that related to the IMRs.
References
Koros WJ, Ma YH, Shimidzu T (1996) Terminology for
membranes and membrane processes. Pure Appl
Chem 68:1479–1489
Mulder M (1996) Basic principles of membrane technol-
ogy. Kluwer Academic Publishers, Dordrecht, The
Netherlands
Sirman J (2006) The evolution of materials and architec-
ture for oxygen transport membranes. In: Sammells
AF, Mundschau MV (eds) Nonporous inorganic mem-
branes. Wiley-VCH, Weinheim, pp 165–184
Ward TL, Dao T (1999) Model of hydrogen permeation
behavior in palladium membranes. J Membr Sci
153:211–231
I
Inert Membrane Reactors
Rune Bredesen
Sustainable Energy Technology, SINTEF
Materials and Chemistry, Oslo, Norway
A membrane, defined as a barrier between two
phases through which transport of one or several
species occurs, can be made from virtually any
solid or liquid material or combinations of both.
Membranes are commonly divided into inor-
ganic, polymeric, hybrid inorganic and poly-
meric, or as dual phase consisting of a solid
phase and a liquid phase. Furthermore, the mem-
brane may either be dense or porous with a con-
tinuous network of pores.
A membrane reactor (MR) is a device for
simultaneously carrying out a reaction and
membrane-based separation in the same physical
enclosure (Koros et al. 1996). In an inert mem-
brane reactor (IMR), the inert membrane (link)
and the catalyst in the form of a separate solid or a
liquid phase are contained in the reactor
(Fontananova and Drioli 2010; Julbe et al. 2001;
Coronas and Santamaria 1999). Figure 1 illus-
trates different catalyst and inert membrane com-
binations in an IMR. Due to the separation of
membrane and catalyst in the IMR, the
membrane-based process and catalytic reactions
occur in sequence. This decoupling of the pro-
cesses can be advantageous with respect to oper-
ation and replacement of membrane and/or
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_310-1
catalyst compared to MRs where the membrane
serves as both catalyst and membrane. The two
main functions of the membrane applied in IMRs
are as an extractor or a distributor (Julbe
et al. 2001; Dalmon 1997) (see Fig. 2). As an
extractor, the inert membrane selectively sepa-
rates a reaction product or intermediate product.
The advantage may be higher conversion
(equilibrium-limited reactions) or/and higher
selectivity (e.g., via extraction of an intermediate
that would otherwise lead to subsequent
unwanted reactions). Extraction of hydrogen
from hydrocarbon dehydrogenation, reforming,
or water gas shift reactions, employing hydrogen
selective membranes in combination with packed
or fluidized catalyst beds, has been widely stud-
ied (Sanchez Marcano and Tsotsis 2002). Dehy-
drogenation and reforming are typically
equilibrium-limited endothermic reactions, and
membrane reactor applications may benefit from
the use of lower operating temperature and/or
higher pressure without sacrificing yield. Esteri-
fication is yet another example of catalyzed
equilibrium-limited reactions where water
extraction by an inert membrane is used to
increase yield (Van der Bruggen 2010). As a
distributor, the inert membrane delivers the reac-
tant in a controlled manner to the catalyzed reac-
tion taking place in the reactor compartment
(Julbe et al. 2001). The typical aim is to enhance
selectivity through careful addition and tempera-
ture control of exothermic oxidation and hydro-
genation reactions. Some common examples are
2 Inert Membrane Reactors

Inert Membrane Reactors, Fig. 1 Inert membrane (a) with solid catalyst, (b) with liquid containing the catalyst, (c)
encapsulating solid catalyst, (d) encapsulating liquid containing the catalyst

Inert Membrane Reactors, Fig. 2 (a) Membrane extractor operation, (b) membrane distributor operation

IMR with packed catalyst bed for oxidative cou-
pling of methane to C2, or oxidative dehydroge-
nation of hydrocarbons, by addition of oxygen
and hydrogenation of alkenes by hydrogen addi-
tion. For some oxidation reactions employing
IMRs, the separation of the bulk of the reactants
by the membrane wall lowers the explosion
potential (Coronas and Santamaria 1999).
As most membrane materials are inert, the
incorporation of many different types into IMRs
has been studied. Cheap polymeric membranes
are advantageous with respect to capital cost,
high packing density, and simple sealing technol-
ogy in modules. However, their low operating
temperature, typically less than 100  C, and lim-
ited chemical stability narrow the range of appli-
cations. More expensive inorganic membranes
enable high temperature operation, but since sta-
bility and transport properties are usually very
temperature dependent, the different inorganic
membranes have a limited window of operation.
Several decades of research have shown that a
number of challenges still exist with respect to
high temperature applications, and commercial
use of IMRs is still a future prospect. To aid
reaching this future prospect, mathematical
modeling and simulation is required to develop
IMR design and provide an understanding of the
optimal operating conditions.
References
Coronas J, Santamaria J (1999) Catalytic reactors based on
porous ceramic membranes. Catal Today 51:377–389
Dalmon JA (1997) Catalytic membrane reactors. In:
Ertl G, Knözinger H, Weitkamp J (eds) Handbook of
heterogeneous catalysis, vol 3. Wiley-VCH
Weinheim, Germany, pp 1387–1398
Fontananova E, Drioli E (2010) Catalytic membranes and
membrane reactors. In: Drioli E, Giorno L (eds) Com-
prehensive membrane science and engineering,
vol 3. Elsevier, Amsterdam, pp 109–133
Julbe A, Farrusseng D, Guizard C (2001) Porous ceramic
membranes for catalytic reactors – overview and new
ideas. J Membr Sci 181:3–20
Inert Membrane Reactors
Koros WJ, Ma YH, Shimidzu T (1996) Terminology for
membranes and membrane processes. Pure Appl
Chem 68:1479–1489
Sanchez Marcano JG, Tsotsis TT (2002) Catalytic mem-
branes and membrane reactors. Wiley-VCH,
Weinheim
3
Van der Bruggen B (2010) Pervaporation membrane reac-
tors. In: Drioli E, Giorno L (eds) Comprehensive mem-
brane science and engineering, vol 3. Elsevier,
Amsterdam, pp 135–163
F
Filler in Membranes
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
Synonyms
Inorganic fillers
Composite perfluorosulfonic acid membranes
containing different types of inorganic fillers
such as hygroscopic oxides, surface-modified
oxides, zeolites, inorganic proton conductors,
etc. have shown an increased conductivity with
respect to the bare perfluorosulfonic membranes
at high temperature (Aricò et al. 1998, 2003). The
presence of hygroscopic inorganic oxides inside
the composite membrane besides extending the
operation of perfluorosulfonic membranes (e.g.,
Nafion®) in the high-temperature range reduces
the crossover effects by increasing the “tortuosity
factor” in the permeation path. Such effects are
particularly serious at high temperature in DMFC
systems. An appropriate tailoring of the surface
chemistry in these nanoparticles is a key step to
enhance water retention at high temperature.
Composite recast Nafion ® membranes containing
inorganic fillers have been employed in high-
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_313-1
temperature (~150  C) direct alcohol (Aricò
et al. 1998) and H2-air fuel cells (Watanabe
et al.1996). These composite membranes were
originally developed for reduced humidification
operation in polymer electrolyte fuel cells
(Watanabe et al.1996) due to the enhanced
water retention inside the membrane by the effect
of the inorganic filler (Aricò et al. 1998).
A further advantage of composite membranes
relies in the barrier effect given by the inorganic
filler for methanol crossover (Ren et al. 1996).
References
Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998)
Comparison of ethanol and methanol oxidation in a
liquid-feed solid polymer electrolyte fuel cell at high
temperature. Electrochem Solid-State Lett 1:66–68
Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
Antonucci V (2003) Influence of the acid–base char-
acteristics of inorganic fillers on the high temperature
performance of composite membranes in direct meth-
anol fuel cells. Solid State Ionics 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells.
J Electrochem Soc 143:L12
Watanabe M, Uchida H, Seki Y, Emori M, Stonehart
P (1996) Self-humidifying polymer electrolyte mem-
branes for fuel cells. J Electrochem Soc 143:3847
I
Inorganic Catalytic Membrane
Rune Bredesen
Sustainable Energy Technology, SINTEF
Materials and Chemistry, Oslo, Norway
An inorganic catalytic membrane is an inorganic
membrane that is catalytically active. Inorganic
membranes are made from metals, ceramics,
glass, and carbon and may be porous or dense.
The term inorganic catalytic membrane is typi-
cally meant in the context of membrane reactors
where yield is enhanced by combining a mem-
brane separation and a catalyzed chemical reac-
tion. Inorganic catalytic membranes can either be
composed of an inherently catalytically active
material or an inert membrane structure to
which a catalytically active phase is added on
the outer surface or inside pores (Specchia
et al. 2006), see Fig. 1. In the latter case, integra-
tion of catalyst material and inorganic membrane
structure is carried out by common deposition
and impregnation methods such as wet (electro)
chemical deposition, chemical vapor deposition,
or physical vapor deposition. Since the mem-
brane is catalytic, reaction and separation occur
in parallel a feature which distinguishes it from
the sequential processes of inert membrane reac-
tors where the inert membrane and catalyst mate-
rial are separated. The function of the membrane
may serve as extractor, distributor, or contactor
depending on application (Dalmon 1997) (see
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_314-2
Fig. 2) and the reaction mechanism can be
(electro)catalytic, photo-catalytic, or
bio-catalytic. The many different concepts and
envisaged applications are described comprehen-
sively in various text books and scientific papers
(Gryaznov et al. 2006; Sanchez Marcano and
Tsotsis 2002; Caro 2010; Fontananova and Drioli
2010).
Inorganic catalytic membranes can operate at
higher temperatures than their polymeric coun-
terpart, which opens a broader window of opera-
tion as high temperature is also required for many
important reactions which are limited by low
yield in traditional reactors. The assembling of
inorganic catalytic membranes in membrane
modules may, however, give too low a catalytic
surface area and limited conversion and therefore
render operation less cost efficient compared to
more conventional reactors. To mitigate this
problem, additional catalyst can be added to the
reactor volume. In order to increase efficiency,
some current development activities are aimed at
manufacturing inorganic thin capillary,
multichannel, and hollow fiber membranes with
high surface area/volume ratio.
The dual operational nature of inorganic cata-
lytic membranes is particularly challenging since
both membrane and catalytic properties must
work satisfactory. Commonly encountered issues
related to degradation processes such as adsorp-
tion, poisoning, clogging, and fouling are all crit-
ical and membrane lifetime may suffer when
trying to achieve the optimal trade-off between
2 Inorganic Catalytic Membrane

a b
c

d e

Inorganic Catalytic Membrane, Fig. 1 Inherently catalytic (a) porous, (b) dense membrane. Inert membrane with
catalyst deposited (c) inside pores, on outer surface of (d) porous, and (e) dense membrane

Inorganic Catalytic Membrane, Fig. 2 Inorganic catalytic membrane in (a) extractor operation, (b) distributor
operation, (c) flow-through contactor operation, (d) liquid–gas contactor operation

membrane and catalyst properties. Common
examples of applications include hydrocarbon
dehydrogenation, hydrocarbon reforming, and
hydrogenation of alkenes for which hydrogen
selective inorganic catalytic membranes can be
used (Sanchez Marcano and Tsotsis 2002). Com-
bination of endothermic (e.g., water splitting to
produce hydrogen) and exothermic (e.g., partial
oxidation of methane) reactions for integrated
mass and heat transport has been demonstrated
by using catalytically active oxygen permeable
membranes (Caro 2010). By feeding oxygen in a
controlled manner, partial oxidation of hydrocar-
bons to form synthesis gas, oxidative coupling of
methane, and oxidative dehydrogenation reac-
tions have been demonstrated using dense and
porous inorganic catalytic membranes (Sanchez
Marcano and Tsotsis 2002; Coronas and
Santamaria 1999; Sammells et al. 2006). When
porous inorganic catalytic membranes are used as
flow-through contactors, a forced close spatial
contact between reactants and catalyst can give
improved conversion efficiency compared to
reactions in catalyst powder beds (Westermann
and Melin 2009). Additionally, higher selectivity
may be achieved due to the short and well-
defined contact time between reactants and mem-
brane catalyst. Yet in another contactor mode, the
porous inorganic catalytic membrane provides a
defined catalytic region for reaction and controls
transport of reactants from both sides of the mem-
brane. For example, in liquid–gas catalytic
contactors, both hydrogenation and oxidative
reactions have been demonstrated.
References
Caro J (2010) Basic aspects of membrane reactors. In:
Drioli E, Giorno L (eds) Comprehensive membrane
science and engineering, vol 3. Elsevier, Amsterdam,
pp 1–24
Coronas J, Santamaria J (1999) Catalytic reactors based on
porous ceramic membranes. Catal Today 51:377–389
Dalmon JA (1997) Catalytic membrane reactors. In:
Ertl G, Knözinger H, Weitkamp J (eds) Handbook of
heterogeneous catalysis, vol 3. Wiley-VCH,
Weinheim, pp 1387–1398
Inorganic Catalytic Membrane
Fontananova E, Drioli E (2010) Catalytic membranes and
membrane reactors. In: Drioli E, Giorno L (eds) Com-
prehensive membrane science and engineering,
vol 3. Elsevier, Amsterdam, pp 109–133
Gryaznov VM, Ermilova MM, Orekhova NV,
Teresschenko GF (2006) Reactors with metal and
metal-containing membranes. In: Cybulski A, Moulijn
JA (eds) Structured catalysts and reactors. Chemical
industries, 2nd edn. Taylor and Francis Group, Boca
Raton, pp 579–614
Sammells AF, White JH, Makay R (2006) Membranes for
promoting partial oxidation chemistries. In: Sammells
3
AF, Mundschau MV (eds) Nonporous inorganic mem-
branes. Wiley-VCH, Weinheim, pp 185–214
Sanchez Marcano JG, Tsotsis TT (2002) Catalytic mem-
branes and membrane reactors. Wiley-VCH,
Weinheim
Specchia S, Fino D, Saracco G, Specchia V (2006) Reac-
tors with metal and metal-containing membranes. In:
Cybulski A, Moulijn JA (eds) Structured catalysts and
reactors. Chemical industries, 2nd edn. Taylor and
Francis Group, Boca Raton, pp 615–661
Westermann T, Melin T (2009) Flow-through catalytic
membrane reactors-principles and applications.
Chem Eng Process 48:17–28
I
Inorganic Scaling
Tony Fane
School of Chemical Engineering, UNSW, The
University of New South Wales, Sydney, NSW,
Australia
Synonyms
Inorganic fouling
Inorganic scaling occurs in reverse osmosis
(RO) applications and is caused by the retention
of sparingly soluble mineral salts such as calcium
carbonate, calcium sulfate, calcium phosphate,
barium sulfate, magnesium salts, silica, etc. Due
to water removal and concentration polarization
(CP), the concentrations build up and can exceed
the saturation level and cause scaling of the mem-
brane surface. Membrane scaling has two path-
ways, namely, surface crystallization and bulk
crystallization. For surface crystallization, CP
causes the sparingly soluble salt concentration
at the membrane surface to exceed the solubility
limit. Consequently, the surface is gradually cov-
ered by the lateral growth of a crystal deposit that
reduces the effective area for permeation. For
fixed imposed flux, the local flux increases in
order to compensate for loss of area, and this
increases the local CP level which exacerbates
the scale formation. In the other pathways, crys-
tals form in the bulk phase when concentrations
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_317-1
exceed saturation level due to high recovery
(defined as fraction of feedwater removed as per-
meate). Crystals in suspension are then deposited
on the membrane and eventually form a porous
cake layer, which provides a hydraulic resistance.
There are many membrane elements connected in
series in a RO plant, and concentration builds up
from the feed to the tail end. Scale formation is
therefore more prevalent in the tail end elements
of the plant. It is likely that both scaling mecha-
nisms, surface and bulk, could occur simulta-
neously in a RO system. This is because a
crystal cake causes “cake-enhanced concentra-
tion polarization” (CECP) (see “Irreversible
Fouling Resistance”), and the increased CP of
the scale formers leads to precipitation on the
membrane and within the cake.
There are several strategies to control scaling
in membrane systems. Bulk crystallization can be
mitigated by controlling the supersaturation level
of the salts by limiting the maximum recovery in
the RO system. The effect of CP on surface con-
centration can be manipulated by the ratio of flux
to crossflow velocity, where lower CP is favored
by modest flux and raised crossflow velocity.
Most scale formers are more soluble at lower
pH, so the injection of acid into the feed stream
can provide some control. The exception to this is
silica scaling which is more serious at lower pH
and requires an increase in pH. If silica and
calcium scalants are both present, it may be nec-
essary to soften the feed by ion exchange to
remove the calcium and then raise the pH. Scale
2 Inorganic Scaling
formation can also be controlled by the use of
antiscalant chemicals. These are proprietary
materials, but include various molecular weight
polycarboxylates and polyacrylates, usually
dosed at a few ppm level. Care needs to be
taken with antiscalant selection as some tend to
promote biofouling.
References
Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
brane processes, Chapter 6. In: Drioli E, Giorno
L (eds) Membrane operations, innovative separations
and transformations. Wiley –VCH. ISBN 978-3-527-
32038-7
I
Ion Exchange Membrane for Fuel
Cells
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
Low-temperature fuel cells can be equipped with
a proton or anion exchange membrane in alterna-
tive to liquid electrolytes (Aricò et al. 2001). The
core of a polymer electrolyte fuel cell (PEMFC)
is the ion exchange membrane. The electrodes
(anode and cathode) are in intimate contact with
the membrane faces. The membrane determines
the fuel cell resistance and the fuel permeation
rate, and it influences the reaction rate. It is well
known that the use of non-noble metal catalysts is
possible in the presence of alkaline electrolytes.
Protons conducting electrolytes have been pre-
ferred to alkaline electrolytes for several decades
for practical reasons, e.g., to avoid carbonation.
The standard electrolyte membrane is usually a
perfluorosulfonic acid membrane such as Nafion.
Most of the electrolytes alternative to Nafion both
proton conducting and alkaline type, e.g., hydro-
carbon type, are significantly cheaper, and in
some cases, they are also characterized by
smaller hydrogen and methanol crossover. How-
ever, lifetime characteristics similar to those
shown by Nafion-type membranes in fuel cells
have not yet been demonstrated for the alterna-
tive membranes. Concerning with the conductiv-
ity, only recently, membrane alternative to
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_326-2
Nafion type have shown similar levels of perfor-
mance. One critical aspect is related to the fact
that the presence of water is a requirement of
low-temperature PEMFCs and DMFCs for the
occurrence of the electrochemical reactions and
to promote ion conductivity (water-assisted con-
ductivity mechanism). High ionic conductivities
are often associated to the presence of large water
uptake by the membrane, but this property often
causes poor mechanical characteristics such as
large swelling and relevant crossover (especially
methanol). Phosphoric acid-doped polybenzoi-
midazole membranes use a Grotthus mechanism
of proton transport and do not require water
(Wang et al.1995). These membranes operate at
about 180–200  C. Whereas composite perfluor-
osulfonic acid membranes or sulfonated hydro-
carbon including inorganic fillers such as silica
rely on the water-assisted mechanism, they can
operate up to 145  C, under particular conditions
(3 bar abs pressure), due to the enhanced water
retention of the filler (Aricò et al. 2003).
Composite recast Nafion® membranes
containing inorganic fillers have been employed
in high temperature (150  C) direct alcohol
(Aricò et al. 1998) and H2-air fuel cells
(Watanabe et al.1996). These composite mem-
branes were originally developed for reduced
humidification operation in polymer electrolyte
fuel cells (Watanabe et al.1996) due to the
enhanced water retention inside the membrane
by the effect of the inorganic filler (Aricò
et al. 1998). A further advantage of composite
2 Ion Exchange Membrane for Fuel Cells
membranes relies in the barrier effect given by
the inorganic filler for methanol crossover (Ren
et al. 1996).
References
Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998)
Comparison of ethanol and methanol oxidation in a
liquid-feed solid polymer electrolyte fuel cell at high
temperature. Electrochem Solid-State Lett 1:66–68
Aricò AS, Srinivasan S, Antonucci V (2001) DMFCs:
from fundamental aspects to technology development.
Fuel Cells 1:133
Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
Antonucci V (2003) Influence of the acid–base char-
acteristics of inorganic fillers on the high temperature
performance of composite membranes in direct meth-
anol fuel cells. Solid State Ionics 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells. J
Electrochem Soc 143:L12
Wang J, Wasmus S, Savinell RF (1995) Evaluation of
ethanol, 1-propanol, and 2-propanol in a direct oxida-
tion polymer-electrolyte fuel cell. J ElectrochemSoc
142:4218
Watanabe M, Uchida H, Seki Y, Emori M, Stonehart P
(1996) Self-humidifying polymer electrolyte mem-
branes for fuel cells. J Electrochem Soc 143:3847
I
Irreversible Flux Decline
Tony Fane
School of Chemical Engineering, The University
of New South Wales, UNSW, Sydney, NSW,
Australia
Singapore Membrane Technology Centre,
Nanyang Technological University, Singapore,
Singapore
Membranes are either operated at constant pres-
sure (P) or constant flux (J); the former is more
typical of lab scale studies and the latter of com-
mercial operation. Fouling leads to flux decline
under constant pressure or a rise in the required
transmembrane pressure DP for constant flux.
These trends are illustrated in Fig. 1. It should
be noted that fouling under constant pressure
becomes self-limiting; the lower the flux, the
slower the fouling. For constant flux operation,
the fouling can be self-accelerating, often leading
to a sudden rise in TMP (DP) as shown for case
(ii) in Fig. 1b. This “TMP jump” could be asso-
ciated with a critical consolidation of the fouling
layer and rapid rise in fouling resistance. Irrevers-
ible flux decline is the drop in flux due to irre-
versible fouling. The effect of irreversible fouling
can also be expressed as irreversible permeability
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_327-1
decline (given by the change in J/DP), and this
can be used for both constant pressure and con-
stant flux operation. However, it is important to
note that fouling is flux driven. As a result it is
more appropriate to compare membranes at the
same initial flux for constant pressure tests. Fig-
ure 1a illustrates two membranes, M1 and M2,
where M1 has an initially higher permeability
and starts at a higher flux. Fluxes for M1 and
M2 both decline due to the increasing fouling
resistance (see ▶ Irreversible Fouling Resis-
tance), and both membranes asymptote to similar
declined fluxes. This is due to the eventual dom-
inance of the fouling resistance (RF) over the
membrane resistance (Rm) (see Eqs. 1 and 2 in
▶ Irreversible Fouling Resistance). If membranes
M1 and M2 were tested at the same constant flux,
it would be easier to identify if one was intrinsi-
cally less prone to fouling.
References
Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
brane processes, Chapter 6. In: Drioli E, Giorno
L (eds) Membrane operations, innovative separations
and transformations. Wiley-VCH, Weinheim. ISBN
978-3-527-32038-7
2 Irreversible Flux Decline

a b

M1
FLUX

TMP
(i)
M2 (ii)

Time Time
Flux vs time for Constant Pressure operation Pressure vs time for Constant Flux operation

Irreversible Flux Decline, Fig. 1 Constant pressure and constant flux operation: fouling trends
I
Irreversible Fouling
Tony Fane
School of Chemical Engineering, UNSW, The
University of New South Wales, Sydney, NSW,
Australia
Singapore Membrane Technology Centre,
Nanyang Technological University, Singapore
Membrane fouling is the accumulation of mate-
rial on the surface of or within the membrane
structure. The foulant may provide a cake or
surface deposit layer, and if the membrane is
microporous, the foulant could cause pore restric-
tion/closure or pore plugging. These fouling
mechanisms are depicted in Fig. 1. Membrane
fouling is prevalent in all the liquid-phase mem-
brane processes. Fouling species can be organic
macromolecules (proteins, polysaccharides,
etc.), inorganics (scale precipitates), and colloi-
dal or biological (biofilms). Fouling is linked to,
but different from, concentration polarization
(CP). CP is a buildup of retained species
(solutes) adjacent to the membrane surface and
can be depicted as a boundary layer concentration
profile based on a balance between convection
(flux driven) and back transport (diffusion). CP
increases with flux but is totally reversible when
flux is ceased; fouling is not totally reversible. In
many situations fouling has both reversible and
irreversible components. The reversible
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_328-1
component may be removed by hydrodynamic
means, such as backwash or increased shear at
the membrane surface. This type of foulant is
usually loosely deposited or bound on the mem-
brane and subject to removal by raised liquid
velocities. However, it is not removed by simply
dropping flux to zero. The irreversible fouling is
material that is tightly held by the membrane. It
could be colloids plugging pores, macrosolutes
bound by adsorption, insoluble salts spreading as
crystals, and biofilms comprising bacteria held in
a matrix of extracellular polymeric substances
(EPS). Irreversible fouling can usually be miti-
gated by feed pretreatment, suitable hydrody-
namics, and careful membrane selection. For
example, pretreatment could remove colloids or
bacteria, or involve the addition of antiscalants.
Hydrodynamic control could match crossflow
velocity to the imposed flux to operate below
the critical flux, where the critical flux is the
flux below which fouling is negligible. Mem-
brane selection would consider pore size, surface
charge, hydrophobicity/hydrophilicity,
etc. Irreversible fouling is usually partially
removable by cleaning regimes, which could
range from daily to monthly, with chemical or
physical agents, depending on the situation.
However, the gradual buildup of residual irre-
versible fouling, over multiple cleaning cycles,
may eventually reach a critical level, and mem-
brane replacement is required.
2 Irreversible Fouling

1 Pore Closure 2 Pore Plugging 3 ‘Cake’ (surface)

deposition

Irreversible Fouling, Fig. 1 Membrane fouling mechanisms

For more information on membrane fouling, References

see “▶ Irreversible Flux Decline” and “▶ Irre-
versible Fouling Resistance.”
Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
brane processes, Chapter 6. In: Drioli E, Giorno
L (eds) Membrane operations, innovative separations
and transformations, Wiley-VCH Weinheim. ISBN:
978-3-527-32038-7
I
Irreversible Fouling Resistance
Tony Fane
School of Chemical Engineering, The University
of New South Wales, Sydney, NSW, Australia
Singapore Membrane Technology Centre,
Nanyang Technological University, Singapore,
Singapore
Flux can be related to the driving force (DP
DP)
and the overall resistance, RT, by,
DP
DP
J¼
mðRT Þ
The osmotic pressure term (DP) can be ignored
for non-osmotic operation (i.e., MF applications).
The resistance components are assumed to be in
series, so,
RT ¼ Rm þ RF
where Rm is the membrane resistance and RF is
the fouling resistance, which may comprise a
reversible (Rrr) and irreversible (Rir) component,
i.e.,
RF ¼ Rrr þ Rir
For a given DP, the flux vs. time data gives the
various resistances. The initial clean water flux
gives Rm, the final “fouled” flux gives RT, and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_329-1
RT – Rm gives RF. A water flush should remove
Rrr, leaving resistances Rm + Rir. Chemical
cleaning should remove Rir, but usually a residual
DRir remains as explained in irreversible fouling.
For constant flux, the DP data can be used to
estimate the various resistances.
For processes like reverse osmosis, the
osmotic pressure term in Eq. 1 is important. The
magnitude of DP is increased in practice by a
factor M, the polarization modulus; this is due to
concentration polarization. Equation 1 becomes:
DP
MDP
J¼ (4)
mðRT Þ
(1)
M is the ratio of solute concentration at the mem-
brane surface to the solute in the bulk, and in a
well-operated RO desalination process, without
fouling, M = 1.1–1.2. The polarization
modulus, M, can be increased if there is a
“cake” layer on the RO membrane surface. The
(2) layer provides an unstirred region where the sol-
ute (salt) concentration builds up. Figure 1
depicts concentration polarization for a clean
and cake fouled RO membrane. The increased
polarization (Fig. 1b) is “cake-enhanced” con-
centration polarization (CECP), and the
increased osmotic pressure is the “cake-
(3) enhanced” osmotic pressure (CEOP) (Hoek and
Elimelech 2003). Both fouling resistance and
CEOP contribute to loss of flux (for fixed DP)
or increased DP for fixed flux.
2 Irreversible Fouling Resistance

Irreversible Fouling a CB b CB
Resistance, Fig. 1 (a)
Concentration
polarization – clean
membrane. (b) Cake-
enhanced concentration
Shear
polarization – fouled Cake
membrane
CW1 CW2
Membrane

CP1 CP2

References Further Reading

Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
Hoek EMV, Elimelech M (2003) Cake enhanced concen- brane processes, chapter 6. In: Drioli E, Giorno L (eds)
tration polarization: a new fouling mechanism for salt- Membrane operations, innovative separations and
rejecting membranes. Environ Sci Technol transformations. Wiley –VCH, Weinheim. ISBN
37:5581–5588 978-3-527-32038-7
H
Hybrid Regenerated Cellulose/
Loaded Lipid Nanoparticle
Membranes: Preparation
and Characterization
Juana Benavente1 and Juan Manuel López-
Romero2
1
Departamento de Fisica Aplicada I, Universidad
de Malaga, Facultad de Ciencias, Malaga, Spain
2
Departamento de Quimica Organica,
Universidad de Malaga, Facultad de Ciencias,
Malaga, Spain
New membrane systems related to medical appli-
cations (drug-release devices, mimetic mem-
branes, or patches) are receiving great attention
(M€ uller et al. 2000). Among them, lipid
nanoparticles (LNPs) prepared using biocompat-
ible components and with tunable properties are
of significant interest (Gupta and Kompella 2006;
Huynh et al. 2009); although, their use is still
limited due to stability problems during contact
with biological fluids, storage, or administration
(Korting and Schäfer–Korting 2010). To over-
come these limitations, polymeric nanosphere
gels were proposed for topical delivery of lipo-
philic molecules (Martins et al. 2007). In this
context, the inclusion of functionalized lipid
nanoparticles (FLNPs) in support to biocompati-
ble membranes (such as regenerated cellulose
membranes) offers an attractive route for con-
trolled release of pharmacologic agents.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_338-3
The LNPs used in this study were prepared by
the ultrasound method (Feng and Huang 2001)
using L-a-phosphatidylcholine and Tween ® 80 as
surfactants and glyceryl tristearate as the main
lipid component, while sunscreen DHB
(2,4-dihydroxybenzophenone) was the active
organic component. The hybrid membrane was
obtained by embedding the DHBLNPs in a dense
highly hydrophilic regenerated cellulose
(RC) support by immersion in a water dispersion
of DHBLNPs (membrane RC/DHBLNPs). The
incorporation of the loaded LNPs was character-
ized by AFM, brilliant field microscopy (Fig. 1a),
TEM (Fig. 1b), and Raman spectroscopy
(Vázquez et al. 2011; Hierrezuelo et al. 2012).
Reductions in material characteristic parameters
(conductivity and dielectric constant) for dry
RC/DHBLNP samples when compared with the
original RC and changes associated to thermal
effects were also obtained.
The stability of the hybrid membrane as a
result of both contact time with NaCl solutions
and osmotic pressure gradients was established
by comparing diffusional permeability (Ps) for
original RC and RC/LNP membranes (Vázquez
et al. 2011; Hierrezuelo et al. 2012). The presence
of the DHBLNPs reduces in approximately 20 %
Ps values for the whole interval of feed concen-
trations studied (0.001  Cf(M)  0.4), and a
constancy in the NaCl flow for at least 20 h was
also observed. The cellulose structure also
2 Hybrid Regenerated Cellulose/Loaded Lipid Nanoparticle Membranes

Hybrid Regenerated Cellulose/Loaded Lipid Nanoparticle Membranes: Preparation and Characterization,

Fig. 1 Hybrid membrane micrographs: (a) brilliant filed microscopy (b) TEM

reduces the DHB delivery from the loaded LNPs,
being the value for the hybrid membrane 5 % of
that for the DHBLNPs (after 30 min).
References
Feng SS, Huang G (2001) Effects of emulsifiers on the
controlled release of paclitaxel (Taxol ®) from
nanospheres of biodegradable polymers. J Control
Release 71:53–69
Gupta RB, Kompella UB (2006) Nanoparticle technology
for drug delivery. Taylor and Francis/CRC Press, New
York
Hierrezuelo J, Benavente J, López–Romero JM, Martı́nez
de Yuso MV, Rodrı́guez–Castellón E (2012) Prepara-
tion, chemical and electrical characterizations of lipid
nanoparticles loaded with dihydroxybenzophenone.
Med Chem 8:541–548
Huynh NT, Passirani C, Saulnier P, Benoit JP (2009) Lipid
nanocapsules: a new platform for nanomedicine. Int
J Pharm 379:201–219
Korting HC, Schäfer–Korting M (2010) Carriers in the
topical treatment of skin disease. Handb Exp
Pharmacol 197:435–468
Martins S, Sarmento B, Ferreira DC, Souto EB
(2007) Lipid–based colloidal carriers for peptide and
protein delivery–liposomes versus lipid nanoparticles.
Int J Nanomedicine 2:595–607
M€
uller RH, Mäder K, Gohla S (2000) Solid lipid
nanoparticles for controlled drug delivery – a review
of the state of the art. Eur J Pharm Biopharm
50:161–177
Vázquez MI, Peláez L, Benavente J, López-Romero JM,
Rico R, Hierrezuelo J, Guillén E, López-Ramı́rez MR
(2011) Functionalized lipid nanoparticles-cellophane
hybrid films for molecular delivery. J Pharm Sci
100:4815–4822
L
Liquid Membrane Separation
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Liquid membrane separation combines the sol-
vent extraction and stripping processes
(re-extraction) in a single step.
This entry has the objective of introducing the
reader to the basic definitions of the liquid mem-
brane field, with classification.
The term liquid membrane transport includes
processes incorporating liquid-liquid extraction
(LLX) and membrane separation in one continu-
ously operating device. It utilizes an extracting
reagent solution, immiscible with water, stagnant
or flowing between two aqueous solutions
(or gases), the source or feed, and receiving or
strip phases. In most cases, the source and receiv-
ing phases are aqueous, and the membrane is
organic, but the reverse configuration can also
be used. A polymeric or inorganic microporous
support (membrane) may be used as bearer (as in
SLM) or barrier (as in BLM technologies) or not
used, as in ELM and layered BLM (see respective
entries: ▶ SLM, ▶ ELM, ▶ BLM).
The great potential for energy saving, low
capital and operating cost, and the possibility to
use expensive extractants, due to the small
amounts of the membrane phase, make LMs an
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_340-1
area deserving special attention. Liquid mem-
brane systems are being studied extensively by
researchers in such fields as analytical, inorganic,
and organic chemistry; chemical engineering, bio-
technology, and biomedical engineering; and
wastewater treatment. Research and development
activities within these disciplines involve diverse
applications of liquid membrane technology, such
as gas separations, recovery of valued or toxic
metals, removal of organic compounds, develop-
ment of sensing devices, recovery of fermentation
products, and some other biological systems.
The general properties of liquid membrane
systems have been a subject of extensive theoret-
ical and experimental studies. Some general char-
acteristics of LM processes are as follows:
1. Liquid membrane separation is a rate process,
and the separation occurs due to a chemical
potential gradient, not by equilibrium between
phases.
2. LM is defined based on its function, not the
material used in fabrication.
Permeation is a general term for the
concentration-driven membrane-based mass
transport process. Differences in the permeability
produce a separation between solutes at constant
driving force. Because the diffusion coefficients
in liquids are typically orders of magnitude
higher than in polymers, a larger flux can be
obtained with liquid membranes. Application of
2 Liquid Membrane Separation

Liquid Membrane
Separation, Fig. 1 Three BLM
configurations of liquid
membrane systems: bulk
(BLM), supported R
F E
(immobilized) (SLM or
ILM), and emulsion
(ELM). F is the source or Porous
Porous
feed phase, E is the liquid Support
Support
membrane, and R is the
receiving phase

SLM
E
F

R
Porous
Support

ELM
E R

F F

a pressure difference, an electric field, or temper-
ature considerably intensifies the process.
There are several different directions in LM
separation classifications: according to module
design configurations (see ▶ SLM, ▶ ELM,
▶ BLM entries), according to transport mecha-
nisms (see ▶ LM Transport Mechanisms),
according to applications, according to carrier
type, and according to membrane support type.
Below, these types of classifications are
described and discussed briefly.
According to configuration definition, three
groups of liquid membranes are usually consid-
ered (see Fig. 1): bulk (BLM), supported or
immobilized (SLM or ILM), and emulsion
(ELM) liquid membrane transport. Some authors
add to these definitions polymeric inclusion
membranes, gel membranes, and dual-module
hollow-fiber membranes, but, to my opinion, the
first two types are the modifications of the SLM,
and the third is the modification of BLM.
According to the transport mechanisms, the LM
techniques may be divided into simple transport,
facilitated or carrier-mediated transport, coupled
counter- or cotransport, and active transport.
According to applications, the LM techniques
may be divided into (1) metal separation-
concentration, (2) biotechnological product
recovery-separation, (3) pharmaceutical product
recovery-separation, (4) organic compound sep-
aration and organic pollutant recovery from
wastewaters, (5) gas separations, (6) fermentation
or enzymatic conversion-recovery-separation
(bioreactors), (7) analytical applications, and (8)
wastewater treatment including biodegradation-
separation techniques.
Classification according to carrier type is as
follows: (1) water-immiscible, organic carriers,
Liquid Membrane Separation
(2) water-soluble polymers, (3) electrostatic,
ion-exchange carriers, and (4) neutral, but polar-
izable carriers.
Classification according to membrane support
type is as follows: (1) neutral hydrophobic,
hydrophilic membranes, (2) charged
(ion-exchange) membranes, (3) flat sheet, spiral
module membranes, (4) hollow-fiber membranes,
and (5) capillary hollow-fiber membranes.
3
Module design configurations are used as a
rule as basic classification.
Practically, there are a lot of opportunities for
liquid membrane separation processes in many
areas of industry. The most interesting develop-
ments for industrial membrane technologies are
related to the possibility of integrating various
membrane operations in the same industrial
cycle, with overall important benefits in terms
of product quality and plant compactness.
M
Macrosolute
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Macrosolute represents an operational term from
the field of membrane filtration which denotes
solute(s) of particle size(s) larger than ones that
pass through a membrane (microsolute) of a spec-
ified pore size or permeability limit. Membrane
filtration may be used to treat such solution
(system with macrosolute, microsolute, and sol-
vent) to concentrate valuable macrosolute in this
solution and to get rid of (or dilute) lower molec-
ular weight impurities (Fig. 1).
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_346-5
Distinction of species considered as
macrosolute depends on membrane process
which is used to treat the solution (Cheryan
1998). In case of:
• Microfiltration – macrosolute is represented by
suspended particles and bacteria bodies.
• Ultrafiltration – macrosolute presents macro-
molecules (typically proteins) and species with
larger particle sizes
• Nanofiltration – dissociated acids and divalent
salts, sugars, and species with larger particle
sizes can be concentrated in solution.
• Reverse osmosis – only water passes through
the membrane, and thus the term macrosolute
stands for any other species present in the
solution.
2 Macrosolute

Macrosolute, Fig. 1 1,50E-04

Comparison of cross-flow

CONCENTRATION OF THE SOLUTE IN

and dead-end filtration in
terms of permeate

THE PERMEATE [mM/ml]

concentration

dead-end
cross-flow with optimum
surface renewal

0,00E+00
0 100 200 300
TIME [s]

References

Cheryan M (1998) Ultrafiltration and microfiltration hand-

book. CRC Press, Boca Raton
M
Manganese Removal by Liquid
Membranes
Argurio Pietro
Depatment of Environmental and Chemical
Engineering, University of Calabria, Arcavacata
di Rende (CS), Italy
Manganese is the chemical element having the
symbol Mn and atomic number 25. It is an essen-
tial trace nutrient in all forms of life: it serves as a
necessary constituent of metalloproteins includ-
ing enzymes since it optimize enzyme and mem-
brane transport function. Although the toxicity of
manganese compounds is lower than those of
other widespread metals, such as nickel and cop-
per, both its excess and deficiency in the body can
cause serious impairment of vital physiological
and biochemical processes. Excessive manganese
intake is most frequently associated with the
so-called manganism, a rare central nervous sys-
tem disorder, characterized by symptoms similar
to Parkinson’s disease (weakness, monotone and
slowed speech, tremor, disorientation, memory
impairment, anxiety, and hallucinations).
Manganese compounds, in which it has vari-
ous oxidation states, are widely used in the indus-
try. Manganese dioxide is used in dry cell batteries
as a depolarizer and in glassmaking as a drying
agent. Depending on their oxidation state, manga-
nese ions have various colors and are used indus-
trially as pigments. The permanganates of alkali
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_347-7
and alkaline earth metals are powerful oxidizers,
so that they are used as a bactericide and algaecide
in water treatment and as an oxidant in organic
chemical synthesis. Since manganese is used in
these and other different industrial processes, its
separation and/or recovery from the various liquid
effluents or wastewater is of practical value.
A variety of separation processes for metal ions
have been developed for industrial needs, includ-
ing precipitation, inorganic and polymeric adsorp-
tion, evaporation, and reverse osmosis. Such
techniques produce water within international
health standards but entail some drawbacks.
Solvent extraction procedures have proven to
be very useful in the separation and/or recovery of
metal ions from aqueous media, but they involve
high capital and operating costs due to large
inventory of solvent, especially in the case of
dilute solutions. Thus liquid membrane has been
proven to be a very powerful technology.
A liquid membrane (LM) is a layer of an
organic phase (the so-called LM phase) that sep-
arates two aqueous solutions. An extractant
(carrier), promoting the so-called facilitated trans-
port from the donor phase (feed) to the acceptor
phase (strip), may be dissolved in the organic
phase (Molinari et al. 2009a, b). LM-based pro-
cesses offer a technology with a lot of advantages
over conventional separation techniques. The
main advantages are (i) combination of extraction
and stripping processes in a single stage, resulting
in a low solvent consumption; (ii) uphill transport
against concentration gradient; and (iii) small
2 Manganese Removal by Liquid Membranes
amounts of extractant needed, resulting in the
possibility to use very selective carriers, which
sometimes are not very cheap.
A widely used important acidic extractant in
hydrometallurgy in metal separation and/or recov-
ery is di(2-ethylhexyl)phosphoric acid
(D2EHPA). It is extensively used also in the
extraction and recovery of manganese from neu-
tral and weakly acidic solutions using supported
liquid membrane and emulsion liquid membrane
(Mohapatra and Kanungo 1992). Some studies
(Yongtao et al. 1992) considered the simultaneous
extraction and concentration of cadmium and
manganese from aqueous solutions obtaining
recoveries of cadmium and manganese in the
range of 92–100 %. Recently a novel method for
Mn(II) extraction from sulfuric acid solutions has
been proposed (Sadyrbaeva 2011) which involves
electrodialysis and a bulk liquid membrane
containing D2EHPA as the carrier. To accelerate
the ion transfer through the liquid ion-exchange
membrane, an electric field was applied. Operat-
ing in this way, the electrodialytic process
(unselective) was coupled with the liquid
membrane-based process, which provides greater
selectivity and permeability with respect to the
traditional solid ion-exchange membrane. Com-
plete removal of Mn(II) from a feed solution
containing 0.01 mol/L of MnSO4 and a maximum
extraction degree of 88 % was obtained under
optimized conditions.
Liquid Membrane as Pre-concentration
Technique
Manganese could be accumulated in tissues and
body fluids, like blood serum and urine.
Considering the very low concentration of trace
elements (manganese in our case) in these fluids, a
pre-concentration step before analysis is required.
According to results from a recent study (Soko
et al. 2003), the D2EHPA-based supported liquid
membrane technique can be used to extract and
pre-concentrate Mn(II) from water, milk, and
blood serum.
References
Mohapatra R, Kanungo SB (1992) Kinetics of Mn
(II) transport from aqueous sulphate solution through
a supported liquid membrane containing di
(2-ethylhexyl) phosphoric acid in kerosene. Sep Sci
Technol 27:1759–1773
Molinari R, Argurio P, Poerio T (2009a) Studies of various
solid membrane supports to prepare stable sandwich
liquid membranes and testing copper(II) removal from
aqueous media. Sep Purif Technol 70:166–172
Molinari R, Argurio P, Poerio T (2009b) Flux enhancement
of stagnant sandwich compared to supported liquid
membrane systems in the removal of Gemfibrozil
from waters. J Membr Sci 340:26–34
Sadyrbaeva TZ (2011) Hybrid liquid
membrane – electrodialysis process for extraction of
manganese(II). Desalination 274:220–225
Soko L, Chimuka L, Cukrowska E, Pole S (2003) Extrac-
tion and preconcentration of manganese(II) from bio-
logical fluids (water, milk and blood serum) using
supported liquid membrane and membrane probe
methods. Anal Chim Acta 485:25–35
Yongtao L, Aixia W, Van Loon JC, Barefoot RR
(1992) Extraction and enrichment of cadmium and
manganese from aqueous solution using a liquid mem-
brane. Talanta 39:1337–1341
M
Mass Intensity
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende, CS, Italy
Membrane operations are well known for their
modularity, compactness, and flexibility; there-
fore, they can be considered as new operations
developed in the logic of process intensification.
Recently, new metrics for comparing membrane
performance with those of conventional units
have been introduced (Curzon et al. 2001;
Brunetti et al. 2011, 2014). These new metrics
take into account the size, the weight, the flexi-
bility, the yield, and the modularity of the plants.
They are useful for having an immediate indica-
tion of the eventual gain that a membrane opera-
tion can offer with respect to a traditional one. In
this sense, they are useful also for selecting the
proper separation technology for a specific
process.
Among them, mass intensity is a measure of
the exploitation of the raw material with respect
to final production or recovery of the desired
product, and it can be intended as a measure of
the efficiency of the process.
In order to compare different systems, it can
have different definitions: it can be calculated
taking into account the product and its fraction
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_348-1
recovered (Eq. 1) as valuable product with
respect to the total mass fed. It can also be calcu-
lated as the ratio between the amount of product
and its fraction recovered with respect to the
steam and cooling water necessary to carry out
the process (Eq. 2). In the ideal situation, the mass
intensity would approach 1 which means that all
the inlet mass has been converted or recovered as
valuable product.
Mass Intensity_1 ¼
Total inlet mass (1)
Mass of desired product recovered
Mass Intensity_2 ¼
Steam and cooling water required (2)
Mass of desired product recovered
References
Brunetti A, Barbieri G, Drioli E (2011) New metrics in
membrane gas separation, chapter 20. In: Drioli E,
BarbCieri G (eds) Membrane engineering for the treat-
ment of gases, vol 2. The Royal Society of Chemistry,
Cambridge, UK, pp 279–301. ISBN 978-1-84973-239-0
Brunetti A, Drioli E, Barbieri G (2014) Energy and mass
intensities in hydrogen upgrading by a membrane reac-
tor. Fuel Process Technol 118:278–286
Curzons AD, Constable DJC, Mortimera DN, Cunning-
ham VL (2001) So you think your process is green,
how do you know?—Using principles of sustainability
to determine what is green–a corporate perspective.
Green Chem 3:1–6
M
Matrimid ® Membranes
Ahmad Fauzi Ismail1 and Juhana Jaafar2
1
Faculty of Petroleum and Renewable Energy
Engineering, Universiti Teknologi Malaysia,
Advanced Membrane Technology Research
Centre (AMTEC), Johor Bahru, Johor, Malaysia
2
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Advanced
Membrane Technology Research Centre
(AMTEC), Johor Bahru, Johor, Malaysia
Matrimid membrane can be developed from
different types of commercially available
polyimide resins such as Matrimid 5218
(3,30 ,4,40 -benzophenonetetracarboxylic
dianhydride and diaminophenylindane), Kapton,
Matrimid 5292A
(4,4-bismaleimidodiphenylmethane), Matrimid
5292B, Matrimid P84, and Matrimid 9725
(micropulverized version Matrimid 5218)
(www.ciba.com; www.huntsman.com). The
employment of commercially available
polyimide resin was found to be more practical
from the economic point of view due to the high
cost of synthesized polyimides on the laboratory
scale (Xiao et al. 2005).
The Matrimid membranes are commonly pre-
pared via solvent evaporation (Sridhar
et al. 2007; Mosleh et al. 2012) and phase inver-
sion (Basu et al. 2010) techniques. The asymmet-
ric (Nistor et al. 2008; Basu et al. 2010) or dense
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_349-6
(Shishatskiy et al. 2006) Matrimid membrane can
be in flat sheet (Shishatskiy et al. 2006; Aziz and
Ismail 2010) or hollow fiber (Dong et al. 2011;
Ding et al. 2008; Jiang et al. 2004) form.
Matrimid especially the Matrimid 5218, an
extremely popular polyimide, has been exten-
sively studied for gas separation, pervaporation
processes, and carbon membrane due to the com-
bination of relatively high gas permeability coef-
ficients and separation factors as well as excellent
mechanical properties, high solubility in
non-hazard organic solvents, and high glass tran-
sition temperature in comparison to polycarbon-
ate, polysulfone, and other materials (Wind 2002;
Nistor et al. 2008). The typical permeation prop-
erties of Matrimid 5218 are tabulated in Table 1.
The overall performance (in terms of perme-
ability and selectivity) of Matrimid membrane in
gas separation processes can be diverse as
reported in the open literatures which was due
to the several factors such as:
(i) Operating conditions of gas permeation test
(ii) Effective (skin layer) membrane thickness
(the thinner the selective skin layer is, the
better the gas flux will be)
(iii) Membrane morphology as a consequence of
the different conditions of phase inversions
of membrane preparation technique
(iv) Properties of the gas tested
The weakness of Matrimid membrane is
always pronounced by the membrane transport
2 Matrimid ® Membranes

Matrimid ® Membranes, Table 1 Typical permeation properties of Matrimid 5218 (David et al. 2011)
Permeability of pure gases (Barrera) Ideal selectivity
Po2 PN2 O2/N2
1.32–1.34b 0.185b 7.2b
1 Barrer = 1010 cm3 (STP) cm cm2 S1 cmHg1 = 7.5  1018 m3 (STP) m m2 S1 Pa1,
a

Pure gas Permeation measurement for O2 and N2 at 3447.3785 kPa, 25  C

b

O O
O
C C CH3
C
N N

C C n
H3C CH3
O O

Matrimid ® Membranes, Fig. 1 Chemical structure of Matrimid

properties that are strongly affected by the gas
separation operating conditions such as pressure
and temperature that are likely relied to the
changes in density, and consequently in the free
volume, of the polymer itself (Rowe et al. 2009;
David et al. 2011). Hence, the presence of minor
components in the feed flow, such as impurities
or water vapor, can strongly affect the gas trans-
port mechanism, thus altering the separation per-
formances (Chen et al. 2011). Moreover, its
glassy nature may lead to plasticization phenom-
ena at high fugacity of gases and vapors and to
aging phenomena that decrease the performances
upon time (Tin et al. 2003). These shortcomings
limit the Matrimid membrane application partic-
ularly in gas separation processes. Due to this
awareness, numbers of modification have been
reported by researchers to improve the Matrimid
membrane properties in order to fulfill the gas
separation performance requirement particularly
to surpass the Robeson boundary line (Basu
et al. 2010). The idea to modify the Matrimid
membrane was initiated by the good processabil-
ity of the polymer itself owing to its carbonyl
functional groups (see Fig. 1) that may lead to the
donation of electrons to form good interaction with
certain electron acceptors (Chung et al. 2003). The
modifications were conducted on the Matrimid
membrane including the incorporation of
mesoporous silica molecular sieve (Kenneth
et al. 2002), bromination (Guiver et al. 2002;
Xiao et al. 2005), blending with other polymers
(Chung et al. 2003), thermal treatment
(Krol et al. 2001), and chemical cross-linking
(Tin et al. 2003).
Due to the excellent properties shown by
Matrimid membrane, which is desirable for gas
separation process, therefore it is worth to accel-
erate relevant modifications on this promising
membrane for better separation performance.
References
Aziz F, Ismail AF (2010) Preparation and characterization
of cross-linked Matrimid ® membranes using para-
phenylenediamine for O2/N2 separation. Sep Purif
Technol 73:421–428
Basu S, Cano-Odena A, Vankelecom IFJ (2010) Asym-
metric Matrimid ®/[Cu3(BTC)2] mixed-matrix mem-
branes for gas separations. J Membr Sci 362:478–487
Chen QG, Scholes CA, Qiao GG, Kentish SE
(2011) Water vapor permeation in polyimide mem-
branes. J Membr Sci 379:479–487
Chung TS, Chan SS, Wang R, Lu Z, He C (2003)
Characterization of Permeability and Sorption in
Matrimid ® Membranes
Matrimid/C60 Mixed Matrix Membranes. J Membr
Sci 211:91–99
David OC, Gorri D, Urtiaga A, Ortiz I (2011) Mixed gas
separation study for the hydrogen recovery from H2/
CO/N2/CO2 post combustion mixtures using a
Matrimid membrane. J Membr Sci 378:359–368
Ding X, Cao Y, Zhao H, Wang L, Yuan (2008) Fabrication
of high performance Matrimid/polysulfone dual-layer
hollow fiber membranes for O2/N2 separation.
J Membr Sci 323:352–361
Dong G, Li H, Chen V (2011) Plasticization mechanisms
and effects of thermal annealing of Matrimid hollow
fiber membranes for CO2 removal. J Membr Sci
369:206–220
Guiver MD, Thi NL, Robertson GP (2002) Composite Gas
Separation Membranes. U S Patent 20020062737.
Jiang L, Chung TS, Li DF, Cao C, Kulprathipanj S (2004)
Fabrication of Matrimid/polyethersulfone dual-layer
hollow fiber membranes for gas separation. J Membr
Sci 240:91–103
Kenneth J, Balkus Jr, Cattanach K, Musselman IH,
Ferraris JP (2002) Selective matrimid membranes
containing mesoporous molecular sieves. MRS
Proc. doi:10.1557/PROC-752-AA4.3. Accessed 2011
Krol JJ, Boerrigter M, Koops GH (2001) Polyimide hol-
low fiber gas separation membranes: preparation and
the suppression of plasticization in propane/propylene
environments. J Membr Sci 184:275–286
Mosleh S, Khosravi T, Bakhtiari O, Mohammadi T (2012)
Zeolite filled polyimide membranes for dehydration of
3
isopropanol through pervaporation process. Chem Eng
Res Des 90:433–441
Nistor C, Shishatskiy S, Popa M, Nunes SP (2008) Com-
posite membranes with cross-linked matrimid selec-
tive layer for gas separation. Environ Eng Manag
J7:653–659
Rowe BR, Freeman BD, Paul DR (2009) Physical aging of
ultrathin glassy polymer films tracked by gas perme-
ability. Polymer 50:5565–5575
Shishatskiy S, Nistor C, Popa M, Nunes SP, Peinemann
KV (2006) Comparison of asymmetric and thin-film
composite membranes having Matrimid 5218 selec-
tive layer. Desalination 199:193–194
Sridhar S, Veerapur RS, Patil MB, Gudasi KB,
Aminabhavi TM (2007) Matrimid polyimide mem-
branes for the separation of carbon dioxide from meth-
ane. J Appl Polym Sci 106:1585–1594
Tin PS, Liu Y, Wang R, Liu SL, Pramoda KP
(2003) Effects of cross-linking modification on gas
separation performance of Matrimid membranes.
J Membr Sci 225:77–90
Wind JD (2002) Improving polyimide membrane resis-
tance to carbon dioxide plasticization in natural gas
separations. PhD Thesis, The University of Texas at
Austin
www.ciba.com
www.huntsman.com
Xiao Y, Dai Y, Chung T-S, Guiver MD (2005) Effects of
brominating matrimid polyimide on the physical and
gas transport properties of derived carbon membranes.
Macromolecules 38:10042–10049
M

Membrane Artificial Organs extracorporeal removal of waste products such

as creatinine and urea and free water from the
Loredana De Bartolo blood when the kidneys are in a state of renal
ITM-CNR, National Research Council of Italy, failure. It involves diffusion of small solutes
Rende, CS, Italy across the semipermeable membrane retaining
protein and molecules with high molecular
weight. Membranes used in the hemodialyzer
Synonyms device have been engineered in order to have
the similar structure of the renal glomerular
Artificial functional organ membrane to ensure a similar performance.
Membrane hollow fiber and glomerular capillary
Membrane artificial organs are membrane
employ a cylindrical cross section in order to
devices that replace the function of natural organs
minimize perimembrane boundary layers and to
like artificial kidneys/dialyzers and artificial
maximize transport efficiency, have same ratio of
lungs/blood oxygenators for the purpose of
wall thickness/cross-sectional diameter, and are
restoring the specific organic functions.
composed of linear hydrophilic polymers that
Polymeric semipermeable membranes and
rely on van der Waals forces and islands of crys-
membrane processes play a pivotal role in
tallinity to retain their integrity. Difference is
replacement therapy for acute and chronic organ
scale: the glomerule has a diameter of 4–8 mm,
failure and in the management of immunological
and synthetic hollow fiber membranes have
disease (De Bartolo and Drioli 1998).
diameters in the range of 200 mm. For example,
In these devices semipermeable membranes
the structure of polyethersulfone membrane that
act as selective barriers for the removal of endog-
is widely used in hemodialyzer is similar to glo-
enous and exogenous toxins from patient’s blood
merular membrane. Both have asymmetric struc-
(hemodialysis, hemofiltration, etc.) or for gas
ture with a selective skin layer supported by a
exchange with blood (blood oxygenation)
sponge layer (Fig. 1). This structure confers to the
(Kawakami 2008). Hemodialysis is an extracor-
membrane an optimal selectivity and high
poreal treatment of patients affected by kidney
mechanical resistance.
failure. The treatment is intermittent, generally
The first hollow fiber hemodialyzers made of
three times weekly for periods between 3 and 5 h
unmodified cellulose were used clinically in the
depending upon the patient clinical requirements.
1960s. Since the first cellulose membranes, sig-
In hemodialyzer, selective membranes play the
nificant efforts have been focused on the devel-
same function of kidneys allowing the
opment of more biocompatible and selective
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_351-4
2 Membrane Artificial Organs
Membrane Artificial Organs, Fig. 1 Comparison of hemodialysis polyethersulfone membrane (a) with glomerular
membrane (b)
membranes with respect to the clearance of “mid-
dle” molecules like b2-microglobulin that is
known to be associated with many dialysis-
related disorders. A variety of synthetic polymers
and modified cellulosic materials including
polysulfone (PSF), polyethersulfone (PES), poly-
amide (PA), polyacrylonitrile (PAN), cellulose
triacetate (CTA), and hemophan (HP) have been
used for preparing hemodialysis membranes
(Humes et al. 2006; Su et al. 2008).
Extracorporeal blood oxygenators are used to
oxygenate the blood during open-heart surgery.
Today, the vast majority of these blood oxygen-
ators use hydrophobic microporous hollow fiber
membranes to separate the blood and gas phases.
Oxygen diffuses from the gas phase through the
gas-filled membrane pores into the blood. Oxy-
gen in the blood plasma binds to hemoglobin
present in the red blood cells. Consequently the
rate of oxygen transfer is enhanced compared to
the oxygenation of water where the oxygen does
not react in the liquid phase (Lewandowski
2000).
Membrane oxygenators in current use utilize
microporous, silicon, or polypropylene mem-
branes. Currently, there are three principal types
of oxygenator: (a) Plaque oxygenators are built
with microporous membranes of expanded poly-
propylene, folded in a Z shape. In these appara-
tuses, blood and gas flow in opposite sides of the
membrane. (b) Spiral oxygenators utilized silicon
membranes that are rolled around a central axis.
(c) Hollow fiber oxygenators are manufactured
with microporous polypropylene membranes,
constituted by hollow fibers or capillary. This is
the most common type of oxygenator used
currently.
The most common membranes for blood oxy-
genator have been engineered in order to have
morphology close to the pulmonary alveoli. For
example oxygenator polypropylene membranes
have massive reticulated surfaces deployed as
fine, porous, open-cell foams, which remind the
saccular form of the alveoli and the very thin
alveoli septa (Fig. 2). In the natural lung, blood
flows through fine capillaries in the alveoli and
exchanges O2 and CO2 across a barrier made up
of capillary endothelial cells; in oxygenators
blood flows on the outside of a large bore fiber,
with diameter of 300 mm, and exchanges respira-
tory gases across a meniscus that forms across the
membrane pore at the interface of blood and gas.
The diffusion of these gases inside the oxy-
genator depends on the type of material of the
membrane and on its thickness and porosity, but
it is also influenced by the thickness of the layer
of blood in contact with the membrane and by the
characteristics of the blood flow
(Wickramasinghe et al. 2005).
Membrane Artificial Organs
Membrane Artificial Organs, Fig. 2 Comparison of oxygenator polypropylene membrane (a) with pulmonary alveoli (b)
References
De Bartolo L, Drioli E (1998) Membranes in artificial
organs. In: Haris PI, Chapman D (eds) Biomedical
and health research, vol 16, New Biomedical
Materials – Basic and Applied Studies. IOS Press,
Amsterdam, pp 167–181
Humes HD, Fissell WH, Tiranathanagul K (2006) The
future of hemodialysis membranes. Kidney Int
69:1115–1119
Kawakami H (2008) Polymeric membrane materials for
artificial organs. J Artif Organs 11:177–181
3
Lewandowski K (2000) Extracorporeal membrane oxy-
genation for severe acute respiratory failure. Crit
Care 4:156–168
Su BH, Fu P, Li Q, Tao Y, Li Z, Zao HS, Zhao CS (2008)
Evaluation of polyethersulfone highflux hemodialysis
membrane in vitro and in vivo. J Mater Sci Med
19(2):745–751
Wickramasinghe SR, Han B, Garcia JD, Specht R (2005)
Microporous membrane blood oxygenators. AIChE J
51:656–670
M
Membrane Bioartificial Organs
Loredana De Bartolo
National Research Council of Italy, Institute on
Membrane Technology, ITM-CNR, Rende (CS),
Italy
Membrane bioartificial organ is a membrane
device containing living cells, which is implanted
or integrated into a human to replace for short or
long term a natural organ. This device is realized
as alternative to organ transplantation or as
bridge for supporting patients until the organ
transplantation. Every year, many patients die
while waiting for an organ transplant. Organs
such as the liver, kidney, and lungs are often in
very high demand by patients with severe ill-
nesses. Historically, the number of available
organ donors has been insufficient to meet the
needs of every patient. For a traditional organ
transplant to succeed, the donor and patient
must be a close biological match. Even when a
replacement organ is available, the immune sys-
tem of the recipient may reject the transplant.
Membrane bioartificial organs have been
designed to solve this problem. Some examples
are represented by membrane bioartificial liver
for the treatment of acute and chronic liver dis-
ease, bioartificial pancreas as alternative
approach to exogenous insulin administration in
the case of insulin-dependent diabetes mellitus,
bioartificial kidney for people with poorly
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_355-3
functioning kidneys, and bioartificial lung for
the treatment of patients with end-stage lung dis-
ease. Membrane capsules containing dopamine-
secreting cells are also being explored for the
treatment of Parkinson’s disease, a progressive
brain disorder characterized by a deficiency of
the neurotransmitter dopamine.
Immunoprotective membrane cell transplants
are being investigated to treat other nervous sys-
tem disorders. Other membrane bioreactors are
used for the adoptive cell therapy for the treat-
ment of malignant diseases or viral infections in
the expansion of T lymphocytes (Jagur-
Grodzinski 2006).
Membrane bioartificial organs involve the
design, modification, growth, and maintenance
of living tissues embedded in natural or synthetic
scaffolds to enable them to perform complex
biochemical functions, including adaptive con-
trol and the replacement of normal living tissues.
In membrane bioartificial organs, cells are com-
partmentalized by means of semipermeable
membranes that permit the transport of nutrients
and metabolites to cells and the transport of
catabolites and specific metabolic products to
the blood (Drioli and De Bartolo 2006). The
membrane must avoid the contact between cells
and patient’s blood to prevent immunological
response and consequent rejection. Membranes
act also as means for cell oxygenation and in the
case of anchorage-dependent cells as substrata
for cell attachment and culture. In these systems,
cells come into contact with the membrane
2 Membrane Bioartificial Organs
surface. Therefore, the response of the cell behav-
ior depends on the surface properties of the used
membrane (Morelli et al. 2010). For this reason,
membranes should be chosen not only on the
basis of their separation properties but also on
the basis of physicochemical and morphological
surface properties. Membrane bioartificial organs
are engineered to be used as extracorporeal
devices or implantable systems. These devices
can be distinguished on the basis of membrane
material configuration, molecular weight cutoff
or pore size, and cell culture technique. Cells can
be compartmentalized in the lumen or shell of
hollow fiber membranes (HFMs) or between flat-
sheet membranes, in a network of HF mem-
branes, spirally wound module, encapsulated or
attached to microcarriers.
The most common membranes used in the
membrane bioartificial organs are hydrophilic
membranes with molecular weight cutoff ranging
from 20,000 to 120,000 daltons, which are chosen
on the basis of the molecules that have to provide
to the cells and removed from them. The creation
of a physiological environment requires the use
of membranes with specific physicochemical,
morphological, and transport properties on the
basis of the targeted tissue or organ (De Bartolo
et al. 2012).
References
De Bartolo L, Leindlein A, Hofmann D, Bader A, de
Grey A, Curcio E, Drioli E (2012) Bio-hybrid organs
and tissues for patient therapy: a future vision for 2030.
Chem Eng Process: Proc Intensif 51:79–87
Drioli E, De Bartolo L (2006) Membrane bioreactor for
cell tissues and organoids. Artif Organs
30(10):793–802
Jagur-Grodzinski J (2006) Polymer for tissue engineering,
medical devices and regenerative medicine. Concise
general review of recent studies Polym. Adv Technol
17:395–418
Morelli S, Salerno S, Piscioneri A, Campana C, Drioli E,
De Bartolo L (2010) Membrane bioreactors for regen-
erative medicine: an example of the bioartificial liver.
Asia Pac J Chem Eng 5(1):146–159
M
Membrane Biocompatibility
Loredana De Bartolo
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende(CS),
Italy
Synonyms
Biocompatibility of membranes
Membrane biocompatibility is the ability of
membrane to perform its intended function with-
out eliciting any host undesirable local or sys-
temic effects. Membrane biocompatibility is a
general term that must be subcategorized on the
basis of the membrane applications in order to be
able to make more narrow definitions. In the case
of membranes used in the hemodialyzers,
hemofilters, hemodiafilters, and blood oxygena-
tor, the more appropriate term is blood compati-
bility or hemocompatibility because of the main
interactions between membrane and blood. When
blood comes into contact with an artificial sur-
face, protein adsorption occurs in the first sec-
onds. Proteins like albumin, immunoglobulin G,
fibrinogen, fibronectin, factor XII, and high
molecular weight kininogen are adsorbed
forming a layer that supports the platelet adher-
ence. The adsorption of thrombin may activate
the clotting cascade (Ulhenbusch et al. 2004).
The protein adsorption process is strongly
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_356-3
dependent on the physicochemical (e.g., surface
charge, functional groups) and morphological
(e.g., porosity, roughness) surface properties of
the membranes (De Bartolo et al. 2004). On the
other hand, the artificial surface may activate the
complement cascade through the membrane-
bound complement factors such as C3b and
iC3b. After the protein adhesion, platelet changes
their morphology, release factors, and aggregate.
The adsorbed proteins activate also the coagula-
tion cascade with the fibrin and thrombus forma-
tion, which occur within several minutes. The
coagulation pathway consists of a series of reac-
tions, each requiring the formation of a surface-
bound enzyme complex. In these reactions, inac-
tive precursor proteins are transformed into
active protease.
Several studies indicated that platelet activa-
tion increases in the positively charged mem-
brane and decreases in the membrane having a
microdomain structure in which hydrophilic and
hydrophobic groups coexist randomly as mole-
cules. Also, the complement activation, which in
the case of biomaterials proceeds via alternative
pathway, is mainly noted with cellulose mem-
branes; free hydroxyl groups on the membrane
surface are bonded with C3b and further with
factor B that promotes the activation. Improve-
ments of biocompatibility of cellulose membrane
can be obtained by surface modification devoted
to graft, for example, alkyl group to the hydroxyl
group.
2 Membrane Biocompatibility
When membranes are used in bioartificial sys-
tems (bioartificial organs and tissues), it is impor-
tant to consider the cytocompatibility of
membrane on which depends the response of the
biological components. In bioartificial systems,
cells come into contact with the membrane sur-
face. Therefore, their morphological and func-
tional response depends on the surface and
transport membrane properties. Physicochemical
properties, including surface composition,
charge, energy, and morphology, may affect cell
adhesion and behavior. In vivo cells are
surrounded by the extracellular matrix (ECM)
that provides physical architecture and mechani-
cal strength to the tissue. The native ECM
exhibits from macro- to nanoscale patterns of
chemistry and topography. For this reason, the
cells can respond to various chemically and/or
topographically patterned features. When cells
are cultured in vitro, they receive very different
physical, chemical, and mechanical stimuli from
the unfamiliar surrounding environment. Micro-
and nanoscale mechanical properties of the mem-
branes are critical because the cells not only
adhere to the surface but also pull on the surface
substrate and on adjacent cells. The surface
chemistry of the membrane affects the adhesion
of cells through the ECM protein adsorption and
stereospecific chemical interactions. Several
approaches have been undertaken to improve
the cytocompatibility of membranes by increas-
ing the wettability or by surface modification
through grafting of functional groups or immobi-
lization of peptides, and proteins, which interact
with the cell receptors (De Bartolo et al. 2005,
2006, Salerno et al. 2009). It is known that the
cytocompatibility of the membrane can be
increased by modulating its surface free energy
and roughness (De Bartolo et al. 2002). It has
been shown a significant enhancement of the
hepatocyte adhesion and metabolic functions on
membrane with high value of surface free energy
base parameters.
References
De Bartolo L, Morelli S, Bader A, Drioli E (2002) Eval-
uation of cell behaviour related to physico-chemical
properties of polymeric membranes to be used in
bioartificial organs. Biomaterials 23(12):2485–2497
De Bartolo L, Gugliuzza A, Morelli S, Cirillo B,
Gordano A, Drioli E (2004) Novel PEEK-WC mem-
branes with low plasma protein affinity related to sur-
face free energy parameters. J Mater Sci Mater Med
15:877–883
De Bartolo L, Morelli S, Lopez L, Giorno L, Campana C,
Salerno S, Rende M, Favia P, Detomaso L, Gristina R,
d’Agostino R, Drioli E (2005) Biotransformation and
liver specific functions of human hepatocytes in cul-
ture on RGD-immobilised plasma-processed mem-
branes. Biomaterials 26(21):4432–4441
De Bartolo L, Morelli S, Rende M, Salerno S, Giorno L,
Lopez LC, Favia P, d’Agostino R, Drioli E (2006)
Galactose derivative immobilized glow discharge
processed PES membranes maintain the metabolic
activity of human and pig liver cells. J Nanosci
Nanotechnol 6:2344–2353
Salerno S, Piscioneri A, Laera S, Morelli S, Favia P,
Bader A, Drioli E, De Bartolo L (2009) Improved
functions of human hepatocytes on NH3
Plasma–grafted PEEK-WC-PU membranes. Biomate-
rials 30:4348–4356
Ulhenbusch I, Bonnie-Schorn E, Grassmann A, Vienken
J (2004) Understanding membranes and dialysers.
Pabst Science Publishers, Lengerich
S
Solubility
Maria Grazia De Angelis
Dipartimento di Ingegneria Civile, Chimica,
Ambientale e dei Materiali, Università di
Bologna, Bologna, Italy
Solubility (C) is a thermodynamic quantity char-
acterizing the distribution of chemical species
between different phases in equilibrium. In par-
ticular, the solubility (of a solute in a solvent)
expresses the amount of chemical species
(solute), dissolved in a fixed amount of an
uptaking species (solvent), at equilibrium. The
equilibrium is reached at the end of a sorption
(or absorption) process, in which the solute mol-
ecules spontaneously move from the original
phase to the solvent phase and form a homoge-
nous mixture (solution) of molecules interacting
with noncovalent bonds. Often the term “solubil-
ity” is also used to indicate the sorption process.
The solubility value is measured when the
solute net mass transfer is zero and an equal
chemical potential of the solute species in the
two phases is attained. The time required to
reach such equilibrium state depends on the dif-
fusivity of the solute in the solvent in the state of
the solution, on the geometry of the system, and
the boundary and initial conditions of the mass
transfer problem. The solubility of a solute in a
solvent depends on the respective chemical
nature and thermodynamic state but also on
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_357-1
binary interactions and can be obtained by solv-
ing the phase equilibrium problem, with an
appropriate model that allows to represent the
chemical potential.
The solubility is thus a measure of solute con-
centration at equilibrium and can be expressed in
mass, molar, or volume terms and using different
units as reported in Table 1.
In membrane processes governed by the
solution-diffusion framework like gas and vapor
separation, pervaporation, and liquid/liquid
separation, the membrane is the solvent in equi-
librium with the feed and permeate fluid phases
on the upstream and downstream side, respec-
tively. The concentration of solute i absorbed
onto the membrane boundaries is equal to
Ci,up and Ci,down, respectively. The difference
DCi ¼ Ci, up  Ci, down ensures solute mass flux
across the membrane, according to Fick’s law.
Solubility can be measured via gravimetric,
manometric, optical methods, etc. (Czichos
et al. 2006) and is usually expressed through
curves (solubility isotherms) reporting
isothermal data.
According to the phase rule, in the system
formed by two phases (the original solute phase
and the solvent phase), one solvent and NS solute
species, the number of variables required to
univocally define the state of the system is NS+1.
The solubility isotherm of a solute i in a sol-
vent reports the solubility of that solute in the
solvent versus the composition of the solute in
2 Solubility

Solubility, Table 1 Units used for solubility C of fluids vapor/liquid saturation point of the pure solute at
in membranes. 1 solute, 2 solvent the same temperature:
g1/g2
g1/cm3a
2
mol1/mol2
f i ðT, p, yi Þ low pyi
mol1/g2 ai ¼
! (1)
f 0i T, pi, SAT ðT Þ pressure pi, SAT ðT Þ
mol1/cm3a
2
cm31(STP)/cm32
STP standard temperature and pressure, 1 atm and 25  C, For pure liquid solute phases, the solubility, as
1 cm3(STP) = 4.461 105 mol many other liquid-state properties, is to all prac-
a
Usually cm3 of pure solvent tical purposes a weak function of pressure, and its
value can be assumed unique at a fixed
temperature.
For multicomponent liquid solute phases, the
the original solute phase, which can be expressed activity ai can be used, being gi the activity
with different quantities depending on the state of coefficient:
aggregation of such phase. Some examples are
given below.
ideal mixture
For a gaseous solute phase, the fugacity fi or ai ¼ x i g i  xi (2)
the partial pressure pi, if the gas phase is ideal,
is used. References
For a vapor solute phase, the activity (ai) is
preferentially used, i.e., the ratio between the Czichos H, Saito T, Smith L (2006) Experimental
measurement of gas and vapor sorption. In: Springer
fugacity in the current state and the fugacity in a
handbook of materials measurement methods.
reference state, that is usually chosen to be the Springer, Berlin, pp 381–385
M
Membrane Biosorption
A. B. Koltuniewicz
Biotechnology and Bioprocess Engineering
Division, Faculty of Chemical and Process
Engineering, Warsaw University of Technology,
Warsaw, Poland
Biosorption, in the biological sense, is the ability
of cells (usually microorganisms) to bind various
substances in a passive way. Bioaccumulation of
cells is the active retrieval from the environment
of certain components needed for life (i.e., metab-
olism). Biosorption can be achieved through a
variety of specific mechanisms, where physical
adsorption, ion exchange, and chemical reactions
play a dominant role. Table 1 (below) shows the
sorption capacity of various microorganisms such
as bacteria, fungi, and algae.
Biosorption is also a new separation process
(Volesky 1990) which depends on the concentra-
tion, temperature, pH, and sorbent properties that
determine the equilibrium and kinetics. Cell
debris may be also regarded as sorbents, which
have even better sorption properties than whole
cells because of greater sorption capacity (see
Table 1) and rate of sorption (see Table 2). The
smaller the particle size, the greater the surface
areas and shorter diffusion paths for the molecules
of xenobiotic (Koltuniewicz and Bezak 2002;
Koltuniewicz and Witek 2004). Due to the special
ability to bind heavy metals, biosorption process
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_358-7
is currently used mainly in metalworking opera-
tions such as processing of ores, the production of
batteries, power, thermal, and nuclear power gen-
eration, and some industrial wastewater treatment
systems (Koltuniewicz and Drioli 2008;
Koltuniewicz 2010). General examples of appli-
cations of biosorption are (I) removal of harmful
substances from the environment and
(II) separation of valuable substances from
multicomponent mixtures. In the first case, the
desired feature and the main value of biosorption
are its low cost and widespread availability of
biosorbents. Dealing with large amounts of con-
taminated water, which must be processed and,
moreover, contains rather diluted substances to
remove, such as heavy metals, organic substances
or radioactive materials, is the biggest challenge
for process engineering. In these cases, almost all
methods of separation fail because their costs are
rising dramatically. Therefore, the use of cheap
biosorbents, which are often waste materials
(algae, fungi, bacteria, sawdust, bark, etc.), may
be helpful, especially for environmental
protection.
In the second case (II), selective and specific
sorbents with a high affinity for precious sub-
stances are sought. This method can also be useful
to concentrate the atoms of noble metals such as
gold, platinum and uranium, from industrial waste
water, or even diluted in sea water.
In both cases, the use of membrane-assisted
biosorption, namely, the “membrane
biosorption,” may be recommended
2 Membrane Biosorption

Membrane Biosorption, Table 1 Maximum uptake of heavy metals on various microorganisms

Maximum uptake
Type of biosorbent (microorganisms) Heavy metal q
(mg metal/g biomass)
Bacillus subtilis bacteria Au 79
Bacillus licheniformis bacteria Fe 45
Aureobasidium pullulans bacteria Pb 220–360
Citrobacter sp bacteria U 800
Sargassum natans algae Au 400
Chlorella vulgaris algae Au 80
Sargassum natans algae Au 400
Chondrus crispus algae Au 76
Ascophyllum nodosum algae Cd 215
Rhizopus arrhizus fungus Ag 54
Rhizopus arrhizus fungus Au 164
Streptomyces noursei fungus Ag 38
Saccharomyces cerevisiae fungus Ag 5
Saccharomyces cerevisiae fungus Cd 20–40
Aspergillus niger fungus Au 176
Penicillium chrysogenum fungus Cd 56

Membrane Biosorption, Table 2 The isotherms of biosorption equilibrium (Pagnanelli et al. 2003)
Isotherm Equation
Langmuir q ¼ qmax  1þbC
bC

1
Freundlich q ¼ k  Cn
1
Langmuir–Freundlich q ¼ qmax  bCn
1
1þbCn
1 1 1
Radke and Prausnitz q ¼ aC þ bCn

Reddlich–Peterson q ¼ 1þbC
aC
n

(Koltuniewicz and Bezak 2002). The membranes next part shows the equations needed to calculate
allow for easy concentration of finely ground the membrane biosorption process.
biosorbents (Fig. 1) or cells (Fig. 2), which is
impossible in the thick layer of packed columns.
Very fine grinding is desirable because of the
Calculations of Membrane Biosorption
possibility of increasing the surface of sorption
Process
and shortening of the diffusion paths to active
sites. This increases the efficiency of sorption,
The obvious drawback of membrane biosorption
even in dilute suspensions. However, the costs of
is the quick saturation of the thin layer of
milling and additional operations such as drying,
biosorbent on membrane surface is rapidly
sorting, etc. should always be taken into account.
progressing with time, until equilibrium is
So in order to make real use of biosorption, the
reached. The equations describing the equilibrium
calculations must be performed in any case. The
and kinetics for biosorption process can be
Membrane Biosorption 3

Membrane Biosorption, a
Fig. 1 Equilibrium
adsorption of copper ions to
the pine sawdust (a). Effect
of temperature (b) and pH
(C). (A) Photomicrograph
of pine sawdust used for the
biosorption of copper ions.
(B) Effect of temperature on
biosorption of copper ions
on the sawdust. (C) Effect
of pH on biosorption of
copper ions on the sawdust

b 24
22
20
18
16
14
q [mg/g]

12
10
8
6
4 T = 20
T = 30
2 T = 40

0
0 20 40 60 80 100
C [mg/I]

c 24

22

20

18

16

14
q [mg/g]

12

10

4 pH = 5.0
pH = 4.0
2 pH = 3.0

0
0 20 40 60 80 100
C [mg/I]
4 Membrane Biosorption
Membrane Biosorption, Fig. 2 Microorganisms on the
membrane surface
Membrane Biosorption, Table 3 Kinetic equation of the biosorption (Pagnanelli et al. 2003)
Reaction type
First-order reaction
Pseudo-second order reaction
Membrane Biosorption, Table 4 Experimentally determined constants m and n in correlation between rate of surface
renewal and average cross-flow velocity in different types of modules (Koltuniewicz 1995)
Module type
Plate and frame (slot 0.15  0.001 m)
Tubular ceramic (Membralox ® 19 tubes)
Capillary (Romicon ®, d = 1 mm)
determined on the basis of experimental data (see
Tables 1, 2, 3, and 4 in Fig. 1).
The concentration in the biosorbent (q)
varies with time, due to its saturation with solute
(i.e., xenobiotic), which can be expressed in the
formula:
qðtÞ ¼ q
 ðq0  q
Þ  ekt
Where:
q(t) [kgsolute/kgbiosorbent] – solute (xenobiotic)
concentration in the biosorbent
q* – equilibrium value of solute concentration in
the biosorbent (maximum uptake see Table 1)
q0 – initial solute concentration in the biosorbent,
e.g., solute concentration in the sorbent which
is supplied with the feed
During dead-end mode of operation, when the
unaffected biosorbent lies on the membrane sur-
face, and the liquid passes through its layer, the
concentration in the fluid changes according to
equilibrium. Change of concentration over time
in the permeate stream can be then calculated from
the mass balance (see Fig. 3) (Koltuniewicz and
Bezak 2002; Koltuniewicz and Witek 2004). The
balance of xenobiotic in an open system, during
the flow of fluid through a layer of biosorbent,
Equation


qðtÞ ¼ q
 1  ekt
1
q ð tÞ ¼ 1
þt
kq
q

Constant – m Constant – n
0.00074 0.75
0.0020 0.80
0.0035 0.66
permeates flow results in a superposition of two
effects: (1) the tendency to reduce the concentra-
tion of xenobiotic in the permeate due to its
biosorption and (2) the tendency to increase the
concentration as a result of inflow of xenobiotic,
with the liquid. Thus, the relationship has a min-
imum of the xenobiotic concentration in the per-
meate after biosorption:
Membrane Biosorption 5

CP ðtÞ ¼ CR Methods to reduce the concentration polarization

k  Xm  d  ðq
 qR Þ h kt i layer are well known in the membrane processes
 e  e  dt
J

Jkd
Where:
CP(t) – instantaneous concentration of solute in
the permeate
CR [kgsolute/m3retentate] – constant concentration of
solute in the retentate inflow,
Xm [kgbiomass/m3retentate] – average biomass con-
centration on the membrane surface
d [m] – thickness of the sorbent layer on the
membrane
k [s1] – biosorption kinetic constant
qR [kgsolute/kgbiomass] – solute concentration in the
sorbent in the retentate
q* – maximum uptake, i.e., equilibrium value of
the solute concentration in the sorbent
J [m3/m2s] – permeate flux
t [s] – real time of the process
It should be underlined that sorption process in
dead-end mode is unpractical because of very
small volume of active biosorbent layer at the
membrane surface. Therefore, to maintain station-
ary conditions of the process, some way to remove
the thin active layer of sorbent from the membrane
surface after appropriate process time must be
found. Duration, after which the concentration of
solute in the permeate is the minimum, may be
selected as a time of the periodic back flushing
and can be calculated from the formula:
 
kd
ln

min  J
t CP ¼
J
k
d
to maximize the permeate flux. They are turbu-
lences or shear forces, shear-induced diffusion,
lifting forces, pinch effects, lateral migrations,
scouring effects, gas sparging, etc. We can now
apply them for controlled renewal of a biosorbent
film from the surface of the membrane by using
hydrodynamic effects during cross flow. Applica-
tion of Danckwerts model allows to determine the
optimal rate of surface renewal (Koltuniewicz and
Witek 2004).
rffiffiffiffiffiffiffiffiffiffi
kJ dCm
sopt ¼ for Cmin
P when
P
¼0
d ds
The optimal conditions for renewing the surface
we get when the lowest concentration of the xeno-
biotic in the permeate (i.e., the highest possible
purity) of cross-flow conditions can be achieved.
This is when the frequency of renewal of the
sorbent film(s) is synchronized with the (i) flow
of permeate “J,” (ii) thickness of the sorbent layer
on the membrane “d,” and (iii) the kinetics of
sorption “k” (see Fig. 1). Then the average con-
centration in the permeate outflow from the entire
surface of the membrane (i.e., the sum of the
concentrations in the streams flowing from all of
its components) can be expressed by the formula
(see also Fig. 3 at continuous line):

2 3
ðkþsÞtp ðdJ þsÞtp

61  e 1e 7 k  X m  d  ð q  qR Þ s
P ¼ CR  4
Cm  5 
kþs J Jkd 1  estp
þs
d
6 Membrane Biosorption

1,50E–04

CONCENTRATION OF THE SOLUTE IN THE

PERMEATE [mM/ml]

dead-end
cross-flow with optimum surface renewal

0,00E+00
0 100 200 300
TIME [S]

Membrane Biosorption, Fig. 3 Purity of permeate after the process of membrane biosorption in dead-end and cross-
flow modes of operation

After the long duration of process, this concentra- References

tion becomes constant, leveling off on the asymp-
totic value independent on time of the process tp Koltuniewicz AB (1992) Predicting permeate flux in ultra-
filtration on the basis of surface renewal concept.
(see Fig. 1 dashed line).
J Membr Sci 68:107–118
Koltuniewicz AB (1995) Yield of the pressure-driven

kds membrane processes in the light of the surface renewal
P ¼ C R  X m  ð q  qR Þ 
Cm
ð J þ s  dÞ  ð k þ s Þ theory. Oficyna Wydawnicza PWr, Wroclaw (in Polish)
Koltuniewicz AB (2010) Integrated membrane operations
in various industrial sectors. In: Drioli E, Giorno
The rate of the surface renewal depends on many L (eds) Comprehensive membrane science and engi-
hydrodynamic parameters and must be deter- neering, 1st edn. Elsevier, Oxford
mined experimentally. However, rough estimates Koltuniewicz AB, Bezak K (2002) Engineering of mem-
brane biosorption. Desalination 144:219–226
assuming close to the water systems can use a Koltuniewicz AB, Drioli E (2008) Membranes in clean
simple exponential dependence on average veloc- technologies-theory and practice. Wiley&KGaA,
ity retentate at different membrane modules, Weinheim
which were presented in Koltuniewicz (1992). Koltuniewicz AB, Witek A (2004) Efficiency of
membrane-sorption integrated processes. J Membr Sci
239:129–141
s ¼ m  un Pagnanelli F, Beolchini F, Biase A, Di Veglio V (2003)
Effect of equilibrium models in the simulation of heavy
All the above data and formulas can be very metals biosorption in single and two-stage UF/MF
membrane reactor systems. Biochem Eng J 15:27–35
helpful in practical use of opportunities and poten-
Volesky B (1990) Biosorption of heavy metals. Ann Arbor,
tial of membrane biosorption as a new separation Boston
process.
M
Membrane Capacitive Deionization
Maarten Biesheuvel
Wetsus, European Centre for Excellence for
Sustainable Water Technology, Leeuwarden,
Netherlands
Membrane capacitive deionization, MCDI, is a
technology for water desalination based on the
use of an assembly of a spacer channel, two ion
exchange membranes, and two porous carbon
electrodes. Of the two electrodes, one is the cath-
ode, in which cations are adsorbed during desali-
nation, and the other is the anode. In front of the
cathode, a cation exchange membrane is placed,
while an anion exchange membrane is placed in
front of the anode. MCDI is a cyclic process, in
which for some time freshwater is produced,
followed by a period in which a concentrate
stream leaves the device. To increase water
recovery, the second period (ion release) must
be short relative to the first period (ion
adsorption).
In MCDI, upon transferring electrical charge
from cathode to anode, against a cell voltage
difference opposing this electrical charge trans-
fer, the ions are removed from the water flowing
through the spacer channel and are adsorbed in
their counter electrode. In this way water is
obtained which is desalinated to a certain degree.
After some time, the electrodes have reached
their adsorption capacity, and the electrical
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_359-5
current is reversed, thereby releasing the ions
from the electrodes, leading to a stream of brine
(concentrate) flowing from the device.
As each layer in the assembly is about
100–300 mm of thickness, a complete cell, includ-
ing also “graphoil” current collectors on either
side, is about 1.0–2.0 mm of total thickness.
Thus, in a “stack” of 10 cm of height, it is possible
to pack up to 100 of such cells. The current
collectors serve to inject the electrical current
from the external circuit into the porous elec-
trodes, which are accessible for the water and
the ions. Ion storage is based on the formation
of electrostatic double layers within the
nanopores in the carbon electrode particles,
where electrical charge is locally charged com-
pensated by counterions.
The advantage of MCDI over the related tech-
nology without membranes, CDI, is that during
the charging or desalination step, co-ions (ions of
the same charge sign as the electrode) are blocked
from leaving the electrode region. This effect
does occur in CDI and limits the charge effi-
ciency, i.e., the amount of salt molecules
removed from the water per amount of charge
transferred. A second advantage of MCDI is
that upon reversing the voltage during cell dis-
charge, it is possible in MCDI to completely
remove all counterions from their electrode,
thereby increasing the desalination capacity in a
next cycle.
M
Membrane Contactor (MC)
A. Criscuoli
Institute on Membrane Technology (ITM-CNR),
Rende (CS), Italy
Membrane contactors are membrane-based
devices that are used to carry out many unit
operations like gas-liquid mass transfers, liquid-
liquid extractions, and distillation (Drioli
et al. 2006). The membranes employed can be
both hydrophobic and hydrophilic and their pore
size usually ranges from 0.05 to 1 mm. The role of
the membrane is to put in contact the involved
phases, and the separation is not due to its selec-
tivity, as in the other membrane operations, but
the mass transport occurs at the interface, where
the two phases are in contact. In particular,
hydrophobic membranes are able to block at
their surface polar phases, whereas hydrophilic
membranes prevent the passage of nonpolar ones
(Fig. 1a, b).
Being each micropore a point of contact for
the phases, and being the number of micropores
in one membrane extremely high, one of the main
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_360-2
advantages of this system, with respect to con-
ventional operations, is the high interfacial area
available in small volumes. Furthermore, the pos-
sibility of having the interface established at each
micropore results in a more stable and better
contact between phases. However, for ensuring
that no mixing of phases occurs, it is mandatory
to do not exceed the so-called breakthrough pres-
sure, that is, the value of pressure at which the
phase blocked at the pore mouths starts to pene-
trate inside the pores. The value of the break-
through pressure depends on different
parameters, like the membrane pore size, the
degree of hydrophobicity of the membrane sur-
face, and the fluid properties and can be calcu-
lated by Laplace’s equation:
DP ¼ ð2scosyÞ=r
with s, surface tension of liquid; y, contact angle
between the liquid and the membrane; and r,
membrane pore radius.
Different are the membrane operations that
belong to the “membrane contactors family”
like membrane strippers and scrubbers, supported
liquid membranes, phase transfer catalysis, and
membrane and osmotic distillation.
2 Membrane Contactor (MC)

Membrane Contactor a b
(MC), Fig. 1 Interface in a
hydrophobic (a) and
hydrophilic (b) membrane
contactor and transport of
the species i through the i i
membrane micropore

Polar phase Apolar phase Polar phase Apolar phase

Membrane Contactor (MC), Table 1 Main advantages and drawbacks of membrane contactors
Main advantages Main drawbacks
High compactness Membrane resistance to the mass transport
Known and stable interfacial area Membrane fouling and loss of membrane properties (like
hydrophobicity)
No need of units downstream for phases Operating pressures dependent on the breakthrough pressure value
separation
Flexibility and modularity

Table 1 summarizes the main advantages and References

drawbacks of membrane contactors.
Drioli E, Criscuoli A, Curcio E (2006) Membrane
contactors: fundamentals, applications and potentiali-
ties. Membrane science and technology series 11,
ISBN:0-444-52203-4 Elsevier, Amsterdam
M
Membrane Distillation (MD)
Francesca Macedonio
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, University
of Calabria, Renede (CS), Italy
Membrane distillation (MD) is a thermal mem-
brane operation known for more than 50 years
(first patent was filed by Bodell on 3 June 1963
(Findley 1967); first MD paper was published
4 years later by Findley (Bodell 1963)). During
the last years, the number of papers published on
MD and the research groups focusing on MD
studies have been increasing (Fig. 1).
MD has great potential as a concentration pro-
cess at low temperature and energy with respect
to conventional processes, such as distillation and
reverse osmosis (RO). MD allows the separation
of volatile components from solutions. If the
solutions contain nonvolatile components, it is
possible to remove solvent by concentrating the
solutions.
In MD, one side (feed side) of a hydrophobic
membrane is brought into contact with a heated,
aqueous feed solution. The hydrophobic nature of
the membrane prevents penetration of the aque-
ous solution into the pores, resulting in a
vapor–liquid interface at each pore entrance.
Here, volatile compounds evaporate, diffuse
and/or convect across the pores, and are con-
densed on the opposite side (permeate) of the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_361-2
system (Fig. 2). The driving force of the process
is linked to the vapor-pressure gradient between
the two membrane sides.
The documented and expected benefits
resulting from MD are as follows:
– The nature of the driving force and the hydro-
repellent character of the membrane allow the
theoretically complete rejection of nonvolatile
components such as macromolecules, colloi-
dal species, and ions.
– Lower temperatures with respect to those usu-
ally used in conventional distillation column
are sufficient to establish interesting trans-
membrane flux, with consequent reduction of
energy costs, thus allowing the efficient recy-
cle of low-grade waste heat streams as well as
the use of alternative energy sources (solar,
wind, or geothermal).
– Lower pressures with respect to those usually
utilized in RO because the required operating
pressures are of the order of few hundred kPa.
Lower operating pressure translates to lower
equipment costs, increased process safety, and
possibility of using plastic equipment, thus
reducing or avoiding erosion problems.
– If compared to RO process, MD permeate flux
is only slightly affected by the concentration
of the feedwater, and thus, productivity and
performance remain roughly the same for high
concentration feedwaters. This means that
MD can be preferentially employed whenever
elevated permeate recovery factors or high
2 Membrane Distillation (MD)

25
Number of article on MD published in Journal

20
of membrane Science

15

10

0
1987

1989

1991

1993

1995

1997

1999

2001

2003

2005

2007

2009

2011
Year

Membrane Distillation (MD), Fig. 1 Number of the papers published in Journal of Membrane Science on MD field
each year up to September 2011 (Drioli et al. 2012)

Membrane Distillation
(MD), Fig. 2 General
scheme of the MD process:
aqueous solution on feed
side whereas four different
solutions can be realized on
permeate side (aqueous
solution or air gap or
vacuum or sweeping gas)
(Lawson and Lloyd 1997)

retentate concentrations are requested. On the distinguish between solution components on

contrary, in MD temperature polarization, a chemical basis, do not act as a sieve, and do
similar to concentration polarization, arises not react electrochemically with the solution;
from heat transfer through the membrane and they can be fabricated from almost any chem-
it is often the rate-limiting step for mass ically resistant polymers with hydrophobic
transfer. intrinsic properties, such as polytetrafluor-
– Since MD membranes act merely as a support oethylene (PTFE), polypropylene (PP), and
for a vapor–liquid interface, they do not polyvinylidene difluoride (PVDF). This
Membrane Distillation (MD)
Membrane Distillation
(MD), Fig. 3 Heat transfer
resistances in MD
1/hf
Tf
characteristic increases membrane life. New
amorphous perfluoro polymers (e.g., Hyflon,
Teflon) can be also utilized neglecting their
still high costs. On the other hand, MD perfor-
mance (in particular the transmembrane flux
and the heat loss by conduction through the
membrane) is intrinsically affected by the
structure of the membrane in terms of thick-
ness, porosity, mean pore size, pore distribu-
tion, and geometry.
– Membrane fouling is less problematic in MD
than in other membrane separations because
(i) the pores are relatively large compared to
RO/UF pores; (ii) the process liquid cannot
wet the membrane – therefore, fouling layers
can be deposited only on the membrane sur-
face but not in the membrane pores; and (iii)
due to the low operating pressure of the pro-
cess, the deposition of aggregates on the mem-
brane surface would be less compact and only
slightly affect the transport resistance.
– On the contrary, one problem that can arise in
MD is the membrane wetting which occurs
when the liquid penetrates into the membrane
pores. Once a pore has been penetrated, it is
said to be “wetted” and the membrane must be
completely dried and cleaned before the wet-
ted pores can once again support a
vapor–liquid interface.
3
1/hms
1/hmg
1/hp
1/hV
Tfm Tpm Tp
In MD process both heat and mass transfer
phenomena occur through the membrane. Fig-
ure 3 illustrates the possible heat transfer resis-
tances in MD with an electrical analogy.
Heat is first transferred from the heated feed
solution of uniform temperature Tf, across the
thermal boundary layer to the membrane surface
at a rate Q = hf ∙ DTf. At the surface of the
membrane, liquid is vaporized and heat is trans-
ferred across the membrane at a rate QV = hV ∙
DTm = N ∙ DHV (where N is the rate of mass
transfer and DHV is the heat of vaporization).
Additionally, heat is conducted through the mem-
brane material and the vapor that fills the pores at
a rate Qm = hm ∙ DTm where
hm ¼ e  hmg þ ð1  eÞhms (e is the membrane
porosity; hmg and hms represent the heat transfer
coefficients of the vapor within the membrane
pores and the solid membrane material, respec-
tively). Conduction is considered a heat loss
mechanism because no corresponding mass
transfer takes place. Total heat transfer across
the membrane is Q = QV + Qm. Finally, as
vapor condenses at the vapor–liquid interface,
heat is removed from the cold-side membrane
surface through the thermal boundary layer at a
rate Q = hp ∙ DTp.
The overall heat transfer coefficient of the MD
process is given by
4 Membrane Distillation (MD)

1 1 1 1 In literature, the recommended range of TPC

¼ þ þ
U hf hm þ hv hp is from 0.4 to 0.7 for well-designed systems
1 (Lawson and Lloyd 1997).
¼ The boundary layer heat transfer coefficients
hf
are almost always estimated from empirical cor-
1
þ

 relations such as the following:
Kg  e þ Km ð1  eÞ N  DHV
þ
d Tfm  Tpm • Sieder–Tate correlation for turbulent liquid
1 flow inside circular tubes
þ
hp
(1) Nu  KT
h¼ , Nu ¼ 0, 023  Re0, 8  Pr1=3 
d
0, 8
1=3
where each h and each T represent the
0, 14 hd dG cp m
corresponding heat transfer coefficients and tem- fm or T ¼ 0, 023   
K m KT
peratures shown in Fig. 3.  0:14
m
The total heat transferred across the mem- mw
brane is given by (4)

Q ¼ U  DT (2) where d is the tube diameter, KT is the thermal

Equation 1 illustrates the importance of minimiz-
ing the boundary layer resistances (maximizing
the boundary layer heat transfer coefficients).
A commonly used measure of the magnitudes of
the boundary layer resistances relative to the total
heat transfer resistance of the system is given by
the temperature polarization coefficient (TPC):
Tfm  Tpm
TPC ¼ (3)
Tf  Tp
• If TPC ! 1, the MD system is well designed,
and it is limited by mass transfer.
• If TPC ! 0f , the MD system is poorly
designed and it is limited by heat transfer
through the boundary layers.
conductivity of the liquid, G is the mass velocity
equal to w/S = <rv>, m is the bulk liquid vis-
cosity, mw is the liquid viscosity at the wall, cp is
the liquid heat capacity, and fm is the heating/
cooling correction factor.
Equation 4 should be used for Re > 6000 and
for tubes with large ratios L/d (where L is the tube
length). For short tubes (L/d < 50), several cor-
rections are available,
 d 0, 7 including
h
¼ þ
h1 1 L where h1 is the heat transfer
coefficient given by Eq. 4.
For the case of a noncircular flow channel,
these correlations can still be used if the equiva-
lent diameter de of the flow channel is substituted:

S across  sectional area of the flow channel

de ¼ 4  rH ¼ 4  ¼4 ðrH ¼ hydraulic radiusÞ
LP lenght of the wetted perimeter of the flow channel
Membrane Distillation (MD) 5

Membrane Distillation
(MD), Fig. 4 Mass transfer
resistances in MD

viscous

1/hf Knudsen molecular 1/hp

surface

• Sarti correlation for laminar liquid flow in The resistances shown in Fig. 4 are arranged as
circular tubes with constant wall temperature: described by the dusty gas model (DGM), which
is a general model for mass transport in porous
media.
0:067  Gz
Nu ¼ 3:66 þ where
1 þ 0:04  Gz2=3 • Mass transfer across boundary layers
_ p
mc
Gz ¼ T A mass balance across the feed side bound-
K L ary layer yields the relationship between
(5) molar flux N, the mass transfer coefficient kx,
and the solute concentrations cm and cb at the
where Gz is the Graetz number, m_ is the mass flow
interface and in the bulk, respectively (Curcio
rate, cp is the liquid heat capacity, KT is the liquid
and Drioli 2005; Mya Tun et al. 2005):
thermal conductivity, and L is the length of the
tubes.
N cm
However, several empirical correlations exist ¼ kx ln (6)
r cb
which allow to estimate the boundary layer heat
transfer coefficients for other geometries and heat
where r is the solution density.
transfer mechanisms.
The method that is used in literature to
The heat transfer across the membrane has
determine the mass transfer coefficient is to
been already described. For what concerns the
employ an analogy between heat and mass
heat transferred by convection within the mem-
transfer. Therefore, Eqs. 4 and 5 can be used
brane pores, this can be also considered but is
to estimate boundary layer mass transfer coef-
negligible because convection accounts for, at
ficients by substituting the Sherwood number
most, 6 % of the total heat lost through the mem-
for the Nusselt number, the Schmidt for the
brane and only 0.6 % of the total heat transferred
Prandtl, and the mass transfer Graetz number
across the membrane (Lawson and Lloyd 1997).
for its heat transfer form. In general, the used
Regarding mass transfer, Fig. 4 illustrates the
correlations are as follows:
possible mass transfer resistances in MD using an
electrical analogy.
6 Membrane Distillation (MD)
Sh ¼ a Reb Scg (7)
where Sh = Sherwood number = (kxdh)/D (dh
hydraulic diameter, D diffusion coefficient in
the liquid), Sc = Schmidt number = m/(rD) (m
is the bulk liquid viscosity; r is the solution
density), and GzM = mass transfer Graetz
_
number = GzM ¼ rDmAB _
L (m is the mass flow
rate; L is the tube length).
As a result of the solvent transmembrane
flux across the membrane, when aqueous solu-
tions containing nonvolatile solutes are con-
sidered, the concentration of the nonvolatile
solutes at the membrane surface (CBm)
becomes higher than that at the bulk feed
(CBb) with time as long as the separation pro-
cess is taking place. Almost 100 % of separa-
tion is obtained. In this case, care must be
taken as supersaturation states may eventually
be achieved affecting the efficiency of the
membrane process. The term concentration
polarization coefficient (CPC) is defined to
quantify the mass transport resistance within
the concentration boundary layer at the feed
side as follows:
cBm
CPC ¼ (8)
cBb
The increased concentration of nonvolatile
compounds next to the membrane surface
would have the influence of reducing the
transmembrane flux due to the establishment
of concentration polarization (CP) layer at the
feed side that acts as a mass transfer resistance
to the volatile molecule species (water). For-
tunately, in MD process, the low to moderate
flow rates and high heat transfer coefficients
reduce the impact of concentration polariza-
tion, which is lower than that of the tempera-
ture polarization effect (Laganà et al. 2000;
El-Bourawi et al. 2006; Drioli et al. 1999;
Srisurichan et al. 2006). In fact, boundary
layers next to the membrane can contribute
substantially to the overall transfer resistance;
heat transfer across the boundary layers is
often the rate-limiting step for mass transfer
in MD because a large quantity of heat must be
supplied to the membrane surface to vaporize
the liquid and because the membrane fabrica-
tion technology has improved in the last
decades so much that MD process has shifted
away from being limited by mass transfer
across the membrane to being limited by heat
transfer through the boundary layers on either
side of the membrane.
• Mass transport through the membrane pores
As stated earlier, the mass transfer process
in MD is driven by the imposed vapor-
pressure gradient between both sides of the
membrane. The mass transport mechanism is
governed by three basic mechanisms known as
Knudsen diffusion, Poiseuille flow, and
molecular diffusion or the combinations
between them known as transition mechanism
(excluding surface diffusion, negligible in MD
because, by definition of the MD phenome-
non, molecule–membrane interaction is low
and the surface diffusion area in MD mem-
branes is small compared to the pore area).
The dusty gas model is usually used as a
general model taking into account the latter
basic mechanisms (Lawson and Lloyd 1997;
Curcio and Drioli 2005; El-Bourawi
et al. 2006):
ND Xn
i  pi Nj
pj N D D
1
i
þ ¼ ∇p (9)
Dkie j¼16¼i D0ije RT i
e r2 p i
Nvi ¼  ∇P (10)
8RTtm
rffiffiffiffiffiffiffiffiffiffiffi
2er 8RT
Dkie ¼ (11)
3t p Mi
e 0
D0ije ¼ D (12)
t ij
where ND is the diffusive flux, NV is the viscous
flux, Dk is Knudsen diffusion coefficient, D0 is
the ordinary diffusion coefficient, pi is the partial
pressure of the component i, P is the total pres-
sure, Mi is the molecular weight of component i, r
Membrane Distillation (MD) 7

Membrane Distillation
(MD), Fig. 5 Common Feed in permeate out Feed in Coolant out
configurations of the
Air gap
membrane distillation
Membrane
process that may be utilized Membrane
to establish the required
driving force (El-Bourawi
et al. 2006) Condensing plate

Feed out permeate in Feed out

Coolant in
Product
DCMD Configuration AGMD Configuration

Sweep gas
Feed in out Feed in Vacuum

Membrane Condenser Membrane Condenser

Permeate Permeate

Feed out Sweep gas in Feed out

SGMD Configuration VMD Configuration

is the membrane pore radius, e is the membrane N ¼ C  DP

porosity (assuming the membrane consists of
uniform cylindrical pores), m is the fluid viscos-
ity, and t is the membrane tortuosity. The sub-
script “e” is indicative of the effective diffusion
coefficient function of the membrane structure.
There is only one problem with the appli-
cation of the DGM to MD, and that lies in the
fact that MD is a non-isothermal process. The
DGM was derived for isothermal flux, but has
been successfully applied to non-isothermal
systems via the inclusion of terms for thermal
diffusion and thermal transpiration. However,
it is easily shown (Lawson and Lloyd 1997)
that these terms are negligible in the MD oper-
ating regime, and Tavg in the membrane is used
in place of T in the DGM equations.
Regardless of which mechanism is involved in
the mass transportation process, the molar
flux, N, must be proportional to the vapor-
pressure difference across the membrane:
where DP is the vapor-pressure difference across
the membrane (function of temperatures and
compositions at the membrane surface) and C is
the membrane distillation coefficient that can be
obtained experimentally. C is a function of tem-
perature, pressure, and composition within the
membrane as well as membrane structure and
depends on the MD configuration employed as
well as on the Knudsen number (Kn, ratio of the
mean free path of the transported gas molecules
(l) through the membrane pores to the mean pore
diameter of the membrane (d)). In fact, Kn num-
ber determines the physical nature of flow
through membrane pores, and since the mem-
branes used in MD exhibit pore size distribution,
more than one mechanism may occur through the
membrane.
Whereas on feed side only an aqueous solution
can be present, the nature of the permeate can be
different and gives origin to the four basic MD
configurations:
8 Membrane Distillation (MD)
Membrane Distillation
(MD), Fig. 6 Basic hydrophobic membrane
channel arrangement and
temperature profile for
PGMD (Winter et al. 2011)
hot feed
– Direct contact MD (DCMD), in which the
permeate is in liquid phase and, therefore, the
membrane is on both sides directly in contact
with aqueous solutions
– Vacuum MD (VMD), in which the vaporized
solvent is recovered by vacuum and con-
densed, if needed, in a separate device
– Air gap MD (AGMD), in which an air gap is
interposed between the membrane and a con-
densation surface
– Sweeping gas MD (SGMD), in which a strip-
ping gas is used as a carrier for the removal of
the produced vapor (Fig. 5)
The type of employed MD depends upon per-
meate composition, flux, and volatility:
• SGMD and VMD are typically used to remove
volatile organic or dissolved gas from an aque-
ous solution.
• Because AGMD and DCMD do not need an
external condenser, they are best suited for
applications where water is the
permeating flux.
• The DCMD configuration, which requires the
least equipment and is simplest to operate, is
best suited for applications such as desalina-
tion or the concentration of aqueous solutions
(orange juice), in which water is the major
permeate component.
• AGMD, which is the most versatile MD con-
figuration, can be applied to almost any
applications.
distillate channel
distillate channel
condenser foil
membrane
condenser
TH
T1
coolant
evaporator
P1 T0
TC
P0
distillate
Some new configurations with improved
energy efficiency, better permeation flux, or
smaller footprint have been proposed such as
material gap membrane distillation, multi-effect
membrane distillation, multi-effect vacuum
membrane distillation, permeate gap membrane
distillation, and hollow fiber multi-effect mem-
brane distillation.
Permeate gap membrane distillation (PGMD)
is an enhancement of DCMD in which a third
channel is introduced by an additional
non-permeable foil (Fig. 6).
One significant advantage of PGMD is the
separation of the distillate from the coolant.
Therefore the coolant can be any other liquid,
such as cold feedwater. This offers the opportu-
nity to integrate an efficient heat recovery system.
Multi-effect membrane distillation (MEMD)
is based on the concepts of multi-stage and
multi-effect distillation for seawater desalination.
The cold feed solution is placed beneath the con-
densation surface as a coolant to condense the
permeated vapors as well as to gain heat at the
same time. The pre-heated feed solution is further
heated before it enters the feed channel.
Vacuum-multi-effect membrane distillation
(V-MEMD) is a modified form of VMD that
integrates the concept of multi-effect distillation
into the VMD. As a general principle of the
process, the vapors produced in each stage are
condensed during the subsequent stages. Vapors
are generated in steam raiser working under vac-
uum by exchanging the heat provided by external
source. The vapors are introduced in first stage
Membrane Distillation (MD)
where these are condensed by exchanging the
heat with feed via a foil. The vapors generated
in first stage are transported through the mem-
brane and collected on the foil in the second
stage. It has been claimed that these modules
have excellent gained to output ratio which is
crucial parameter for industrial applications
(Zhao et al. 2013). A condenser is used to con-
dense the vapors generated in final stage. The
vapor pressure in each stage is less than its pre-
ceding stage.
Material gap membrane distillation (MGMD)
consists of filling the gap between the membrane
and the condensation plate with different mate-
rials having different characteristics such as poly-
urethane (sponge), polypropylene mesh, sand,
and deionized water in order to increase trans-
membrane flux with respect to AGMD.
Osmotic distillation (OD) represents another
extension of the MD concept: a microporous
hydrophobic membrane separates two aqueous
solutions that are kept in contact at different
solute concentrations; this difference in activity
causes a vapor-pressure difference that activates
mass transport through the membrane. Because
OD operates essentially at room temperature, it is
appropriate for applications in the agro-food
industry (such as in integrated membrane system
for the clarification and the concentration of cit-
rus and carrot juices that has been proposed as an
alternative and efficient approach to the tradi-
tional techniques currently in operation), in phar-
maceutical biotechnology, and medicine (more
information can be found in Drioli et al. (2006),
Drioli et al. (2015)).
To date, the slow progress of MD has been
related with the unavailability of appropriate
membranes and modules for MD applications,
high energy consumption with respect to RO
that increases the overall energy demand, mem-
brane wetting, and low flux. However, thanks to
the recent and growing extensive research activ-
ities carried out in various areas of MD, the pro-
cess has become much more attractive due to the
9
availability of better membranes and to the pos-
sibility to utilize alternative energy sources in
niche applications.
References
Bodell BR (1963) Silicone rubber vapor diffusion in saline
water distillation. US Patent 285,032
Curcio E, Drioli E (2005) Membrane distillation and
related operations-a review. Sep Purif Rev 34:35–85
Drioli E, Lagana F, Criscuoli A, Barbieri G (1999) Inte-
grated membrane operations in desalination processes.
Desalination 122:141–145
Drioli E, Criscuoli A, Curcio E (2006) Membrane
contactors: fundamentals, applications and potentiali-
ties, vol 11, Membrane science and technology series.
Elsevier, Amsterdam/Boston
Drioli E, Macedonio F, Ali A (ed) (2012) Membrane dis-
tillation: basic aspects and applications – Virtual Spe-
cial Issue of Journal of Membrane Science. Elsevier
Drioli E, Ali A, Macedonio F (2015) Membrane distilla-
tion: recent developments and perspectives. Desalina-
tion 356:56–84
El-Bourawi MS, Ding Z, Ma R, Khayet M (2006) Review.
A framework for better understanding membrane dis-
tillation separation process. J Membr Sci 285:4–29
Findley ME (1967) Vaporization through porous mem-
branes. Ind Eng Chem Process Des Dev 6(2):226–230
Laganà F, Barbieri G, Drioli E (2000) Direct contact
membrane distillation: modeling and concentration
experiments. J Membr Sci 166:1–11
Lawson KW, Lloyd DR (1997) Membrane distillation.
J Membr Sci 124:1–25
Mya Tun C, Fane AG, Matheickal JT, Sheikholeslami
R (2005) Membrane distillation crystallization of con-
centrated salts – flux and crystal formation. J Membr
Sci 257:144–155
Srisurichan S, Jiraratananon R, Fane AG (2006) Mass
transfer mechanisms and transport resistances in direct
contact membrane distillation process. J Membr Sci
277:186–194
Winter D, Koschikowski J, Wieghaus M (2011) Desalina-
tion using membrane distillation: experimental studies
on full scale spiral wound modules. J Membr Sci
370:104–112
Zhao K, Heinzl W, Wenzel M, B€ uttner S, Bollen F,
Lange G, Heinzl S, Sarda N (2013) Experimental
study of the memsys vacuum-multi-effect-membrane-
distillation (V-MEMD) module. Desalination
323:150–160
M
Membrane Distillation Applications
Francesca Macedonio
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Renede
(CS), Italy
Membrane distillation (MD) is a non-isothermal
process that allows the separation of volatile
components from solutions. If the solutions con-
tain nonvolatile components, it is possible to
remove solvent by concentrating the solutions.
MD has been applied for separation of nonvola-
tile components from water like ions, colloids,
and macromolecules (El-Bourawi et al. 2006;
Lawson and Lloyd 1996, 1997; Mengual and
Pena 1997; Khayet et al. 2003, 2006; Sudoh
et al. 1997; Drioli et al. 1986; Zolotarev
et al. 1994); for the removal of trace volatile
organic compounds from water such as benzene,
chloroform, and trichloroethylene (Lawson and
Lloyd 1997; Duan et al. 2001; Banat and Simandl
1996, 2000; Sarti et al. 1993; Qureshi et al. 1994;
Banat and Al-Shannag 2000); or for the extrac-
tion of other organic compounds such as alcohols
from dilute aqueous solutions (Lawson and Lloyd
1997; Garcia-Payo et al. 2000; Banat and
Simandl 1999; Bandini et al. 1997; Bandini and
Sarti 1999). As a consequence, MD is suited for
both concentration of aqueous solutions and
water production. In fact, MD has been applied
for water desalination where near 100 % rejection
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_362-1
of nonvolatile ionic solutes is easily achieved
(an example can be found in the European-funded
project MEDINA (Drioli et al. 2011)), wastewa-
ter treatment and food processing (concentration
of juice and raw cane sugar), and biomedical
applications (such as water removal from blood
and treatment of protein solutions) (El-Bourawi
et al. 2006). Moreover, thanks to its characteristic
to work at lower temperatures with respect to
those usually used in thermal processes and thus
allowing the efficient use of alternative energy
sources (solar, wind, or geothermal), MD has
been considered a valid desalination operation
in arid areas with abundant solar energy
available.
However, a lot of other interesting applica-
tions of MD have been explored due to less foul-
ing tendency of the process and the potential to
treat complex feed solutions. Separation of
azeotropic aqueous mixtures such as
alcohol–water mixtures, concentration of radio-
active solutions and application for nuclear desa-
lination, wastewater treatment in which a less
hazardous waste can be discharged to the envi-
ronment specially in textile waste treatment that
is contaminated with dyes, concentration of cool-
ant (glycol) aqueous solutions, treatment of
humic acid solutions, pharmaceutical wastewater
treatment, and in areas where high-temperature
applications lead to degradation of process fluids
can be attractive (Banat and Simandl 1996).
In addition, due to the chemical stability of the
employed membranes, MD can also be applied for
2 Membrane Distillation Applications

Membrane Distillation Applications, Table 1 Applications of MD mentioned in different recent studies (Reprinted
with permission from Drioli et al. 2015, Elsevier)
MD
Feed Target Used membranes configuration References
Seawater Boron removal PVDF DCMD Hou et al. (2013)
Simulated water Chromium removal PTFE DCMD Bhattacharya
et al. (2014)
Produced water Desalination PTFE DCMD Singh and Sirkar
(2012)
Aqueous solution of Concentration of PP VMD Shao et al. (2014)
N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
solution
Cooling tower blow-down Desalination FS PP DCMD Yu et al. (2013)
water
Aqueous ammonia solution Removal of ammonia PVDF capillary DCMD and Qu et al. (2013)
MDCMD
Olive oil waste mill water Concentration of FS PTEF DCMD Xie et al. (2013)
phenolic compounds
Produced water Desalination FS PTFE AGMD Alkhudhiri
et al. (2013)
Model lactose solution Ethanol production PP capillary DCMD Tomaszewska
membrane and Białończyk
(2013)
Synthetic solution of trace Removal of complex FS PTFE DCMD Wijekoon
OC trace organic et al. (2014)
compounds
Aqueous H2SO4 solution Concentration of H2SO4 PP hollow fiber Multi-effect Li et al. (2012)
solution MD
Retentate of NF and RO Improvement of water PVDF hollow DCMD Tun and Groth
RF and salt fibers (2011)
crystallization
Water from Great Salt Lake Recovery of minerals FS PTFE and PP DCMD Hickenbottom
and Cath (2014)
Zabłocka Thermal Brine Brine concentration PP hollow fiber DCMD Gryta (2013)
accrual
Glycerol fermentation broth Separation of acetic Accurel PP hollow DCMD Gryta
acid from the broth fiber et al. (2013)
Synthetic radioactive Removal of radioactive Hydrophobically DCMD Khayet (2013)
wastewater elements modified FS PS or
PES
Wastewater containing Removal of arsenic PP and PVDF FS VMD Criscuoli
arsenic in different et al. (2013)
concentrations

the concentration of acids (Tomaszewska 1993;
Tomaszewska et al. 1995; Tang et al. 2003).
A list of innovative and potential uses of MD for
various applications mentioned in the recent liter-
ature is provided in Table 1.
More recently membrane distillation has been
also used in membrane bioreactor configuration
(MDBR) for the treatment of industrial and
municipal used waters, in order to retain effec-
tively small size and persistent contaminants
(Phattaranawik et al. 2008). The possibility to
combine MD with the production of high-quality
crystals extracted from the brine of nanofiltration
(NF) and reverse osmosis (RO) is particularly
Membrane Distillation Applications
interesting and promising as suggested in Drioli
et al. (2011), Macedonio et al. (2007), and
Macedonio and Drioli (2010). Moreover, mem-
brane distillation can be also utilized in integrated
system with pressure retarded osmosis (PRO) or
reverse electrodialysis (RED) for utilizing salin-
ity gradient for energy production (the so-called
blue energy). An example can be found in the
Megaton project (Kurihara and Hanakawa 2013)
in Japan and in the SeaHero project (Kim
et al. 2009, 2011) in South Korea. In the last
part of these two projects, hybrid systems with
MD and PRO units have been proposed for the
extraction of valuable resources from the brine,
the minimization of the environmental impact of
the brine, and the recovery of energy.
List of Symbols
AGMD Air gap membrane distillation
DCMD Direct contact membrane distillation
FS PP Flat sheet polypropylene
FS PS or PES Flat sheet polysulfone or
polyethersulfone
FS PTEF Flat sheet polytetrafluoroethylene
MDCMD Modified direct contact membrane
distillation
PP and PVDF FS Polypropylene and
polyvinylidene difluoride flat sheet
PP Polypropylene
PTFE Polytetrafluoroethylene
PVDF Polyvinylidene difluoride
VMD Vacuum membrane distillation
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(2003) Hydrochloric acid recovery from rare earth
chloride solutions by vacuum membrane distillation
(1) Study on the possibility. J Rare Earths 21:78–82
Tomaszewska M (1993) Concentration of the extraction
of fluid from sulphuric acid treatment of
phosphogypsum by membrane distillation. J Membr
Sci 78:277–282
Tomaszewska M, Białończyk L (2013) Production of eth-
anol from lactose in a bioreactor integrated with mem-
brane distillation. Desalination 323:114–119
Tomaszewska M, Gryta M, Morawski AW (1995) Study
on the concentration of acids by membrane distillation.
J Membr Sci 102:113–122
Tun CM, Groth AM (2011) Sustainable integrated mem-
brane contactor process for water reclamation, sodium
sulfate salt and energy recovery from industrial efflu-
ent. Desalination 283:187–192
Wijekoon KC, Hai FI, Kang J, Price WE, Cath TY,
Nghiem LD (2014) Rejection and fate of trace organic
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M
Membrane Distillation Bioreactor
(MDBR)
Tony Fane
School of Chemical Engineering, UNSW, The
University of New South Wales, Sydney, NSW,
Australia
Singapore Membrane Technology Centre,
Nanyang Technological University, Singapore
The Membrane Distillation Bioreactor (MDBR)
combines a wastewater bioreactor with mem-
brane distillation (MD) (Fane et al. 2012). It is
shown schematically in Fig. 1. The MDBR is a
member of the Membrane Bioreactor (MBR)
family but with important differences from the
conventional MBR. The conventional MBR uses
microporous membranes, either microfiltration
(MF) or ultrafiltration (UF), to retain biomass,
or mixed liquor, within the reactor. The MDBR
employs a MD membrane to retain the mixed
liquor and provide the treated wastewater. The
MDBR membranes can be either submerged in
the bioreactor or located in a sidestream. An
elevated temperature, typically 50–60  C, is
used to drive water across the membrane and
this means that thermophilic biomass are
required. In addition the hydrophobic membrane
retains nonvolatile salts that accumulate in the
reactor. Therefore the MDBR biomass need to
be salt tolerant (halotolerant). The MDBR con-
cept provides a “high retention” MBR, wherein
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_363-1
low molecular weight molecules do not leave the
reactor through the membrane, as they would
through MF or UF membranes in the conven-
tional MBR. This means that the organic reten-
tion time (ORT) in the MDBR can be
significantly longer than the hydraulic retention
time (HRT) and recalcitrant organics are given
longer to degrade. In contrast the conventional
MBR has ORT equal to HRT. The MDBR, in
common with other MBRs, typically has a small
“bleed”, or wastage, stream to maintain a steady-
state concentration of mixed liquor suspended
solids (MLSS). The proportion wasted daily
determines the “sludge retention time” (SRT);
for example 5 % removal per day gives SRT of
20 days, 10 % removal gives SRT of 10 days
etc. The accumulation of nonvolatile and
nonbiodegradable species in the reactor is deter-
mined by the ratio of SRT/HRT, which represents
the concentration factor and could exceed 20x.
Retained salts can reach significant levels, but
with acclimatization the biomass can cope.
The MDBR can provide a high-quality treated
water, suitable for reuse. This is due to the unique
separation properties of the typical MD mem-
brane. In common with other membrane pro-
cesses, the MDBR can experience fouling, and
this can be controlled by bubbling and occasional
cleaning. Experience indicates that the fouling is
usually a combination of inorganic scale
(calcium salts) and biofouling. Fluxes of the
order of 10 l/m2h can be sustained.
2 Membrane Distillation Bioreactor (MDBR)

W/Water

Negligible
TOC
Waste or Solar QIN
Heat QOUT

Biomass
(thermophilic) MD
Module
FS or HF

S Air

Membrane Distillation Bioreactor (MDBR), Fig. 1 Membrane distillation bioreactor

The MDBR is a developmental concept and References

not widely used. However it has been demon-
strated in the petrochemical industry (Khaing Fane AG, Phattaranawik J, Wong FS (2012) Contaminated
inflow treatment with membrane distillation bioreac-
et al. 2010) providing a highly treated water,
tor. US Patent 8,318,017B2 (PCT June 2006)
and driven by waste heat. Other target industries Khaing T-H, Li J, Li Y, Wai N, Wong FS (2010) Feasibil-
include food and pharmaceutical wastewaters. ity study on petrochemical wastewater treatment and
Another opportunity could be water reclamation reuse using a novel submerged membrane distillation
bioreactor. Sep Purif Technol 74:138–143
where an analysis shows a 30 % lower electrical
energy usage than a combined MBR and RO
process. Recently the MDBR has been operated
under anaerobic conditions with the generation of
biogas.
F
Fouling
Lidietta Giorno and Napoleone D’Agostino
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, University
of Calabria, Rende(CS), Calabria, Italy
Synonyms
Fouling in membranes; Membrane fouling
An intrinsic phenomenon of all membrane sepa-
ration processes is the decline of the flux through
the membrane as a function of time, due to con-
centration polarization effects and the formation
of cake or gel layers by feed solution constituents
retained by the membrane. Equally devastating
for the performance of a process is membrane
fouling. Membrane fouling is a general term. It
may be the result of concentration polarization; it
may also be the consequence of adsorption of
feed solution constituents at the membrane sur-
face and especially in microfiltration also within
the membrane structure. The control of concen-
tration polarization and membrane fouling is a
major engineering aspect in the design of mem-
brane separation processes and equipment (Brian
1966; Blatt et al. 1970; Jonsson and Boesen 1984;
Bian et al. 2000; Hoek and Elimelech 2003;
Cornelissen et al. 2004).
Concentration polarization effects will occur
in all membrane separation processes. Its
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_366-1
consequences, however, are especially severe in
pressure-driven membrane processes. When in a
mass separation procedure a molecular mixture is
brought to a membrane surface, some compo-
nents will permeate the membrane under a
given driving force, while others are retained.
This leads to an accumulation of retained mate-
rial and to a depletion of the permeating compo-
nents in the boundary layers adjacent to the
membrane surface. This phenomenon is referred
to as concentration polarization. The causes and
consequences of concentration polarization may
be rather different in different membrane pro-
cesses. Often the adverse effects of concentration
polarization are intensified by an adsorption of
certain feed mixture constituents at the mem-
brane surface. This phenomenon is referred to
as membrane fouling.
Concentration polarization can be minimized
by hydrodynamic means such as the feed flow
velocity and the membrane module design. The
control of membrane fouling, however, is more
difficult. The transition between concentration
polarization and fouling can be expressed by the
concept of “critical flux.” This concept was intro-
duced in the 1990s (Field et al. 1995; Howell
1995; Bacchin 2004), and it is the flux value
below which a decline of flux with time does
not occur, above it fouling is observed. Critical
flux values depend on numerous parameters, such
as properties of solutions to be treated (particle
size, concentration, ionic strength, pH), surface
interactions (zeta potential, surface tension), and
2 Fouling
Fouling,
Fig. 1 Schematic diagram
flux
illustrating the difference
between the flux decline
due to concentration
polarization and due to
membrane fouling
hydrodynamic conditions (axial velocity)
(Bromley et al. 2002; Chen 1998; Ingmar
et al. 1999; Belfort et al. 1994).
When operating below the critical flux, it is
possible to observe a linear correlation between
flux and transmembrane pressure. Above it, fur-
ther increase in transmembrane pressures lead to
additional layer deposit on the membrane sur-
face, until a point where the deposit fully com-
pensates the increase in pressure drop. At this
stage the liming flux is reached, which represents
the maximum stationary permeation flux. After
operating above the critical flux value, decreasing
the transmembrane pressure will not lead to the
previous flux behavior.
However, experimental evidences show that,
although operating at subcritical flux, gradual
fouling develops in membrane materials, and it
proves to be hydraulically irreversible after a
long period experimentation (Ognier et al. 2004).
The formation of a gel or cake layer is one
cause for membrane fouling. Gel or cake layer
formation may be caused by a variety of materials
including inorganic precipitates such as CaSO4,
Fe(OH), and other metal hydroxides; organic
materials such as proteins, humic acids, and
other macromolecular materials; and biological
components such as microorganisms and prod-
ucts of their metabolism (biofouling). Membrane
fouling may also occur without concentration
polarization, i.e., a direct transport to the mem-
brane surface. The attachment of the substances
to the membrane surface may be caused by
adsorption due to hydrophobic interactions, van
der Waals force attractions, or electrostatic
forces. The fouling layer itself may be rather
pure water flux
concentration polarization
membrane fouling
time
porous and thus permeable for aqueous solutions
as some inorganic precipitants or highly imper-
meable as some films of mineral oils or hydro-
phobic surfactants. The fouling mechanism
depends also on the membrane process. In elec-
trodialysis fouling is caused mainly by the pre-
cipitation of polyelectrolytes or sparingly soluble
salts such as CaSO4 or CaCO3. Membrane foul-
ing in electrodialysis affects mainly the anion-
exchange membranes because most of the colloi-
dal and macromolecular polyelectrolytes present
in natural waters such as humic acids or proteins
are negatively charged. In ultra- and
microfiltration of biological solutions, but also
in reverse osmosis of sea water, biological foul-
ing is a severe problem affecting the economics
of the processes. In biomedical applications pro-
tein adsorption and protein denaturation at the
membrane surface is often impairing the perfor-
mance of the membranes. In membrane distilla-
tion, adsorption of molecules can change surface
energy and hydrophobic properties.
The difference between concentration polari-
zation and membrane fouling or scaling is illus-
trated schematically in Fig. 1.
Concentration polarization is a reversible pro-
cess based on diffusion and takes place over a few
seconds; it can be described adequately by a
simple mathematical model and easily be con-
trolled by the proper process design. Fouling is
generally irreversible and the flux decline takes
place over many minutes, hours, or even days.
A constant flux is generally not reached at all.
Membrane fouling is more difficult to describe
and to control by experimental means. Membrane
fouling is determined by a variety of different
Fouling 3

Methods to reduce concentration polarization

Reduce pressure Reduce concentration Reduce solids

at membrane surface in feed

Mixing perpendicular Low concentration Remove concentration Increase mass

to membrane factor at membrane surface transfer of solids
back

Paddle Static Boundary layer Mechanical

mixers mixers skimming scouring

High velocity gradient Increase diffusivity Thin Short flow

channels length
Move Move Increase
membrane liquid temperature

Fouling, Fig. 2 Methods to reduce concentration polarization

parameters including the feed solution constitu-
ents and their concentration, membrane material,
and the fluid dynamic system design. Membrane
fouling can be caused by simple precipitation of
insoluble materials or reversible and irreversible
adsorption of components at the membrane sur-
face and within the membrane pores.
The means of preventing or at least controlling
membrane fouling effects are as heterogeneous as
the different material and mechanisms causing
the fouling (Ridgway et al. 1983; Nilson 1998).
The main procedures to avoid or control concen-
tration polarization and fouling involve:
• Pretreatment of the feed solution
• Membrane surface modifications
• Hydrodynamic optimization of the membrane
module
• Membrane cleaning with the proper chemical
agents
A list of various methods to reduce concentra-
tion polarization is reported in Fig. 2.
A pretreatment of the feed solution may
include chemical precipitation, prefiltration, pH
adjustment, chlorination, or carbon adsorption. In
some membrane module, design concepts as, for
instance, in hollow fiber modules, the elimination
of all particulate materials is of great importance
for the proper function of the membrane.
Membrane surface modifications include the
introduction of hydrophilic moieties or charged
groups in the membrane surface by chemical
means or plasma deposition.
Increasing the shear rate imposed by the feed
solution on the membrane surface will in many
cases reduce the membrane fouling. High feed
flow velocities and the proper module design are
efficient tools in controlling membrane fouling
(Fig. 3).
When in spite of an adequate membrane and
module design the membrane flux is decreasing
with operation time to an unacceptable low value,
it is necessary to clean the membrane to restore
the flux in part or completely. Typical cleaning
agents are acids and bases, such as HNO3 and
NaOH, complexing agents, enzymes, and deter-
gents. Another very effective method to mini-
mize the effects of membrane fouling in
microfiltration is backflushing (Fig. 4). In
backflushing, the applied pressure is reversed
and the permeate is pushed through the mem-
brane, lifting off fouling material that had been
precipitated on the feed side membrane surface
and washing it out of the filtration device.
4 Fouling
Fouling, Fig. 3 Effect of axial velocity on concentration polarization
Fouling,
Fig. 4 Backflushing
method to reduce fouling Suspension
Jv
Backflushing is done in certain time intervals for
a couple of seconds.
References
Bacchin P (2004) A possible link between critical and
limiting flux for colloidal systems: consideration of
critical deposit formation along a membrane.
J Membr Sci 235:111–122
Belfort G, Davis RH, Zydney AL (1994) The behaviour of
suspensions and macromolecular solution in crossflow
microfiltration. J Membr Sci 98:1–58
Bian R, Yamamoto K, Watanabe Y (2000) The effect of
shear rate on controlling the concentration polarization
and membrane fouling. Desalination 131:225–236
Blatt WF, Dravid A, Michaels AS, Nelsen LM (1970) Sol-
ute polarization and cake formation in membrane
Suspension
Backflushing
With
backflushing
Without
backflushing
t
ultrafiltration: cause, consequences and control tech-
niques. In: Flinn JE (ed) Membrane science and tech-
nology. Plenum Press, New York, pp 47–97
Brian PTL (1966) Mass transport in reverse osmosis. In:
Merten U (ed) Desalination by reverse osmosis. MIT
Press, Cambridge, MA, p 161
Bromley AJ, Holdich RG, Cumming IW (2002) Particulate
fouling of surface microfilters with slotted and circular
pore geometry. J Membr Sci 196:27
Chen V (1998) Performance of partially permeable
microfiltration membranes under low fouling condi-
tions. J Membr Sci 147:265
Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin
J-J, Oo H, Wessels LP (2004) Membrane fouling and
process performance of forward osmosis membranes
on activated sludge. J Membr Sci 319:158–168
Field RW, Wu D, Howell JA, Gupta BB (1995) Critical
flux concept for microfiltration fouling. J Membr Sci
100:259
Fouling
Hoek EMV, Elimelech M (2003) Cake-enhanced concen-
tration polarization: a new fouling mechanism for salt-
rejecting membranes. Environ Sci Technol
24:5581–5588
Howell J (1995) Subcritical flux operation of
microfiltration. J Membr Sci 107:165
Ingmar HH, Eert V, Gun T, Christian T (1999) The influ-
ence of the membrane zeta potential on the critical flux
for crossflow microfiltration of particle suspensions.
J Membr Sci 156:153
Jonsson G, Boesen CE (1984) Polarization phenomena in
membrane process. In: Belfort G (ed) Synthetic mem-
brane processes. Academic, New York
5
Nilson JL (1998) Fouling of an ultrafiltration membrane
by dissolved whey protein concentrate. J Membr Sci
36:147
Ognier S, Wisniewski C, Grasmick A (2004) Membrane
bioreactor fouling in sub-critical filtration conditions:
a local critical flux concept. J Membr Sci 229:171
Ridgway HF, Justice C, Kelly A, Olson BH (1983) Micro-
bial fouling of reverse osmosis membranes used in
advanced wastewater treatment technology: chemical,
bacteriological and ultrastructural analyses. Appl
Environ Microbiol 45:1066
M
Membrane Reactor Equilibrium
Conversion
Giuseppe Barbieri
Institude on Membrane Technology, Italian
National Research Council, Rende(CS), Italy
The equilibrium constant of any reaction is func-
tion of temperature only. The equilibrium of a
conventional/traditional reacting system is func-
tion only of the thermodynamic variables
(temperature, pressure, and mixture composi-
tion). It is independent from the reactor model
(continuous stirred tank reactor, plug flow reac-
tor, batch reactor, etc.), fluid dynamics (mixing,
diffusion, etc.), heat exchange (isothermal, adia-
batic, or no-isothermal reactor), reactor size,
etc. since the equilibrium is reached when varia-
tion in temperature, pressure, and composition is
no longer present in the chemical system.
This condition is mathematically expressed by
the following equations set valid for a reacting
closed (no mass transfer with the environment)
system consisting of N reactions.
N Gas   uij
Kpj ¼ ∏ PReaction xi ðX1 , X2 ,::, XN Þ
i¼1
j ¼ 1,::, N Reaction
The formulation in terms of Kp constants enables
for the evaluation of reaction conversion and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_368-1
hence the equilibrium composition of the
reacting system kept under a set reaction pres-
sure. As well known, the equilibrium expresses
the highest limit for reaction conversion, and it
will be here indicated as TREC (Traditional
Reactor Equilibrium Conversion).
The conversion of a real chemical reactor
(of finite size) depends on several factors, e.g.,
reactor model, feed flow rate, residence time, and
heat transfer with the environment in addition to
the variables before indicated. Thus, its conver-
sion is always lower than the equilibrium one.
A membrane reactor (MR) has, in addition to
the traditional reactor, another chamber/volume:
the one named permeate. Therefore, it consists of
two (reaction and permeation) volumes separated
by a selective membrane. One can image each
chamber is provided with a piston moving with-
out friction, for keeping a constant pressure; con-
sequently, the reaction and permeation volumes
change according to the pistons movement. In
addition, the reaction pressure can be different
from the permeate pressure. During the reaction,
the chamber volumes change for achieving the
chemical and permeating equilibria. As the reac-
tive equilibrium, the permeative one has a
dynamic character such as the reactive one; this
means molecules (if any) permeating the mem-
(1)
brane from reaction side to permeate side are
equal in number to the molecules permeating in
the opposite direction.
Temperature, pressure, and composition of the
permeate can be different from those or reaction
2 Membrane Reactor Equilibrium Conversion

Membrane Reactor Equilibrium Conversion, Table 1 Thermodynamics table for water gas shift reaction (CO +
H2O = CO2 + H2) in an MR. Both reaction and permeating equilibrium are taken into account
Reaction CO H2O CO2 H2
Initial state n0 m n0 m1 n0 m2 n0
Reaction conversion x n0 x n0 x n0 x n0
Reactive equilibrium state n0 (1x) n0 (mx) n0 (m1 + x) n0 (m2 + x)
Permeation – – – z [n0 (m2 + x)]
Reactive and permeative equilibrium state n0 (1x) n0 (mx) n0 (m1 + x) n0[(m2 + x) (1z)]
Total mole number n0[1 + m + m1 + m2  z (m2 + x)]
Where, m > =x; x = MREC; z permeate hydrogen fraction
m, m1, and m2 are the feed molar ratio with respect to CO of H2O, CO2, and H2, respectively

volume. These variables have also to be taken
into account for evaluating the equilibrium of an
MR. Nevertheless, another constrain is required
for the equilibrium of an MR in addition to the
one defined by Eq. 1 for the traditional reactor.
This is the permeation equilibrium expressed as
the equality of the chemical potentials (e.g., par-
tial pressures for a gas phase reaction) (Barbieri
et al. 2001, 2005; Marigliano et al. 2003) on both
membrane sides of any permeable species Eq. 2.

ChemicalPotentialEquilibrium
i ¼ ChemicalPotentialReaction
i ¼ ChemicalPotentialPermeation
i
Equilibrium (2)
Pressurei ¼ Pressurei
Reaction
¼ Pressurei
Permeation
8 permeable species

This condition is independent from the mem-
brane type and permeation rate. As chemical
equilibrium in a conventional reactor, and in an
MR as well, is independent from the reaction
path, similarly the MR equilibrium is indepen-
dent from permeation rate.
The hydrogen permeates Pd-based mem-
branes following the Sieverts law. Even though,
the membrane characteristics (e.g., Pd, Pd-Ag,
thickness, etc.) influence the permeation rate
and hence the time necessary to reach the equi-
librium, the value of these parameters does not
affect the MR equilibrium.
The equilibrium depends on the extraction
capacity of the membrane system which is a
function of the temperature, pressure, and com-
position of the MR permeate volume that directly
gives the condition of Eq. 2.
The MREC (Membrane Reactor Equilibrium
Conversion) can be easily calculated using the
constrains of Eqs. 1 and 2. MREC can be also
calculated using the thermodynamics table for
the reaction(s) adding to it the terms related to
the permeative equilibrium.
CO þ H2 O ¼ CO2 þ H2 DH0298
¼ 41 kJ mol1
Table 1 reports the thermodynamics table for
calculating the equilibrium conversion of the
water gas shift reaction in a Pd-based MR, all
the figures are in moles. The procedure for calcu-
lating the number of moles at the equilibrium is
the one known since long time from chemistry as
the fourth row “reactive equilibrium state” of
Table 1 shows. In fact, in absence of a membrane
this conversion is the one of a traditional reactor
and here is identified as TREC. The presence of a
selective membrane contributes to product
(hydrogen) removal and hence to increase the
equilibrium conversion because of the mass law
effect or the Le Ch^atelier–Braun principle.
Therefore, the equilibrium conversion of a
Membrane Reactor Equilibrium Conversion 3

Membrane Reactor Equilibrium Conversion, Table 2 Number of moles determination at reactive and permeative
equilibrium in a membrane reactor
Moles n-butane n-butene Isobutene Hydrogen
Initial state n0 – – –
Reactive state of reaction 1  n0 x n0x – n0 x
Reactive state of reaction 2  n0 x w n0 x w
Permeation state – – –  n0 x z
Permeative and reactive equilibrium state n 0 ð 1  xÞ n0 x ð 1  w Þ n0 x w n0 x ð1  zÞ
Total number of moles n0 ð1 þ x  xzÞ
Where, x = MREC for reaction 1, w = MREC for reaction 2, z permeate hydrogen fraction
The initial concentration of n-butene, isobutene, and hydrogen was chosen as zero

reactor conversion (here named MREC) is
always higher than TREC. MREC is equal to
TREC in absence of any permeation.
The fifth row includes the term (z) for hydro-
gen permeation through a Pd-based membrane,
whereas the sixth row reports the moles present in
the reaction volume under the reactive and per-
meative equilibrium condition.
The total mole number in an MR owing to
permeation is lowered by the reducing term
{z [n0 (m2 + x)]} with respect to traditional
reactor.
The equilibrium constant of the reaction
(reactive constrain, see Eq. 1) for WGS reaction
considering the reactive and permeative equilib-
rium terms can be expressed as
ðm1 þ xÞ½ðm2 þ xÞð1  zÞ
KP ¼
ð1  x Þðm  x Þ
The other, permeative constrain Eq. 2 for the
hydrogen, the only permeating species is
PEquilibrium
H2 ¼
n0 ½ðm2 þ xÞð1  zÞ
PReaction
n0 ½1 þ m þ m1 þ m2  zðm2  xÞ
CO conversion and the hydrogen fraction perme-
ate the membrane are calculated resolving this set
of two equation in two unknowns: the conversion
(MREC) and the hydrogen permeated the
membrane.
Another example of using thermodynamics
table is reported for the n-butane dehydroisome-
rization (Al-Megren et al. 2013). This reaction
(reaction 3) involves the dehydrogenation of
n-butane (reaction 1) and successive isomeriza-
tion to isobutene (reaction 2). The main products
measured were normal butenes, isobutane, and
isobutene.

n  butane ¼ n  butene þ H2 DHReaction ð@25  CÞ ¼ 130 kJ mol1 (reaction1)

n  butene ¼ isobutene DHReaction ð@25  CÞ ¼  17 kJ mol1 (reaction2)

n  butane ¼ isobutene þ H2 DHReaction ð@25  CÞ ¼ 1137 kJ mol1 (reaction3)

From the thermodynamics table (Table 2), after reaction 1 and reaction 2 and the permeation
some algebra, the equilibrium constants for equilibrium condition are:
4 Membrane Reactor Equilibrium Conversion

x2 ð1  zÞð1  wÞ Reaction side References

K P1 ¼ P
ð1 þ x  xzÞð1  xÞ
Al-Megren HA, Barbieri G, Mirabelli I, Brunetti A,
Drioli E, Al-Kinany MC (2013) Direct conversion of
w
K P2 ¼ n-butane to isobutene in a membrane reactor: a ther-
ð1  wÞ modynamic analysis. Ind Eng Chem Res
52:10380–10386. doi:10.1021/ie400006c
x ð1  zÞ Barbieri G, Marigliano G, Perri G, Drioli E (2001)
PEquilibrium ¼ PReaction side Conversion–temperature diagram for a palladium
hydrogen
ð1 þ x  xzÞ membrane reactor. Analysis of an endothermic reac-
tion: methane steam reforming. Ind Eng Chem Res
This is a set of three equation in three unknowns 40:2017–2026. doi:10.1021/ie0006211
that resolved for x, w, and z gives the conversion Barbieri G, Brunetti A, Granato T, Bernardo P, Drioli
E (2005) Engineering evaluations of a catalytic mem-
values (MRECs) of the reaction 1 and reaction 2 brane reactor for water gas shift reaction. Ind Eng
and the permeate hydrogen fraction. Chem Res 44:7676–7683. doi:10.1021/ie050357h
Marigliano G, Barbieri G, Drioli E (2003) Equilibrium
conversion for a palladium membrane reactor. Depen-
dence of the temperature and pressure. Chem Eng
Process 42:231–236. doi:10.1016/S0255-2701(02)
00092-2
M

Membrane Wettability gLW  ð1 þ cos YÞ2

gLW
s ¼ l
(2)
4
Annarosa Gugliuzza
Institute on Membrane Technology - Research gl  ð1 þ cos YÞ ¼ 2
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ffi
National Council, ITM-CNR, Rende (CS), Italy pffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffi
þ
 þ
gs  gl þ gs  gl þ gs  gl
LW LW  

The concept of wettability (S) is referred to the
ability of a liquid to wet a surface (Hsu
et al. 2011). The degree of wettability, also
known as a wetting or spreading, is controlled
by interfacial forces established between a liquid
(L), solid (S), and vapor (V) phase at the mini-
mum equilibrium distance. These interaction
types are usually expressed as surface tensions
(g) and can be correlated to the wettability coef-
ficient by a mathematical equation:
S ¼ gSV  ðgSL þ gLV Þ
The surface tension, expressed as a force per unit
length [N/m] or energy per unit surface area
[J/m2], is a direct measurement of the cohesive
energy required for minimizing the free surface
area at the interface, where the number of similar
species is more restricted than bulk and attractive
forces are unequal and unbalanced in all direc-
tions (Fig. 1).
This parameter and related polar and nonpolar
components can be estimated by a set of mathe-
matical equations (Good and Van Oss 1992):
(3)
pffiffiffiffiffiffiffiffiffiffi
gAB
s ¼ 2 gþs gs
þ (4)
where the Lifshitz–van der Waals forces
gLW[mJ/m2], polar gAB[mJ/m2], acid (electron
acceptor) g+[mJ/m2], and base (electron donor)
g[mJ/m2] are the components of the surface free
energy g [mJ/m2] and can be calculated from
mean values of the apparent contact angle (ya),
expressed in a somewhat simplified form by the
Young’s equation:
(1)
gSV  gSL
cos ðYa Þ ¼ (5)
gLV
It is a convention to consider y = 90 as a bound-
ary value between hydrophilicity and hydropho-
bicity. Values less than 90 indicate hydrophilic
membrane surfaces with a positive liquid spread-
ing, whereas angle values higher than 90 are
measured on hydrophobic membrane surfaces
with negative spreading values (Fig. 2). Rolling
water droplets can be observed on super-
hydrophobic surfaces with y > 150 and S<<0.

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_370-6
2 Membrane Wettability

Membrane Wettability, Air

Fig. 1 Representative Interface
scheme of cohesive forces Cohesive forces
at an interface

Substrate

Attractive forces

a S>0 q < 90° b S<0 q < 90° c S << 0 q > 150°

Hydrophilic surface Hydrophobic surface Super-hydrophobic surface

Membrane Wettability, Fig. 2 Water droplets on wettable (a), non-wettable (b), and super-hydrophobic surfaces

In all cases, the apparent contact angle can be
regarded as the result of combined morphological
(i.e., tailed and loopy polymer segments,
grooves, and pores) and chemical (i.e., functional
binding or nonbinding sites) elements. Both two
contributions can go to the same or opposite
direction, depending on the nature of the chemi-
cal and physical forces established at the inter-
face. Normally, large membrane surface affinity
toward a liquid produces extensive spreading,
while higher surface roughness minimizes
it. The roughness factor or rugosity (R) is associ-
ated with an irregularity of the membrane surface
and can reduce the adhesion between liquid and
substrate, causing an increase in the apparent
contact angle (Thomas 1999). In this respect,
Wenzel and Cassie–Baxter equations describe
the wettability better than Young’s equation,
which is considered valid for ideal surfaces only
(Fig. 3).
In the Wenzel model, the surface grooves are
completely filled by the liquid and the contact
angle is determined by
 
g  gSL
cos ðYw Þ ¼ R SV (6)
gLV
Combining this equation with the Young’s one, a
simplified relation can be achieved:
cos ðYw Þ ¼ R  cos ðYa Þ (7)
Instead, in the Cassie–Baxter model, grooves as
well as pores are filled by air, which reduces the
adhesion line between liquid and substrate,
resulting in higher contact angle values:
cos ðYCB Þ ¼ f s  cos ðYa Þ þ f v  cos ðYv Þ (8)
Membrane Wettability
a b
gLV
Droplet
gSV gSL Droplet qa
qa
Soft surface Rough surface
d Zigzag profile
Membrane Wettability, Fig. 3 Effects of the roughness
factor on the contact line between droplet and surface: (a)
a flat surface described by Young’s equation, (b) a rough
where ya is the angle measured on the flat surface,
whereas fs and fv are the fractions of the solid and
vapor on the surface, respectively.
Some authors have proposed a “zigzag” geo-
metric model that corrects for roughness factor
for contact angle measurements, thereby making
possible an evaluation of the surface chemistry
effects (Taniguchi and Belfort 2002).
Contact angle measurements are powerful
tools able to reveal variations of the supramolec-
ular chemistry owing to adsorption, fouling,
affinity, or dry–wet switch taking place on the
membrane surfaces during separation processes.
In this respect, useful indication can be obtained
about the opportunity to put in contact mem-
branes with chemical streams without damages
and/or special treatments. Cleaning against dirty
or chemical contaminations can be monitored as
well as energy cohesive can be determined in
order to detect the nature of the interfacial forces
that control adhesion processes. Also, swelling
along with wetting and dewetting phenomena
can be studied under the action of specific trig-
gers. Static and dynamic contact angle modes
take the advantage of investigating all these
supramolecular changes in real time (Gugliuzza
and Drioli 2007; Gugliuzza and Drioli 2004,
Gugliuzza et al. 2006, 2007). In static mode, a
predetermined volume of liquid is placed on the
membrane surface and changes against time can
be monitored. In dynamic mode, the liquid is
3
c
Droplet
qa
Pillar surface
surface described by Wenzel equation, (c) a pillar surface
described by Cassie–Baxter equation, and (d) zigzag pro-
file section responsible for increased surface roughness
constantly pumped into (advancing mode, yadv)
and out (receding mode, yrec) a droplet in contact
with the membrane. The advancing contact angle
gives indirect indication about hydrophobic
domains distributed throughout the surface; the
receding one reveals the ability of local chemical
moieties to rearrange when coming in contact
with the liquid phase. The hysteresis expresses
the difference between two plateau values, due to
chemical and morphological effects at the
liquid–surface interface.
References
Good RJ, Van Oss CJ (1992) In: Schrader ME, Loeb GL
(eds) Modern approaches to wettability. Plenum Press,
New York
Gugliuzza A, Drioli E (2004) Role of additives in the
water vapor transport through block co-poly (amide/
ether) membranes: effects on surface and bulk polymer
properties. Eur Polym J 40/10:2381–2389
Gugliuzza A, Drioli E (2007) PVDF and HYFLON AD
membranes: ideal interfaces for contactor applications.
J Membr Sci 300:51–62
Gugliuzza A, Fabiano R, Garavaglia MG, Spisso A, Drioli
E (2006) Study of the surface character as responsible
for controlling interfacial forces at membrane–feed
interface. J Colloid Interface Sci 303(2):388–403
Gugliuzza A, Fabiano R, Garavaglia MG, Spisso A, Drioli
E (2007) Corrigendum to study of the surface character
as responsible for controlling interfacial forces at
membrane-feed interface. J Colloid Interface Sci
306(1):192–193, vol 303, pg 388, 2006
4 Membrane Wettability

Hsu S-H, Woana K, Sigmund W (2011) Biologically
inspired hairy structures for superhydrophobicity.
Mater Sci Eng R Rep 72/10:189–201
Taniguchi M, Belfort G (2002) Correcting for surface
roughness: advancing and receding contact angles.
Langmuir 18:6465–6467
Thomas TR (1999) Rough surfaces, 2nd edn. Imperial
College Press, London
M
Metal-Organic Frameworks (MOFs)
Tania Rodenas
Max Planck Institute f€
ur Chemische
Energiekonversion, M€ ulheim an der Ruhr,
Germany
Metal-organic frameworks (MOFs), also
called porous coordination polymers (PCPs),
are a class of crystalline solid materials whose
structure consists of a regular, two- or three-
dimensional network of metal cations or metal
oxide clusters (so-called nodes) connected by
organic molecules (so-called linkers). Figure 1a
depicts conceptually how the three-dimensional
structure of a MOF is built by assembling metal
(oxide) nodes and organic linkers, while Fig. 1b
shows a representative scanning electron micro-
graph of MOF crystals. First reports on metal-
organic frameworks date back to 1959
(Kinoshita et al. 1959). Attention toward this
class of materials was boosted in the 1990s by
more rational approaches to their “reticular”
design and synthesis (Hoskins and Robson
1989). Since then, extensive research efforts
have led to several thousand experimentally
reported MOF structures and have notably
broaden the scope of their potential applications
(MacGillivray 2010; MacGillivray and Lukehart
2014). Generally MOFs are synthesized in solu-
tion by reacting a salt of the metal node precur-
sor with the organic linker (precursor)
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_375-1
molecules. Conventionally, the driving force
for reaction, nucleation, and crystal growth is
provided by convective (or microwave) heating.
Alternatively, electrochemical and mechano-
chemical synthesis methods, among others,
have been described (Stock and Biswas 2012).
The MOF crystal size and morphology can be
modified by adjusting the synthesis conditions to
alter the relative rates of nucleation and crystal
growth processes or to favor growth along cer-
tain crystallographic directions.
The internal structure of MOFs displays high
mass-specific surface areas (typically in the range
of 300–6000 m2/g). It typically defines pores and
cavities in the micropore range (<2 nm) or, less
often, in the mesopore range (2–50 nm). Owing to
the large surface areas and porosities, along with
their amenability to be designed with adjustable
surface properties and pore sizes, in the range of
molecular dimensions, via either the judicious
selection of the node and linker building units or
post-synthesis modifications, MOFs have been
long considered ideal solid adsorbents for sepa-
ration applications.
The capacity of MOFs to separate molecules is
generally ascribed to either one or an interplay of
several of the following main mechanisms:
1. The “molecular sieving” effect, by virtue of
which certain molecules are prevented from
penetrating the pores of the MOF while other
molecules can enter and adsorb, depending on
their molecular size and/or shape.
2 Metal-Organic Frameworks (MOFs)
a b
Synthesis
Organic Metal oxide
‘linker’ ‘node’
Extened MOF structure
Metal-Organic Frameworks (MOFs), Fig. 1 (a) Sche-
matic representation of how an extended MOF structure is
built upon the assembly of metal (oxide) nodes and
organic linkers (Adapted from image courtesy of
2. Selective adsorption based on adsorbate-
surface interactions, whereby certain intrinsic
properties of the molecules such as their polar-
ity or capacity to establish H-bonds determine
different adsorption strengths on the surface of
the MOF and therefore the preferential
adsorption of certain compounds over others.
In certain cases, the selective adsorption of a
given molecule is favored owing to its distinct
capacity to adopt an energetically favored
packing on the surface of the MOF adsorbent
via not only adsorbate-surface but also
adsorbate-adsorbate interactions.
3. Adsorbate-induced framework
rearrangements. A number of MOF structures
exhibit flexibility, i.e., the capacity of their
framework to rearrange upon the uptake of
certain adsorbates. Strong interaction of the
MOF surface with an adsorbate can contract
the framework, resulting in a narrower pore
aperture. On the contrary, the framework of
certain MOFs can expand when the uptake of
an adsorbent surpasses a given threshold, giv-
ing rise to a wider pore aperture. The latter is
widely known as “gate-opening” effect. Such
dynamic MOF structural modifications are
often highly selective to certain adsorbates
and play a determinant role in the discrimina-
tion of molecules via either “molecular siev-
ing” or selective adsorption.
As a result of their outstanding potential for
molecular discriminations, metal-organic
Dr. Christian J. Doonan (University of Adelaide)). (b)
Representative scanning electron micrograph of NH2-
MIL-53 (Al) MOF crystals
frameworks are considered a prominent example
of solid adsorbents for separation applications
both in the gas phase and in the liquid phase
(Li et al. 2012). Fine-tuning of the pore size/
geometry via either direct synthesis or surface
modifications has resulted in MOF materials
capable of discriminating even between stereo-
isomeric molecules, i.e., those having an identi-
cal bond of constituent atoms but differing in the
orientation of these atoms in space. Attesting
their large potential as functional materials for
separation applications, MOF synthesis has
recently reached industrial scale (http://www.
chemistryviews.org/details/news/861963/1st_In
dustrial-scale_MOF_Synthesis.html).
MOFs can be applied in adsorption-desorption
separations, to which end they are shaped in the
form of macroscopic pellets or coated on
pre-shaped monoliths or meshes. They have also
been explored as constituents of membranes (Pera-
Titus 2014). On one hand, continuous, thin-film,
pure MOF membranes can be prepared by deposit-
ing or growing MOF crystals on a porous substrate,
as illustrated in the cross-sectional scanning elec-
tron membrane micrograph included in Fig. 2a. On
the other hand, composite or mixed-matrix mem-
branes incorporating MOF crystals as filler material
embedded within a polymer matrix have recently
attracted a substantial interest as they potentially
combine the easy fabrication and processing of
polymeric membranes with the intrinsic molecular
discrimination properties or MOFs. Figure 2b
(bottom) depicts a FIB-SEM micrograph of the
Metal-Organic Frameworks (MOFs)
Metal-Organic Frameworks (MOFs), Fig. 2 (a) Cross-
sectional scanning electron micrograph of a membrane
incorporating a thin film of MOF crystals on a porous
a-Al2O3 substrate (Adapted with permission from Ranjan
and Tsapatsis (2009), copyright (2009) American Chem-
ical Society). (b) Scanning electron micrograph of an
internal cross section, exposed upon milling with a
internal cross section of a mixed-matrix membrane
incorporating discrete MOF crystals within a con-
tinuous polymer matrix.
Cross-References
▶ Composite Membranes
▶ FIB-SEM Tomography, Membrane Micrograph
▶ Gas Phase
▶ Liquid Phase
▶ Mixed Matrix Membranes
▶ MOF Membrane
▶ Molecular Sieving
▶ Selective Adsorption
▶ Separation
▶ Surface Modifications
References
Hoskins BF, Robson R (1989) Infinite polymeric frame-
works consisting of three dimensionally linked
rod-like segments. J Am Chem Soc 111:5962–5964
3
focused ion beam, of a mixed matrix membrane. MOF
crystals appear as lighter objects on the darker gray back-
ground corresponding to the polymer matrix (Adapted
from Rodenas et al. (2014)). The bottom-left inset shows
a close-up detail where the different components and
boundary voids have been labeled
http://www.chemistryviews.org/details/news/861963/
1st_Industrial-scale_MOF_Synthesis.html. Accessed
6 May 2014
Kinoshita Y, Matsubara I, Higuchi T, Saito Y (1959) The
crystal structure of bis(adiponitrilo)copper(I) nitrate.
Bull Chem Soc Jpn 32:1221–1226
Li J-R, Sculley J, Zhou H-C (2012) Metal-organic frame-
works for separations. Chem Rev 112:869–932
MacGillivray LR (2010) Metal-organic frameworks:
design and application. Wiley-VCH, Weinheim
MacGillivray LR, Lukehart CM (2014) Metal-organic
framework materials. Wiley-VCH, Weinheim
Pera-Titus M (2014) Porous inorganic membranes for
CO2 capture: present and prospects. Chem Rev
114:1413–1492
Ranjan R, Tsapatsis M (2009) Microporous metal
organic framework membrane on porous support
using the seeded growth method. Chem Mater
21:4920–4924
Rodenas T, van Dalen M, Garcia-Perez E, Serra-Crespo P,
Zornoza B, Kapteijn F, Gascon J (2014) Visualizing
MOF mixed matrix membranes at the nanoscale:
towards structure-performance relationships in CO2/
CH4 separation over NH2-MIL-53(Al)@PI. Adv
Funct Mater 24:249–256
Stock N, Biswas S (2012) Synthesis of metal-organic
frameworks (MOFs): routes to various MOF topolo-
gies, morphologies, and composites. Chem Rev
112:933–969
M
Microcapsules
Angela C. Macedo1,2 and F. Xavier3
1
ISMAI – University Institute of Maia, Avenida
Carlos Oliveira Campos, Avioso S. Pedro,
Portugal
2
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
3
Department of Chemical Engineering,
University of Porto, Porto, Portugal
Microcapsules are discrete portions of an aque-
ous medium (core) suspended in another aqueous
medium, with immiscibility (and hence stability)
being assured usually by a lipid layer (membrane)
that resembles the phospholipid bilayer of cell
membranes. They are often spherically shaped
with a continuous membrane surrounding the
core, but may take asymmetrical shapes – e.g.,
with a number of smaller droplets of the core
material embedded throughout the microcapsule;
microcapsules may also have one or multiple
walls around the core, arranged in strata of vary-
ing thickness. The core – i.e., the encapsulated
substance – has also been termed active ingredi-
ent, nucleus, or internal phase; the membrane –
i.e., the encapsulating material – is also referred
to as coating or wall (Jyothi et al. 2009).
The purpose of microencapsulation is to con-
fine the core material within the capsule mem-
brane and protect it. Alternatively, core materials
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_381-5
may be encapsulated so that they will be released
gradually through the membrane (known as con-
trolled release or diffusion) or when release is
intended to occur after a given period of
time – upon a change in external conditions that
trigger the wall to rupture, melt, or dissolve.
Microcapsules can be classified, according to
the type of membrane, as slow release, imperme-
able, and smart (Jackson and Lee 1991).
In the case of slow-release membranes, the
encapsulated component is released from the cap-
sules for a longer time, depending on the final
usage intended therefore. The release time
depends on the membrane type – in particular
its composition and thickness – and may vary
from few days to several months (Marini
et al. 1991). The core component may be water-
or solvent-based and may assume a solid or a
liquid state. Applications that regularly resort to
such a type of membrane are fragrances and
flavors, pesticides, and reactive chemicals. An
example of the former is chewing gum – in
which flavors are supposed to last longer than
the first bites. Another example is when flavor-
ings are comprised of two reactive components
that should not react and thus lose their flavor
potential prematurely; in this case, the two com-
ponents are microencapsulated individually. Pes-
ticides are also encapsulated to bring about
release over time, thus allowing farmers to
apply them less often and at lower (and thus less
toxic) concentrations than in a single use; the
environment is better protected, and a more
2 Microcapsules
efficient strategy for pest control results. Many
varieties of oral and injected pharmaceutical for-
mulations are microencapsulated as well – not
only to effect release of the active component
(s) over a longer period of time but also to guar-
antee release only at certain locations in the body.
One example is aspirin, which can cause peptic
ulcers and bleeding if doses are introduced all at
once: slow release decreases its detrimental risks
on the stomachal mucosa (Arshady 1993).
Impermeable membranes have the active
component encapsulated inside the membrane;
the chief purpose is to prevent release and thus
assure complete isolation from the environment.
This solution has been proven useful for phase
change materials targeted at textile and building
industries: the said materials absorb or release
heat in response to changes in environmental
temperatures – when temperatures rise, they
melt thus absorbing excess heat and causing a
sensation of cool; conversely, as temperatures
fall, phase change materials release heat as they
solidify, thus providing a sensation of warmth.
This unique property of microencapsulated phase
change materials can be harnessed to increase the
comfort level of users of sports equipment and
military clothing; they have even been used in
NASA-patented thermal protection systems for
spacecraft. Additionally, the use of impermeable
membranes is useful in retaining volatile flavors:
encapsulation extends the shelf life of the food
product, by retaining flavors that would otherwise
evaporate and be readily lost.
Finally, when the core substances should be
released only in certain circumstances (e.g., when
pH or temperature changes or when exposed to
mechanical forces), smart membranes are
selected. Successful examples are
microencapsulated fragrances that operate on
the principle of scratch and sniff for release and
some flavorings that must be protected from oxi-
dation caused by exposure to light – so they
should not be released prior to mastication
(Obeidat 2009).
References
Arshadi R (1993) Microcapsules for food.
J Microencapsul 10:413–435
Jackson LS, Lee K (1991) Microencapsulation and the
food industry. Lebensm Wiss Technol 24:289–297
Jyothi NVN, Prasanna M, Prabha S, Ramaiah PS,
Srawan G, Sakarkar SN (2009) Microencapsulation
techniques. Internet J Nanotechnol 3. doi:10.5580/
27bb
Marini JO, Mendes RW, Rekhi GS, Jambhekar SS
(1991) Some factors affecting the release of drug
from membrane coated slow release tablets. Drug
Dev Ind Pharm 17:865–877
Obeidat WM (2009) Recent patents review in microen-
capsulation of pharmaceuticals using the emulsion
solvent removal methods. Recent Pat Drug Deliv
Formul 3:178–192
M
Microcapsule Production by
Membrane Operations
Angela C. Macedo1,2 and F. Xavier3
1
ISMAI – University Institute of Maia, Avenida
Carlos Oliveira Campos, Avioso S. Pedro,
Portugal
2
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
3
Department of Chemical Engineering,
University of Porto, Porto, Portugal
Microencapsulation is the technology of packag-
ing individual particles of solid, liquid, or gas-
eous materials in capsules in the micrometer to
millimeter range, which can release their contents
at controlled rates or under specific conditions
(Chabala et al. 1978). Upon microencapsulation,
liquid and gaseous materials are more easily han-
dled since they acquire a solid-like form; it may
also afford extra protection, owing to the barrier
around hazardous materials.
Processes of microencapsulation have tradi-
tionally been categorized into two groups: chem-
ical and physical (or mechanical) processes
(Prasad and Sarkar 1992). Indication of which
category is at stake may come from whether the
microcapsules are produced in a liquid-
containing tank as in chemical processes, as
opposed to physical processes that employ a gas
phase. There are in practice seven major methods
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_382-6
of microcapsule production: coacervation, inter-
facial polymerization, phase separation, spray
drying, fluid bed coating, centrifugal extrusion,
and rotational suspension.
Coacervation takes advantage of the reaction
between aqueous solutions of cationic and
anionic polymers, e.g., gelatin and Arabic gum;
such polymers form a concentrated, complex
phase called coacervate – which maintains an
equilibrium with a dilute supernatant phase. As
the water-immiscible core material is introduced
into the system, thin films of coacervate coat the
dispersed droplets of core material, which are
then solidified – thus conferring a harvestable
form to the capsules (Klaassen and Jansen
2001). This is probably the most common method
of microencapsulation (Ocak et al. 2011); its
major advantage is the very high payload (up to
99 %) and controlled release possibilities
(Jun-Xia et al. 2011).
The method of interfacial polymerization is
characterized by membrane formation via rapid
polymerization of monomers at the surface of the
particles of (dispersed) core material.
A multifunctional monomer is accordingly
dissolved in the core material, and this solution
is dispersed in an aqueous phase; a reactant with
the monomer is added to the aqueous phase, so
polymerization quickly ensues at the surfaces of
the core particles to eventually form the wall.
This method is appropriate for preparation of
bigger microcapsules, although the commercial
size ranges are 20–30 mm and 3–6 mm.
2 Microcapsule Production by Membrane Operations
Phase separation is generally grouped with
other chemical encapsulation techniques, despite
realization that no actual chemical reaction is
usually involved in the process. It utilizes two
polymers soluble in a common solvent, but
which do not mix with each other in solution;
hence, they form two separate phases – one rich
in the polymer intended to form the membrane,
and the other rich in the incompatible polymer
meant to induce phase separation. The latter will
not be a part of the finished microcapsule mem-
brane, except for traces caught inside the capsule
as impurities.
During spray drying, an emulsion is prepared
by dispersing the core material (usually an oil or
active ingredient immiscible with water) into a
concentrated solution of membrane material until
the desired size of drops is attained. This emul-
sion is then atomized into a spray of droplets by
pumping the slurry through a rotating disk into
the heated compartment of a spray drier: the
water portion of the emulsion consequently evap-
orates, thus yielding dried microcapsules of var-
iable shape and containing scattered droplets of
core material. The microcapsules are finally col-
lected via continuous discharge from the spray-
drying chamber.
Fluid bed coating is restricted to encapsulation
of solid core materials, including liquids
absorbed into porous solids. Such particles are
suspended on a jet of air and then covered by a
spray of liquid coating material; the microcap-
sules are then moved to an area to allow solidifi-
cation of their membranes via cooling or solvent
vaporization. The process of suspending,
spraying, and cooling may be iterated until the
walls attain the intended thickness. When the
spray nozzle is located at the bottom of the fluid-
ized bed of particles, the process is usually known
as the Wurster process.
Centrifugal extrusion processes generally lead
to microcapsules of a larger size, typically from
250 mm up to a few mm. The core and membrane
materials (which are supposed to be immiscible)
are pushed through a spinning two-fluid nozzle;
this procedure forms an unbroken rope that natu-
rally splits into round droplets directly after clear-
ing the nozzle. The continuous walls of these
droplets are solidified either via cooling or by a
gelling bath depending on the composition and
features of the coating material.
When applying the rotational suspension sep-
aration (or spinning disk) method, the internal
phase is dispersed into the liquid wall
material – and the mixture is admitted onto a
turning disk. Droplets of pure membrane material
are thrown off of the rim of that disk – along with
discrete particles of core material enclosed in a
skin of wall material. After solidification by
cooling, the microcapsules are collected sepa-
rately from the particles of membrane material.
References
Chabala M, Duckova K, Vitkova M (1978) Microcapsules
and micro-coated compressed tablets. I. Names, defi-
nitions and preparation methods of microcapsules.
Farm Obz 47:449–458
Jun-xia X, Hai-yan Y, Jian Y (2011) Microencapsulation
of sweet orange oil by complex coacervation with
soybean protein/gum Arabic. Food Chem
125:1267–1272
Klaassen R, Jansen AE (2001) The membrane contactor.
Environmental applications and possibilities. Environ
Prog 20:37–43
Ocak B, G€ ul€
umser G, Baloğlu E (2011) Microencapsula-
tion of Melaleuca alternifolia (tea tree) oil by using
simple coacervation method. J Essent Oil Res 2:58–65
Prasad R, Sarkar KK (1992) Membrane-based solvent
extraction. In: Ho WSW, Sirkar KK (eds) Membrane
handbook. van Nostrand Reinhold, New York
M
Microchannel Emulsification
Goran Vladisavljevic1, Isao Kobayashi2 and
Mitsutoshi Nakajima3
1
Chemical Engineering Department,
Loughborough University, Leicestershire, UK
2
National Food Research Institute, National
Agriculture and Food Research Organization,
Tsukuba, Ibaraki, Japan
3
Faculty of Life and Environmental Sciences,
University of Tsukuba, Tsukuba, Ibaraki, Japan
Microchannel (MC) emulsification is a process of
forming emulsions by injecting a dispersed phase
through a multitude of microfabricated MC
arrays into the continuous phase. Single-crystal
silicon MC arrays can be fabricated in the form of
horizontal grooves (Kikuchi et al. 1992) or verti-
cal straight-through holes (Kobayashi
et al. 2002).
Grooved-type MC plates are fabricated by
photolithography and anisotropic wet etching
and can be used in dead-end or cross-flow con-
figuration. In a dead-end module (Fig. 1a), paral-
lel grooves fabricated on a terrace are arranged on
all four sides of the plate. The dispersed phase
supplied through a central hole is forced to flow
through MCs, because the plate is sealed with a
transparent cover plate. The dispersed phase
takes a disklike shape on terrace, and this shape
is characterized by a higher interfacial area per
unit volume than a spherical shape, resulting in
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_383-22
hydrodynamic instability. This instability is a
driving force for spontaneous transformation of
dispersed phase into spherical droplets (Sugiura
et al. 2002).
Dead-end modules provide a dispersed phase
flow rate less than 0.1 mL h–1, due to limited
number of MCs (less than 2,000). Cross-flow
modules with grooved MC arrays are suitable
for higher production scales because multiple
cross-flow channels with MC arrays can be incor-
porated on a single plate (Kobayashi et al. 2010).
The simplest cross-flow module (Fig. 1b) has
only one cross-flow channel and two holes at its
both ends for introduction and withdrawal of the
continuous phase. The purpose of cross flow is to
collect droplets from the module and not to con-
trol the droplet size. In the dripping regime, the
droplet size is independent on the flow rate of
dispersed or continuous phase. Cross-flow MC
plates with multiple cross-flow channels are
available with a maximum cross section of
6060 mm and 12,000 MCs arranged in 14 par-
allel arrays (Kobayashi et al. 2010).
Modules with grooved-type plates have a lim-
ited throughput, because MCs are arranged on the
plate surface in longitudinal direction, and feed
channels for the dispersed and continuous phase
are provided on the plate surface. A vertical array
of straight-through MCs fabricated by photoli-
thography and deep reactive ion etching allows
better utilization of the plate surface resulting in
significantly higher throughputs. Straight-
through MCs may have a symmetric and
2 Microchannel Emulsification

a Dead end MC module b Cross flow MC module

dispersed phase

Continuous
terrace phase

dispersed phase
Glass plate
MC
Glass plate

Oil
Continuous
phase

Oil
Stagnant Continuous phase

Microchannel Emulsification, Fig. 1 Grooved-type MC plates for MC emulsification (Published with permission
from Vladisavljević et al. 2012)

a Symmetric MC plate b Asymmetric MC plate c Symmetric MN plate

Glass plate Glass plate Glass plate

dispersed phase dispersed phase dispersed phase

Microchannel Emulsification, Fig. 2 Straight-through MC plates for MC emulsification (Published with permission
from Vladisavljević et al. 2012)

asymmetric structure. Symmetric MCs (Fig. 2a) size uniformity than circular MCs, and an aspect
are of the same size and shape (e.g., circular or ratio of the slots should be at least 3 (Kobayashi
rectangular) along the whole cross section of the et al. 2004). Asymmetric MC plate has circular
plate. Rectangular MCs provide higher droplet channels on the upstream (bottom) side and slots
Microchannel Emulsification
on the downstream (top) side (Fig. 2b). Asym-
metric plate is useful when the dispersed phase
viscosity is less than 1 mPa s, e.g., when the
dispersed phase is a volatile hydrocarbon
(Kobayashi et al. 2005). Straight-through
micronozzle (MN) array (Fig. 2c) are used to
increase the velocity of continuous phase around
the growing droplets during detachment, because
the channel outlets are above the plate surface,
which could be useful if the viscosity of the
dispersed phase is high (Sugiura et al. 2005).
References
Kikuchi Y, Sate K, Ohki H, Kaneko T (1992) Optically
accessible microchannels formed in a single-crystal
silicon substrate for studies of blood rheology.
Microvasc Res 44:226–240
Kobayashi I, Nakajima M, Chun K, Kikuchi Y, Fujita
H (2002) Silicon array of elongated through-holes for
monodisperse emulsion droplets. AIChE
J 48:1639–1644
3
Kobayashi I, Mukataka S, Nakajima M (2004) Effect of
slot aspect ratio on droplet formation from silicon
straight-through microchannels. J Colloid Interface
Sci 279:277–280
Kobayashi I, Mukataka S, Nakajima M (2005) Novel
asymmetric through-hole array microfabricated on a
silicon plate for formulating monodisperse emulsions.
Langmuir 21:7629–7632
Kobayashi I, Wada Y, Uemura K, Nakajima M (2010)
Microchannel emulsification for mass production of
uniform fine droplets: integration of microchannel
arrays on a chip. Microfluid Nanofluid 8:255–262
Sugiura S, Nakajima M, Kumazawa N, Iwamoto S, Seki
M (2002) Characterization of spontaneous
transformation-based droplet formation during
microchannel emulsification. J Phys Chem
B 106:9405–9409
Sugiura S, Oda T, Izumida Y, Aoyagi Y, Satake M,
Ochiali A, Ohkohchi N, Nakajima M (2005) Size
control of calcium alginate beads containing living
cells using micro-nozzle array. Biomaterials
26:3327–3331
Vladisavljević GT, Kobayashi I, Nakajima M (2012) Pro-
duction of uniform droplets using membrane,
microchannel and microfluidic emulsification devices.
Microfluid Nanofluid 13:151–178
M

Microsolute • Microfiltration – Microsolute is represented

Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Microsolute represents an operational term which
denotes any diffusible (able to pass through a
membrane) solute(s) in a solution that also con-
tains nondiffusible (retained by membrane) sol-
ute(s), macrosolute. Membrane filtration may be
used to treat such solution to recover microsolute
which is valuable from solution or to filter
microsolute which is regarded as impurity out of
the solution.
Distinction of species considered as
microsolute depends on membrane process
which is used to treat the solution (Cheryan
1998), in the case of:
by macromolecules and species with smaller
particle sizes.
• Ultrafiltration – Microsolute represents disso-
ciated acids, divalent salts, sugars, and species
with smaller particle sizes.
• Nanofiltration – Undissociated acids and
monovalent salts can be recovered or
filtered out.
• Reverse osmosis – Only water passes through
membrane and thus can be considered as
microsolute.
References
Cheryan M (1998) Ultrafiltration and microfiltration hand-
book. CRC press, Boca Raton

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_385-6
M
Milk Fat Hydrolysis
Angela C. Macedo1,2 and F. Xavier3
1
ISMAI – University Institute of Maia, Avenida
Carlos Oliveira Campos, Avioso S. Pedro,
Portugal
2
LEPABE - Laboratory of Engineering of
Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
3
Department of Chemical Engineering,
University of Porto, Porto, Portugal
Milk contains ca. 3.4 % total milk fat – which has
probably the most complex fatty acid profile of
all edible fats. Despite the over 400 individual
fatty acid residues identified, only 15–20 account
for 90 % of milk fat: saturated (4:0, 6:0, 8:0, 10:0,
12:0, 14:0, 16:0, and 18:0), monounsaturated
(16:1 and 18:1), and polyunsaturated (18:2 and
18:3). Some of these fatty acids are found to be in
very low levels, but they are also characterized by
very low odor thresholds – so they contribute
unique and desirable flavor keynotes.
Milk fat can be degraded chiefly by oxidation
upon exposure to light and hydrolysis in the pres-
ence of enzymes; these two chemical processes
follow quite different chemical mechanisms.
Enzymes able to hydrolyze fat are called lipases
(or glycerol ester hydrolases, EC 3.1.1.3), and the
process is often referred to as lipolysis. These
enzymes possess a catalytic triad similar to
those in proteases but along evolution have
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_387-7
developed a portion of the peptide chain into a
lid that covers the active site – which opens (and
thus permits access to substrate) only when a
water/lipid interface is present; this unique fea-
ture makes their action distinct from that of clas-
sical esterases in that they are activated by lipids
in emulsified form.
Lipases suitable for modification of milk
fat – toward incorporation into baked goods and
the like – are commercially obtained from a range
of sources: milk (lipoprotein lipase), pancreas
(pancreatic lipase), molds (e.g., Aspergillus
niger, Geotrichum candidum, and Penicillium
roqueforti), bacteria (e.g., Achromobacter
lipolyticum and Pseudomonas fluorescens), and
the gastrointestinal tract (kid and lamb pregastric
esterases). Several genetically engineered micro-
organisms may also produce such enzymes, both
in endogenous and exogenous forms (Fox and
McSweeney 1998).
Lipases also have the ability to catalyze the
reverse of hydrolysis – i.e., ester synthesis, under
microaqueous conditions. These two basic pro-
cesses may then be combined in a sequential
fashion to lead to interesterification reactions.
The underlying catalytic mechanism resembles
closely natural metabolic pathways, so lipase-
based processes are viewed as more environment
friendly than typical bulk chemical syntheses.
Because of their low activation energies, lipase-
mediated processes require mild temperature and
pH, so energy consumption is small and there is
little thermal damage to either reactants or
2 Milk Fat Hydrolysis
products. Owing to their chemical selectivity and
stereoselectivity, lipases may generate high
added-value products that are not readily avail-
able in natural feedstocks.
The essential manufacturing steps of hydro-
lyzed (or lipolyzed) milk fat include: preparation
of condensed milk or butter oil, preparation of
standardized lipase system in water, combination
of milk fat substrate and lipase system, homoge-
nization to form a stable emulsion (thereby pro-
moting maximum interfacial enzyme activity),
incubation at controlled temperature (until a
specified degree of hydrolysis has been
achieved), pasteurization (to completely inacti-
vate residual lipase), and final standardization,
spray drying (or alternative formulation), and
packaging.
Controlled enzymatic hydrolysis of milk fat
has been a common practice in the dairy industry
to produce butter- or cheese-like products and
flavor additives (Walstra et al. 1999). The intrin-
sic composition of lipolyzed milk fat can indeed
impart a range of effects on the sensory profiles of
foods: at very low addition levels, a sensation of
richness is obtained without any detectable acid-
ity; as addition levels increase, the resulting
flavors resemble cream or butter; and when addi-
tion levels are even higher, the outcome flavor
suggests cheese.
References
Fox PF, McSweeney PLH (1998) Milk lipids. In: Fox PF,
McSweeney PLH (eds) Dairy chemistry and biochem-
istry. Blackie Academic/Professional Publishers, Lon-
don, pp 67–146
Walstra P, Geurts TJ, Noomen A, Jellema A, van Boekel
MAJS (1999) Dairy technology, principles of milk
properties and processes. Marcel Dekker, New York
Further Reading
Balcão VM, Paiva AL, Malcata FX (1996) Bioreactors
with immobilized lipases: state of-the-art. Enzyme
Microb Technol 18:392–416
M
Mixed Conducting Membranes
Juergen Caro
Institute of Physical Chemistry and
Electrochemistry, Leibniz University Hannover,
Hannover, Germany
Synonyms
Electronic and ionic conductivity
A mixed conducting membrane can transport
both electrons and ions as shown in the scheme
below (Fig. 1); in most cases the ionic conductiv-
ity is based on oxygen ions or protons, but in
principle also other ions like halogenide or chal-
cogenide anions are mobile and can be
transported. Perovskites with the crystallographic
structure ABO3 (derived from the mineral perov-
skite CaTiO3) are a prominent example for a
materials class with mixed conductivity: Oxygen
ions can be transported via vacancies in the oxy-
gen lattice (denoted as oxygen deficiency d in the
perovskite structure ABO3-d ), and electrons can
be transported via redox cycles of the cations if
they can occur in different oxidation states (e.g.,
Fen+, Con+, Tin+). The concentration of vacancies
in the oxygen lattice can be engineered by bring-
ing cations with a low valency on the position of
high-valency cations (Sunarso et al. 2008).
In contrast to mixed conducting membranes,
the membranes used in fuel cells for electricity
generation show only ionic conductivity: In the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_388-1
solid oxide fuel cell (SOFC), the membrane
material such as Ce0.8Gd0.2O2-d (CGO) shows
only oxygen ionic conductivity and no electronic
conductivity, and the electrons have to go there-
fore an outer circuit, whereas the oxygen ions
move through the CGO. In the case of the poly-
mer electrolyte membrane (PEM) fuel cell, the
membrane material Nafion shows also only pro-
ton conductivity (Grotthuss mechanism) but no
electronic conductivity, and also here the elec-
trons have to go an outer circuit, whereas the
protons can diffuse through the hydrated Nafion
pores.
Therefore, mixed conducting materials are
often called materials with an inner shortcut
since oxygen ions and electrons or protons and
electrons move through the material.
In the scheme below (Fig. 1), the phenomenon
of mixed conductivity is illustrated for a perov-
skite membrane. On the membrane side with a
high oxygen partial pressure (e.g., air), molecular
oxygen is split at the surface into atoms, the
atoms become ionized, and the oxygen ions
occupy empty oxygen ion positions in the oxygen
lattice (vacancy) and become transported by a
diffusion mechanism to the membrane side with
a lower oxygen partial pressure (vacuum, sweep
gas) where they back-transform into molecular
oxygen. For most perovskites, the electronic con-
ductivity is orders of magnitude higher than the
ionic one.
2 Mixed Conducting Membranes
Mixed Conducting Membranes, Fig. 1 Schema of
oxygen transport through a perovskite membrane with
mixed conductivity (copyright Caro, Uni Hannover):
Molecular oxygen is split at the membrane side with
high oxygen partial pressure (normally air) into atomic
oxygen species O* which are adsorbed at the surface.
After ionization, the oxygen ions O2 enter the mixed
conducting membrane material. By a diffusional hopping
process among the vacancies in the oxygen lattice, the
oxygen ions can enter the membrane side facing a low
oxygen partial pressure. Here the reverse process takes
References
Shao Z, Dong H, Xiong G, Cong Y, Yang W (2001)
Performance of a mixed-conducting ceramic mem-
brane reactor with high oxygen permeability for meth-
ane conversion. J Membr Sci 183:181–192
place: The oxygen ions decompose into atomic surface
oxygen O* and electrons, and the latter diffuse to the air
side where they are consumed in the oxygen ionization.
The surface oxygen species O* dimerize and form molec-
ular oxygen which is desorbed into the gas face. To keep
the oxygen partial pressure low on the permeate side
(driving force for permeation), the molecular oxygen has
to be removed by pumping or a sweep gas; it can be
also consumed in a chemical oxidation reaction
(Shao et al. 2001)
Sunarso J, Baumann S, Serra JM, Meulenberg WA, Liu S,
Lin YS, Diniz da Costa JC (2008) Mixed
ionic–electronic conducting (MIEC) ceramic-based
membranes for oxygen separation. J Membr Sci
320:13–41
M
Modified Cellulose
Hongyang Ma, Benjamin S. Hsiao and
Benjamin Chu
Department of Chemistry, Stony Brook
University, Stony Brook, NY, USA
Modified cellulose refers to chemical modifica-
tions of mainly hydroxyl groups in the cellulose
backbone. There are primary and secondary
hydroxyl groups in each cellulose unit, where
the C6-hydroxyl group, being the primary one,
exhibits higher reactivity. Typical reactions of
hydroxyl groups in cellulose, including oxida-
tion, esterification, etherification, urethanization,
amidation, and non-covalent modifications
(Habibi 2014), are shown in Fig. 1.
There are two approaches to modify cellulose
for membrane preparation: homogeneous and
heterogeneous. A well-known membrane pre-
pared from homogeneously modified cellulose
is the cellulose acetate-based reverse osmosis
membrane, fabricated by the phase inversion
method (Strathmann et al. 1971). Cellulose
esters, including nitrocellulose, have also been
employed to fabricate commercially available
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_390-1
microfiltration membranes by using the phase
inversion method for drinking water purification
(Ulbricht 2006). The goals for homogeneous
modification of cellulose are to adjust the prop-
erties of cellulose for specific applications. How-
ever, cellulose cannot be dissolved in common
organic solvents. Thus, ionic liquids have been
used to dissolve cellulose, thereby expanding the
family of homogeneously modified cellulose for
membrane fabrication (Ma et al. 2010). Never-
theless, heterogeneous modification of cellulose
has, so far, been more frequently used. As an
example, cellulose nanofibers extracted from nat-
ural cellulose with a heterogeneous oxidation
reaction followed by mechanical treatment
(Isogai et al. 2011) can afford viable surface
modifications. The surface of cellulose
nanofibers with a nanoscaled diameter is covered
with hydroxyl, carboxylate, and aldehyde groups
which can be further modified following the
above strategy. Cross-linked cellulose nanofibers
with functional surfaces have been used as a
barrier layer in micro- and ultrafiltration mem-
branes for water purification to remove contami-
nants. These membranes showed superior
filtration efficiency when compared with com-
mercial membranes (Ma et al. 2011).
2 Modified Cellulose

O O
R
R HN O Cellulose
O OH
Cellulose Cellulose

O R
R H O
R NCO
O
O
OH O R
COONa X
OH R
TEMPO/NaBr/NaClO O HO
O Cellulose
Cellulose O
HO OH O
OH n
O O

HX R1 O R2
HNO3
O
X O R1(R2)
Cellulose Cellulose
NO2
O
Cellulose

Modified Cellulose, Fig. 1 Chemical modifications of cellulose for membrane science and technology

References containing cellulose barrier layer. J Mater Chem

Habibi Y (2014) Key advances in the chemical modifica-
tion of nanocelluloses. Chem Soc Rev 43:1519–1542
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized
cellulose nanofibers. Nanoscale 3:71–85
Ma H, Yoon K, Rong L, Mao Y, Mo Z, Hollander Z,
Gaiteri J, Hsiao BS, Chu B (2010) High-flux thin-
film nanofibrous composite ultrafiltration membranes
20:4692–4704
Ma H, Burger C, Hsiao BS, Chu B (2011) Ultra-fine
cellulose nanofibers: new nano-scale materials for
water purification. J Mater Chem 21:7507–7510
Strathmann H, Scheible P, Baker RW (1971) A rationale
for the preparation of Loeb-Sourirajan-Type cellulose
acetate membranes. J Appl Polyner Sci 15:811–828
Ulbricht M (2006) Advanced functional polymer mem-
branes. Polymer 47:2217–2262
M
Modularity
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende (CS), Italy
The modularity takes into account the changes of
the plant size due to variations of the plant pro-
ductivity (Criscuoli and Drioli 2007). It is a typ-
ical property of membrane operations, since it is
possible to add modules, also without having
foreseen the expansion of the system in the sys-
tem design phase.
To compare the modularity of membranes
with that of traditional units, a modularity index
is defined. Given a variation of the plant
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_392-1
productivity (e.g., from productivity1 to produc-
tivity2), this metric compares the variations of the
area (for membranes) with those of the volume
(for conventional systems). The membrane sys-
tem has a higher modularity if the modularity
metric is lower than 1; modularity values higher
than 1 are in favor of the traditional system.
 
Membrane area2 Productivity2

Membrane area1 Productivity1
Modularity ¼  
Conventional unit volume2 Productivity2

Conventional unit volume1 Productivity1
References
Criscuoli A, Drioli E (2007) New metrics for evaluating
the performance of membrane operations in the logic
of process intensification. Ind Eng Chem Res
46:2268–2271
M
Mosaic Membranes
Karel Friess
Department of Physical Chemistry, University of
Chemistry and Technology Prague, Prague,
Czech Republic
Synonyms
Charged mosaic membrane; Ion-exchange
mosaic membranes
Mosaic membranes (MM) are composed of mac-
roscopic fixed domains of cation exchange
(negatively charged) and anion exchange
(positively charged) arranged in parallel resins
separated by a neutral polymer or ion-exchange
channel matrix (see Fig. 1) (Soellner 1932;
Strathmann 2004; Wu et al. 2006). Inside chan-
nels with positive charge is higher concentration
of negatively charged anions and vice versa. MM
are effective in concentrating of diluted electro-
lytes in the presence of hydrostatic pressure and
chemical potential gradient (piezodialysis) (Sata
2004). Mosaic membrane can be used also for
separation of electrolytes from nonelectrolytes.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_395-1
MM can be prepared (Sata 2004) by various
methods: (i) cross-linking reaction of two differ-
ent copolymers with ion-exchange resins;
(ii) cutting a laminated block of alternating cat-
ion-/anion-exchange membranes into films
(perpendicular to the membrane surface); (iii)
casting (layer-by-layer) a block-copolymer film
with one exchange groups, insulating layer, and
block-copolymer film with opposite exchange
groups; (iv) casting of a film using a dispersion
containing ion-exchange microsphere gels and
polymer.
Alternative approaches of preparation of MM
consist in ion-exchange asymmetric membrane
with a uniform distribution of counterion-
exchange particles in the dense integral skin
layer (Linder and Kedem 2001) or in use of
hybrid materials containing both positive and
negative charges (Liu et al. 2005).
Cross-References
▶ Ion-Exchange Membranes
▶ Piezodialysis
2 Mosaic Membranes
Mosaic Membranes, Fig. 1 Schematic draw of struc-
ture of mosaic membrane configurations: cation- and
anion-exchange domains in neutral matrix (left), cation-
References
Linder C, Kedem O (2001) Asymmetric ion exchange
mosaic membranes with unique selectivity. J Membr
Sci 181:39–56
Liu J, Xu T, Gong M, Fu Y (2005) Fundamental studies of
novel inorganic-organic charged zwitterionic hybrids:
3. New hybrid charged mosaic membranes prepared by
modified metal alkoxide and zwitterionic process.
J Membr Sci 260:26–36
Sata T (2004) Ion exchange membranes. Preparation,
characterization, modification and application. RSC
exchange domains in anion-exchange matrix (middle),
and anion-exchange domains in cation-exchange matrix
(right)
Advancing the Chemical Science, The Royal Society
of Chemistry, Cambridge
Soellner K (1932) Über mosaik membranen. Biochem
Z 244:370–381
Strathmann H (2004) Ion-exchange membranes. Separa-
tion processes. Elsevier, Amsterdam
Wu C, Xu T, Liu J (2006) Charged hybrid membranes by
the sol-gel approach: present states and future perspec-
tives. In: Newman AM (ed) Focus on solid state chem-
istry. Nova Science Publishers, New York
M
Multilayered Thin Film Composite
Membranes
Suzana Pereira Nunes
Division of Biological and Environmental
Sciences and Engineering, Nanostructured
Polymeric Membranes Lab, King Abdullah
University of Science and Technology (KAUST),
Thuwal, Saudi Arabia
A thin film composite (TFC) membrane is a
bilayer of multilayer membrane constituted by
an asymmetric porous structure and a thin and
dense-selective film. The asymmetric structure
gives mechanical stability to the membrane,
without restricting flux. It is normally obtained
by phase inversion and frequently based on
polysulfone. In the most known TFC membranes,
the thin layer is based on polyamide and is pre-
pared by interfacial polymerization (Nunes and
Peinemann 2006). Having a typical thickness
lower than a micrometer, the dense layer gives
the needed selectivity for salt (reverse osmosis)
or other small solutes, without adding a high
barrier for water transport. Interfacial polymeri-
zation as a simple and effective method for TFC
membranes started to be explored by Cadotte
et al. (1980) in the 1960s. Initially polyethy-
lenimine and diisocyanate were used as mono-
mers, resulting in what was known as NS-100
membrane. The most used system for thin film
preparation is currently a combination of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_398-1
m-phenylenediamine (MPD) and trimesoyl chlo-
ride (TMC), as shown in Fig. 1. The porous
asymmetric support is filled with an aqueous
solution of MPD and immersed in an organic
solution containing TMC (e.g., in hexane). By
choosing immiscible solvents, the reactants will
only contact each other at the interface. The reac-
tion takes place immediately to form a defect-free
polymeric film. Once the film is formed, the
monomers are no longer in contact anymore,
limiting the thickness. The system in Fig. 1 led
to the development of reverse osmosis mem-
branes such as FT-30, commercialized by Dow,
which has dominated great part of the desalina-
tion market with salt rejection higher than 99.2 %
and fluxes of around 1 m3 m 2 day 1.
Comprehensive reviews on thin film compos-
ite membranes for reverse osmosis and
nanofiltration were published by Petersen
(1993) and, more recently, by Lee et al. (2011).
Despite of the success of the polyamide mem-
branes shown in Fig. 1, a drawback is still the
chlorine resistance, which was also poor for the
NS-100. Other chemical compositions have been
proposed over the years to improve resistance,
such as polypiperazine-amide-based films. How-
ever, the overall combination of high flux and salt
rejection is the most important target. The devel-
opment of TFC membranes had a strong contri-
bution to the widespread implementation of
desalination plants from seawater.
TFC membranes are now applied also for
emergent processes such as forward osmosis
2 Multilayered Thin Film Composite Membranes
Multilayered Thin Film
Composite Membranes,
Fig. 1 Interfacial
polymerization in the
formation of thin film
composite membranes
Multilayered Thin Film Composite Membranes,
Fig. 2 Scanning electron microscopy image of a polyam-
ide TFC membrane
and pressure retarded osmosis. The requirements
for these applications are different, which operate
at much lower pressure than reverse osmosis
(RO). High flux is even more important. While
the resistance to compaction is not as important
as for RO, an opener support is desired to avoid
accumulation of draw solutes in the membrane
and concentration polarization effects.
A typical ridge-and-valley structure is
observed on TFC membranes, as seen in Fig. 2.
The morphology of the thin layer is affected
by the porosity of the substrate. Larger pores can
promote convection at the interface during the
polymerization and a rougher structure. Changes
in the monomer concentrations and addition of
solvents of intermediate miscibility affect the
morphology and thickness, as well as the integra-
tion of hydrophilic intermediate layers
(Livazocic et al. 2015). More recently TFC has
been applied to filtration in organic solvents
(Karan et al. 2015) reaching permeances of
more than 112 l m 2 h 1 bar 1.
Apart from the thin film composite mem-
branes prepared by interfacial polymerization,
other methods can be used to form a selective
layer leading to composite membranes:
(a) Dip coating of a diluted polymer solution on a
porous support, followed by solvent
evaporation
(b) Film deposit by plasma
(c) Separated casting, delamination, and deposit
on a support
(d) Dip coating of a monomer solution, followed
by reaction (e.g., by UV radiation or heat)
References
Cadotte JE, Petersen RJ, Larson RE, Erickson EE
(1980) A new thin-film composite seawater reverse
osmosis membrane. Desalination 32:25–31
Karan S, Jiang Z, Livingston AG (2015) Sub–10 nm poly-
amide nanofilms with ultrafast solvent transport for
molecular separation. Science 348:1347–1351
Lee KP, Arnot TC, Mattia D (2011) A review of reverse
osmosis membrane materials for
Multilayered Thin Film Composite Membranes
desalination – development to date and future poten-
tial. J Membr Sci 370:1–22
Livazocic S, Behzad AR, Peinemann K-V, Nunes SP
(2015) Cellulose multilayer membranes manufacture
with ionic liquid. J Membr Sci 490:282–293
3
Nunes SP, Peinemann KV (2006) Membrane technology
in the chemical industry. Wiley-VCH, Weinheim
Petersen RJ (1993) Composite reverse osmosis and
nanofiltration. J Membr Sci 83:81–150
N
Nanocomposite Membranes
Fabio Bazzarelli and Lidietta Giorno
Institute on Membrane Technology, National
Research Council, ITM-CNR, Rende (CS), Italy
Synonyms
Mixed matrix membranes (MMMs)
Nanocomposite membranes or mixed matrix
membranes (MMMs) are heterogeneous mem-
branes having inorganic particles dispersed into
polymeric matrices, with the aim of improving
the performance of membranes by synergistic
combinations of the properties of both compo-
nents. The nanocomposite materials possess
enhanced properties compared with the single
organic or inorganic material. Such improvement
is either with respect to separation performance
(higher selectivity and permeability) or to physi-
cochemical properties (hydrophilicity, porosity,
charge density, and mechanical, optical, electri-
cal, and thermal properties). In addition, the
introduction of nanoparticles into organic poly-
mers can improve the resistance to chemical
reagents and antifouling properties in the water
treatment processes.
Nanocomposite membranes appear as an
interesting approach for overcoming the problem
of the trade-off relationship between selectivity
and permeability of the pure polymeric
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_402-1
membranes (Robeson 2008). The properties of
polymer composites depend on the nanoparticles
that are incorporated, including their size, shape,
concentration, and interactions with the polymer
matrix. Numerous polymers, both in glassy and
rubbery states, have been studied as continuous
matrices in MMMs. Some glassy polymers were
investigated including perfluorinated materials,
polyimides, polysulfone, polyetheretherketone,
and polymer of intrinsic microporosity (PIM-1).
Rubbery polymers are also attracted as continu-
ous matrices such as silicone, polyethylene, and
polybutadiene. Often natural polymers
(polysaccharides, collagen, and chitosan) are
also employed as the matrix. Nanoparticles of
various natures were embedded in the polymer
matrix. They have been widely used in optical,
electrical, and magnetic fields. Nanoparticles
consist of conventional fillers (zeolites, carbon
molecular sieves (CMSs), silicas, and metal
oxides) and alternative fillers (carbon nanotubes
(CNTs), metal organic frameworks (MOFs),
graphenes, and layered silicates) (Rezakazemi
et al. 2014). The successful implementation of
nanocomposite membrane depends on the disper-
sion and distribution of fillers in the continuous
phase as well as for the interface compatibility
between the particles and the polymer. The
homogeneous dispersion of nanoparticle in com-
posites is a challenge because of the immiscibil-
ity of polymer and nanoparticles due to a missing
interaction. Therefore, it is necessary to modify
the particles to overcome their tendency to
2 Nanocomposite Membranes
Nanocomposite Membranes, Table 1 Several nanocomposite membranes and their applications
Polymer matrix/fillers
Poly(butadiene)/MgO
Polyamide/CNTs
Poly(lactic acid)/graphene oxide
Nafion/CNTs
Chitosan-gelatin/ZnO
Poly(vinyl alcohol)/zeolitic imidazolate frameworks
(ZIF-8)
aggregate and improve their dispersion in poly-
mer matrices. The main defects at the polymer-
particle interface, including interfacial voids or
sieves-in-a-cage, rigidified polymer layer around
the particles and finally the particle pore block-
age. Surface modification of inorganic particles is
a popular technique because it produces excellent
integration and an improved interface between
inorganic filler and the polymer matrix. There
are two main approaches for modification of the
surface of the nanoparticles: modification of the
surface of the inorganic particles by chemical
treatment and grafting of functional polymeric
molecules to the hydroxyl groups existing on
the particles (Hong and Chen 2015). Basically
there are three general ways to prepare
nanocomposite membranes, including: sol-gel
process, in situ/interfacial polymerization and
phase inversion method (Souza and Quadri
2013).
The sol-gel technique is the method most
applied for the preparation of polymer-inorganic
nanocomposite membranes with highly homoge-
neous and controlled morphology. In this
method, organic monomers, oligomers, or poly-
mers and inorganic nanoparticle precursors are
mixed together in the solution. The inorganic
precursors then hydrolyze and condense into
well-dispersed nanoparticles in the polymer
matrix.
In in situ/interfacial polymerization, the
nanoparticles are well mixed with organic
Application Aim
Gas separation Increasing CO2 permeability
Reverse Antifouling and antioxidant properties
osmosis Improving flux
Packaging Enhancement gas barrier performance
Fuel cell Increasing electronic conductivity
Biomedical Antibacterial and improving
mechanical properties
Pervaporation Improving flux
monomers, and then the monomers are polymer-
ized. There are often some functional groups such
as hydroxyl or carboxyl on the surface of the
inorganic particles, which can generate initiating
radicals, cations or anions under high-energy
radiation, plasma, or other circumstances to ini-
tiate the polymerization of the monomers on their
surface.
In the phase inversion method, the preparation
of nanocomposite membranes can be grouped by
the following general procedure:
• Separate preparation of a polymer solution
and a suspension of inorganic material.
• Mixing of both resulting in a mixed matrix
solution.
• Casting solution is cast as film (or spinning)
followed by phase inversion process. It can be
induced by evaporation of solvent, immersion
precipitation using nonsolvent, or by thermal
precipitation.
The development of nanocomposite mem-
branes finds applications in different fields such
as gas separation, pervaporation, fuel cell, pack-
aging, and water and wastewater treatment. In
addition, nanocomposite membranes are of huge
interest to biomedical technologies such as con-
trolled drug delivery, tissue engineering, dental
applications, and bone replacement/repair. In
Table 1 are reported some types of
nanocomposite membrane and their applications.
Nanocomposite Membranes
References
Hong RY, Chen Q (2015) Dispersion of inorganic
nanoparticles in polymer matrices: challenges and
solutions. Springer, Berlin, pp 1–38
Rezakazemi M, Amooghin AE, Montazer-Rahmati MM,
Ismail AF, Matsuura T (2014) State-of-the-art mem-
brane based CO2 separation using mixed matrix
3
membranes (MMMs): an overview on current status
and future directions. Prog Polym Sci 39:817–861
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320:390–400
Souza VC, Quadri MGN (2013) Organic-inorganic hybrid
membranes in separation processes: a 10-year review.
Braz J Chem Eng 30:683–700
N
Natural Gas Sweetening
A. Baudot
Physics and Analysis Division, IFP Energies
Nouvelles, Solaize, France
Introduction
Though raw natural gas is mainly composed of
methane (generally from 75 % to 90 %), it also
contains undesired components such as acid gas-
eous impurities such as carbon dioxide or hydro-
gen sulfide that should be removed in order to
prevent pipeline corrosion.
Permeation Membrane-Based CO2
Removal
Gas permeation constitutes the latest carbon
dioxide extraction technology applied to natural
gas treatment. Membranes offer several strong
advantages over conventional solvent columns:
compacity (which makes membranes particularly
well-suited for offshore operations (Cooley and
Dethloff 1985)), low investment costs, low main-
tenance costs, and at least with single-stage con-
figurations that do not operate compressors. The
current level of commercial membranes CO2/
CH4 selectivity is comprised between 12 and
25 in field conditions (Baker 2002; Roman
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_405-1
et al. 2001; White et al. 1995; Baker and
Lokhandwala 2008).
Several studies have been carried out since the
adoption of membranes by natural gas operators,
aiming at comparing membrane-based carbon
dioxide removal operations with conventional
absorption operations. Several trends can be
issued from these studies, depending on the var-
ious considered gas treatment scenari:
– Moderate natural gas flows (lower than
25,000–30,000 Nm3/h (Chapel and Mariz
1999; Mckee et al. 1991)) containing high
carbon dioxide concentrations: it appears that
membranes are more profitable than absorp-
tion processes. In 1995, it was shown that
commercial permeation membranes were
more competitive than DEA/MDEA-based
absorption when the carbon dioxide content
was higher than 20 % (Meyer and Gamez
1995). Another study realized by Kelloggs &
Co. sets this limit at approximately 16 % for a
gas price of 1.5 USD/MMBtu (Mckee
et al. 1991).
– High natural gas flows with low carbon diox-
ide concentrations: absorption processes
prove to be more profitable than gas perme-
ation modules.
– High natural gas flows combined with high
carbon dioxide content: an association of
membranes and absorption seems to be the
most profitable option (McKee et al. 1991).
Membrane modules, located before the
2 Natural Gas Sweetening
absorption column, carry out a bulk removal
of carbon dioxide, while the absorption col-
umns allow the final polishing of the
natural gas.
Permeation Membrane-Based
Hydrogen Sulfide Removal
Three main types of polymer membrane have
been only tested at lab scale or pilot scale in
order to remove hydrogen sulfide from
natural gas.
Membranes Based on Rubbery Polymer
Selective Layers
This type of polymer materials generally offer
very high permeability values for low molecular
weight components. The selectivity of this type
of polymer is then essentially based on the affin-
ity (i.e., the sorption coefficient) difference
between several components to be separated. In
the literature, three main polymer families can be
identified:
• Apolar rubbery polymers, such as silicones
(PDMS and PTMSP). As a general rule, the
H2S/CH4 selectivity of these materials is
rather modest, as methane diffuses more rap-
idly than hydrogen sulfide (Merkel
et al. 2001).
• Apolar rubbery polymers impregnated with
polar solvents: two patents have been issued
by UOP in the mid-1980s about the use of
PEG- or glycerol-impregnated silicone mem-
branes. The addition of polar solvent, which
displays a high affinity for hydrogen sulfide,
leads to a very significant increase of the selec-
tivity of these membrane materials toward
hydrogen sulfide (Kulprathipanja and Sudhir
1985; Kulprathipanja 1985).
• Polar rubbery polymers: these types of poly-
mer have mainly been studied by academic
teams and display high values of H2S/CH4
selectivities associated with high H2S perme-
abilities. To the authors’ knowledge, though,
those materials have not been studied on larger
scale than at lab (Chatterjee et al. 1997; Orme
and Stewart 2005).
Membranes with a Selective Layer Made
of Block Polymers
This type of membrane materials has been prin-
cipally studied by MTR Inc. which has developed
commercial spiral-wound membranes with a
selective layer made of various polyether block
amides (commercialized under the trademark
®
PEBAX by Arkema). Tests under industrial con-
ditions were conducted on production facilities
operated by Shell and located in West Texas
(Amo et al. 1998). It was shown that the
®
PEBAX -based membranes/sulfatreat process
association was leading to significant operation
costs (from 20 % to 40 %) over amine process
alone for flow gases containing few percents of
H2S and lower than 140,000 Nm3/h while a
®
PEBAX membrane/amine coupling was more
valuable than a stand-alone amine process for
gas flows containing more than 5 % H2S and
higher than 23,000 Nm3/h.
Membranes with a Selective Layer Made
of Glassy Polymers
Those stiff polymeric materials, used mainly for
commercial carbon dioxide removal applications
(polyimides, cellulose acetate, polysulfones),
have their selectivity mainly based on molecular
sieving effects. Despite their affinity for polar
compounds (those membranes are also
recommended by membrane manufacturers for
gas dehydration applications), it appears that
those membrane materials have rather low H2S/
CH4 selectivities (Hao et al. 2008; Bhide
et al. 1998). This can be mainly attributed to the
fact that the kinetic diameters of hydrogen sulfide
and methane are rather close, resulting in close
values of their respective diffusion coefficients
through glassy polymer-based selective layers.
References
Amo K, Baker RW, Helm VD, Hofman T,
Lokhandwala K, Pinnau I, Ringer M, Su TT, Toy L,
Natural Gas Sweetening
Wijmans JG (1998) Low-quality gas sulfur removal/
recovery.DOE final report DE-AC21-92MC28133-01
Baker RW (2002) Future directions of membrane gas
separation technology. Ind Eng Chem Res
41:1393–1411
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res 47
(7):2109–2121
Bhide BD, Voskericyan A, Stern SA (1998) Hybrid pro-
cesses for the removal of acid gases from natural gas.
J Membr Sci 140:27–49
Chapel DG, Mariz CL (1999) In: Ernest J Recovery of
CO2 from flue gases: commercial trends. Oral Presen-
tation Canadian Society of Chemical Engineers
Annual Meeting, Saskatoon, Sakatchewan, Canada,
October 4-6 1999
Chatterjee G, Houde AA, Stern SA (1997) Poly(ether
urethane) and poly(ether urethane urea) membranes
with high H2S/CH4 selectivity. J Membr Sci
135:99–106
Cooley TE, Dethloff WL (1985) Field-tests show mem-
brane processing attractive. Chem Eng Prog 81:45–50
Hao J, Rice PA, Stern SA (2008) Upgrading low-quality
natural gas with H2S- and CO2-selective polymer
membranes – Part II. Process design, economics, and
sensitivity study of membrane stages with recycle
streams. J Membr Sci 320:108–122
3
Kulprathipanja S (1985) Separation of gases from non
polar gases. US Patent 4,606,740
Kulprathipanja S, Sudhir SS (1985) Separation of polar
gases from non polar gases. US Patent 4,608,860
Mckee RL, Changela MK, Reading GJ (1991) CO2
removal – membrane plus amine. Hydrocarb Process
70:63–65
Merkel TC, Gupta RP, Turk BS, Freeman BD
(2001) Mixed-gas permeation of syngas components
in poly(dimethylsiloxane) and poly(1-trimethylsilyl-1-
propyne) at elevated temperatures. J Membr Sci
191:85–94
Meyer HS, Gamez JP (1995) Gas separation membranes:
coming of age for carbon dioxide removal from natural
gas. Abstract of the 45th Laurence Reid gas condition-
ing conference, pp 284–306
Orme CJ, Stewart FF (2005) Mixed gas hydrogen sulfide
permeability and separation using supported
polyphosphazene membranes. J Membr Sci
253:243–249
Roman IC, Ubersax RW, Fleming GK (2001) New direc-
tions in membrane for gas separation. Chim Ind 83:1–3
White LS, Blinka TA, Kloczewski HA, Wang IF
(1995) Properties of a polyimide gas separation mem-
brane in natural-gas streams. J Membr Sci 103:73–82
n
n-C4H10/CH4 Separation
Arnaud Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
Before treatment, natural gas comes with close to
saturation higher hydrocarbons such as ethane,
propane, butane, or higher hydrocarbons. It is
necessary to remove those compounds for the
following reasons:
– Prevent condensation troubles in pipelines: as
an illustration, the dew point specification in
the US interstate pipeline is fixed at 20  C.
– Propane, butane, or higher hydrocarbons can
be valued as liquids and are particularly prized
as steam cracker feeds to produce short olefins
(ethylene, propylene).
– If the natural gas is used locally as fuel for
combustion engines operating compressors or
power-generating turbines, the presence of
higher hydrocarbons can cause combustion
problems or even accelerate aging of the
engines.
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_407-1
The conventional technologies used in the
industry to remove such “heavies” are condensa-
tion or lean oil absorption.
Several companies have been proposing vapor
permeation modules to operate heavy hydrocar-
bon recovery from small natural gas flowstream
since the 1990s: MTR Inc., Borsig, and GKSS. All
the membranes in operation are based on
silicone-selective layer which offer mixed-gas
propane/methane separation selectivity com-
prised between 3 and 5 (Baker and Lokhandwala
2008; Alpers et al. 1999) and butane/methane
separation selectivity ranging from 5 to
10 (Baker and Lokhandwala 2008; Alpers
et al. 1999).
References
Alpers A, Keil B, Ludtke O, Ohlrogge K (1999) Organic
vapor separation: process design with regards to high-
flux membranes and the dependence on real gas behav-
ior at high pressure applications. Ind Eng Chem Res
38:3754–3760
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47:2109–2121
N

NELF Model T and p. Polymer density must be assigned as

additional nonequilibrium state variable, e.g., on
Giulio C. Sarti the bases of direct experimental or other equiva-
Department of Chemical Engineering, Mining lent information; it represents the departure from
and Environmental Technology, University of the equilibrium of the glassy phase and is for-
Bologna, Bologna, Italy mally treated as an internal state variable (Sarti
and Doghieri 1998). From the general results of
NET-GP (Doghieri et al. 2004a, 2006; Giacinti
The nonequilibrium lattice fluid (NELF) model Baschetti et al. 2005a), the Helmholtz free energy
(Doghieri and Sarti 1996; Sarti and Doghieri of the glassy phase is formally given by the same
1998) allows to calculate the thermodynamic expression of the equilibrium Helmholtz free
properties of a solute in a glassy polymeric energy, as a function of T, ri, and rpol, where
phase. It represents the suitable extension to the the latter is a nonequilibrium value.
nonequilibrium glassy phase of the equilibrium The most relevant result of the model is
lattice fluid equation of state by Sanchez and embodied by the following explicit expression
Lacombe (1976, 1978) and Lacombe and of the chemical potential of each solute i in the
Sanchez (1976), according to the general rules glassy mixture, as a function of temperature,
of the nonequilibrium thermodynamics for glassy composition, and polymer density:
polymers (NET-GP) (Doghieri et al. 2004a,
2006; Giacinti Baschetti et al. 2005a), which ðSÞ  
mi r i  r 0i
requires in general that the state of a isotropic ¼ lnðe
r fi Þ  r i þ
0
RT e
r
homogeneous glassy phase is given by
temperature T, pressure p, densities of all solutes  lnð1  e r Þ  ri
" #
ri, and density of the polymer species rpol r 0i vi  X
Np  
 
(polymer mass per unit volume of the mixture). e r p þ fj pj  Dpij þ 1
RT i j¼1
The latter quantity is the value prevailing in the
nonequilibrium state of the glass, at the tempera- (1)
ture, pressure, and composition considered; it
depends on the thermomechanical prehistory of The quantities used by the model are defined in
the polymer phase and is a due to the kinetic Table 1. The model expressions contain pure
hindrance offered by the glassy phase which component parameters and one binary interaction
does not allow the polymer density to reach the parameter for each couple of components in the
value minimizing Gibbs free energy at the given mixture. The pure component parameters for the

# Springer-Verlag Berlin Heidelberg 2012

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_408-2
 2

NELF Model, Table 1 List of symbols and properties used in the NELF model
Symbol Name Definition/property
Pure component ri* Characteristic density of pure component i
i pi* Characteristic pressure of pure component i
Ti* Characteristic temperature of pure component i
ri0 Number of lattice sites occupied by a mole of pure component i r 0i ¼ rM vi
i i

vi* Volume occupied by a mole of lattice sites of pure substance RT i

vi ¼ pi

Mixtures N Total number of moles

T Temperature
p Pressure
r Density
ri Density of species i ri ¼ oi r
rpol Density of polymer species rpol ¼ opol r
oi Mass fraction, i = 1, 2,. . ., Np oi ¼ rri
fi Volume fraction o =r
fi ¼ X i i 
oi =ri
i
X oi
r* Characteristic density of the mixture 1
r¼
i
ri
X X X
p* Characteristic pressure of the mixture p ¼ fi pi  12 fi fj  Dpij
i i j6¼i
 ffi
pffiffiffiffiffiffiffiffiffiffiffiffi
Dpij Binary parameter Dpij ¼ pi þ pj  2 1  kij pi  pj
kij, Cij Dimensionless binary parameter Cij ¼ 1  kij
NELF Model
 X
r Molar average number of lattice sites occupied by a molecule in the r¼ xi r i
mixture i
T* Characteristic temperature of the mixture  X T i  
T  ¼ pr xi r 0i ¼ p Rv
NELF Model

i
pi

e* Characteristic energy e ¼ Tk

v* Average close-packed mer molar volume in the mixture v ¼ RT
p
e
r Dimensionless density e
r ¼ rr
T~ Dimensionless temperature T~ ¼ TT
p~ Dimensionless pressure p~ ¼ pp
Eq " #
A Total equilibrium Helmholtz free energy   NXp þ1
AEq 1 1 fi
rNRT  ¼ e
r þ T~ 1 lnð1  e 
r Þ þ r lnðerÞ þ lnðfi Þ
er ri
i¼1

mNE Chemical potential of solute i in the nonequilibrium glass ðSÞ  

i mi r i  r 0i
¼ lnðer fi Þ  r 0i þ 
RT e
r
" Np
#
 
r 0i vi  X  
lnð1  e r
r Þ  ri  e p þ fj pj  Dpij þ 1
RT i j¼1
3
4 NELF Model
polymers are obtained from volumetric data
above the glass transition temperature (Doghieri
and Sarti 1996; Sarti and Doghieri 1998); alter-
native techniques have been proposed for the
polymers degrading before glass transition is
reached (Galizia et al. 2012). The pure compo-
nent parameters for gases are obtained from vol-
umetric data; for vapors and liquids, vapor
pressure data are also used.
A collection of pure component parameters
for polymers of interest in membrane separations
is reported in Table 2, while for relevant pene-
trants, pure component parameters are reported in
Table 3. The binary interaction parameters are
generally used as fitting quantities, even though
a predictive method has been proposed (Rodgers
and Sanchez 1993), and often the first order
approximation of kij = 0 is also acceptable.
Remarkably, the nonequilibrium model, using
T and rpol as input, is much less sensitive to the
binary parameter than the corresponding equilib-
rium model, using temperature and pressure as
input.
The phase equilibrium (or more properly
pseudo-equilibrium) conditions between the
glassy nonequilibrium phase and an external
fluid phase, either gaseous or liquid, are
represented as usual:
ð SÞ ðexternal fluidÞ
mi ¼ mi (2)
By using Eq. 1 for the chemical potential of
species i dissolved in the glassy phase and usual
equilibrium expression for the chemical potential
of species i in the external fluid phase, from Eq. 2
one obtains solubility isotherms for pure pene-
trants (Doghieri and Sarti 1996, 1998; Sarti and
Doghieri 1998; Giacinti Baschetti et al. 2001; De
Angelis et al. 2007) as well as for mixed gases
(Doghieri et al. 2004b; Minelli et al. 2011), in
pure glassy polymers, in polymer blends (Grassia
et al. 2004), as well as in glassy-mixed matrices
(Maria Grazia De and Sarti 2008; Maria-Chiara
et al. 2010). The model is also suitable to calcu-
late the solubility of liquids in glassy polymers
(Sarti and De Angelis 2012).
Whenever the binary interaction parameters
are known from data above the glass transition
temperature, and polymer density is known, the
model is entirely predictive (Doghieri and Sarti
1996; Sarti and Doghieri 1998). Under
non-swelling conditions the polymer density
remains equal to the value of the pure
unpenetrated polymer (Doghieri and Sarti 1998;
Giacinti Baschetti et al. 2001). At high pressures
and for swelling penetrants, volume dilation of
the polymers is required, e.g., through the use of a
swelling coefficient (Giacinti Baschetti
et al. 2001). Remarkably, the model also shows
that in all cases, both at low and high free volume,
it is sufficient to consider only molecules
dissolved in the glassy phase, without the need
of an arbitrary differentiation between hypothet-
ically different populations of penetrant
molecules.
The interested users can freely download the
code for the solubility isotherms of binary mix-
tures (http://serwebdicma.ing.unibo.it/polymers/
index.htm).
NELF Model 5

NELF Model, Table 2 NELF model pure component parameters for different polymers
Symbol/ T* p* r*
acronym Name [K] [MPa] [g/cm3] Source
PC Poly(carbonate) 755 534 1.275 (Doghieri and
Sarti 1996)
TMPC Tetramethyl poly(carbonate) 761.6 446.4 1.174 (Doghieri and
Sarti 1998)
PMMA Poly(methyl methacrylate) 695 560 1.27 (Doghieri and
Sarti 1998)
PEMA Poly(ethyl methacrylate) 602 567.5 1.221 (Giacinti
Baschetti
et al. 2005a)
PPO Poly(2,6-dimethyl-1,4-phenylene oxide) 739 479 1.177 (Doghieri and
Sarti 1998)
PSF Poly(sulfone) 830 600 1.31 (Doghieri and
Sarti 1998)
PVAC Poly(vinyl acetate) 592 510 1.284 (Doghieri and
Sarti 1998)
PVC Poly(vinyl chloride) 736 415 1.458 (Doghieri and
Sarti 1998)
HFPC Hexafluoro poly(carbonate) 716.5 446 1.618 (Sarti and
Doghieri 1998)
AF1600 Tetrafluoroethylene (TFE) – 2,2-bis 575 280 2.16 (De Angelis
(trifluoromethyl)-4,5-difluoro-1,3-dioxole (BDD) et al. 2002)
(25–65 mol)
AF2400 Tetrafluoroethylene (TFE) – 2,2-bis 624 250 2.13 (De Angelis
(trifluoromethyl)-4,5-difluoro-1,3-dioxole (BDD) et al. 2002)
(13–87 mol)
PTFE Poly(tetrafluoroethylene) 618 371 2.25 (De Angelis
et al. 2002)
PS Poly(styrene) 750 360 1.099 (Sarti and
Doghieri 1998)
PEUT Poly(ether urethane) 550 450 1.132 (Giacinti
Baschetti
et al. 2003)
PTMSP Poly(trimethylsilyl propyne) 610 380 1.125 (Giacinti
Baschetti
et al. 2005b)
TMSP/ 1-trimethylsilyl-1-propyne/1-trimethylsilyl-1-n- 515 580 1.25 (Giacinti
TMSE hexyne 70/30 copolymer Baschetti
70/30 et al. 2005b)
TFE/ Tetrafluoroethylene – perfluoromethyl vinyl ether 509 395 2.244 (Prabhakar
PMVE49 (50.7–49.3 mol) et al. 2005)
PTMSN Addition type poly(trimethylsilyl norbornene) 406 360 1.345 (Galizia
et al. 2012)
LDPE Low density poly(ethylene) 693 400 0.883 (Giacinti
Baschetti
et al. 2005a)
6 NELF Model

NELF Model, Table 3 NELF model pure component parameters for different solutes
Symbol/acronym Name T* [K] p* [MPa] r* [g/cm3] Source
H2 Hydrogen 46 37 0.078 (Doghieri and Sarti 1998)
O2 Oxygen 180 214 1.25 (De Angelis et al. 1999)
N2 Nitrogen 145 160 0.943 (Doghieri and Sarti 1998)
He Helium 9.3 4 0.148 (De Angelis et al. 2007)
Ar Argon 190 180 1.31 (De Angelis et al. 2006)
Xe Xenon 304 351 3.36 (De Angelis et al. 2007)
CH4 Methane 215 250 0.5 (Doghieri and Sarti 1998)
CO2 Carbon dioxide 300 630 1.515 (Doghieri and Sarti 1998)
SO2 Sulfur dioxide 430 630 1.734 (De Angelis et al. 2006)
N2O Nitrous oxide 319 524 1.408 (De Angelis et al. 2007)
H2O Water 670 2,400 1.05 (De Angelis et al. 2007)
CH3OH Methanol 510 1,080 0.9 (De Angelis et al. 2007)
C2H5OH Ethanol 470 880 0.915 (De Angelis et al. 2007)
C3H7OH 1-propanol 500 700 0.913 (Galizia et al. 2012)
(CH3)2CO Acetone 484 533 0.92 (De Angelis et al. 2007)
CH3CN Acetonitrile 505 910 0.855 (Giacinti Baschetti et al. 2003)
VCM Vinyl chloride 450 390 1.115 (Doghieri and Sarti 1998)
CF4 Tetrafluoromethane 230 265 1.92 (De Angelis et al. 1999)
C2F6 Perfluoroethane 296 227 1.95 (De Angelis et al. 1999)
C3F8 Perfluoropropane 335 225 2.05 (De Angelis et al. 1999)
C6H6 Benzene 523 444 0.994 (De Angelis et al. 2007)
C7H8 Toluene 543 402 0.966 (Giacinti Baschetti et al. 2005a)
C2H4 Ethylene 295 365 0.68 (Doghieri and Sarti 1998)
C2H6 Ethane 320 330 0.64 (De Angelis et al. 1999)
C3H8 Propane 375 320 0.69 (De Angelis et al. 1999)
n-C4H10 n-Butane 430 290 0.72 (De Angelis et al. 2002)
n-C5H12 n-Pentane 451 304 0.752 (Prabhakar et al. 2005)
n-C6H14 n-Hexane 476 298 0.77 (Prabhakar et al. 2005)
c-C5H12 c-Pentane 478 389 0.88 (Prabhakar et al. 2005)
c-C6H14 c-Hexane 497 383 0.902 (Prabhakar et al. 2005)
n-C7H16 n-Heptane 498 295 0.780 (Galizia et al. 2012)
n-C8H18 n-Octane 502 308 0.815 (Sanchez and Lacombe 1976)
n-C9H20 n-Nonane 517 307 0.828 (Sanchez and Lacombe 1976)
n-C10H22 n-Decane 530 304 0.837 (Sanchez and Lacombe 1976)
n-C11H24 n-Undecane 542 303 0.846 (Sanchez and Lacombe 1976)
n-C12H26 n-Dodecane 552 301 0.854 (Sanchez and Lacombe 1976)

References (dimethylsiloxane): comparison of experimental data

De Angelis MG, Sarti GC (2008) Solubility and diffusiv-
ity of gases in mixed matrix membranes containing
hydrophobic fumed silica: correlations and predictions
based on the NELF model. Ind Eng Chem Res
47(15):5214–5226
De Angelis MG, Merkel TC, Bondar VI, Freeman BD,
Doghieri F, Sarti GC (1999) Hydrocarbon and fluoro-
carbon solubility and dilation in poly
with predictions of the Sanchez–Lacombe equation of
state. J Polym Sci B Polym Phys 37:3011–3026
De Angelis MG, Merkel TC, Bondar VI, Freeman BD,
Doghieri F, Sarti GC (2002) Gas sorption and dilation
in poly(2,2-bistrifluoromethyl-4,5-difluoro-1,3-
dioxole-co-tetrafluoroethylene): comparison of exper-
imental data with predictions of the nonequilibrium
lattice fluid model. Macromolecules 35:1276–1288
De Angelis MG, Sarti GC, Doghieri F (2006) An interpre-
tation of the relation between infinite dilution gas
NELF Model
solubility and critical temperature in glassy polymers
based on the NE-LF model. Desalination 199:466–468
De Angelis MG, Sarti GC, Doghieri F (2007) NELF model
prediction of the infinite dilution gas solubility in
glassy polymers. J Membr Sci 289:106–122
Doghieri F, Sarti GC (1996) Nonequilibrium lattice fluids:
a predictive model for the solubility in glassy poly-
mers. Macromolecules 29:7885–7896
Doghieri F, Sarti GC (1998) Predicting the low pressure
solubility of gases and vapors in glassy polymers by
the NELF model. J Membr Sci 147:73–86
Doghieri F, Quinzi M, Rethwisch DG, Sarti GC (2004a)
Predicting gas solubility in glassy polymers through
non-equilibrium EOS. In: Pinnau I, Freeman BD (eds)
Advanced materials for membrane separations, ACS
symposium series, vol 876. ACS, Washington, DC,
pp 74–90
Doghieri F, Canova M, Sarti GC (2004b) Solubility of
gaseous mixtures in glassy polymers: NELF predic-
tions. In: ACS Symposium Series, vol 733 (1999).
ACS, Washington, DC, pp 179–193
Doghieri MQ, Rethwisch DG, Sarti GC (2006) Predicting
gas solubility in glassy polymers through
non-equilibrium EOS. In: Yampolskii Y, Pinnau I,
Freeman BD (eds) Materials science of membrane
for gas and vapor separations. Wiley, New York,
pp 137–158
Ferrari M-C, Galizia M, De Angelis MG, Sarti GC
(2010) Gas and vapor transport in mixed matrix mem-
branes based on amorphous Teflon ® AF1600 and
AF2400 and fumed silica. Ind Eng Chem Res
49:11920–11935
Galizia M, De Angelis MG, Sarti GC (2012) Sorption of
hydrocarbons and alcohols in addition-type poly
(trimethyl silyl norbornene) and other high free vol-
ume glassy polymers. II: NELF model predictions.
J Membr Sci 405–406:201–211
Giacinti Baschetti M, Doghieri F, Sarti GC (2001) Solu-
bility in glassy polymers: correlations through the
nonequilibrium lattice fluid model. Ind Eng Chem
Res 40:3027–3037
Giacinti Baschetti M, Piccinini E, Barbari TA, Sarti GC
(2003) Quantitative analysis of polymer dilation
7
during sorption using FTIR-ATR spectroscopy. Mac-
romolecules 36(25):9574–9584
Giacinti Baschetti M, De Angelis MG, Doghieri F, Sarti
GC (2005a) Solubility of gases in polymeric mem-
branes. In: Galan MA, Martin del Valle E (eds) Chem-
ical engineering: trends and developments. Wiley,
Chichester, pp 41–61
Giacinti Baschetti M, Ghisellini M, Quinzi M, Doghieri F,
Stagnaro P, Costa G, Sarti GC (2005b) Effects on
sorption and diffusion in PTMSP and TMSP/TMSE
copolymers of free volume changes due to polymer
ageing. J Mol Struct 739:75–86
Grassia F, Giacinti Baschetti M, Doghieri F, Sarti GC
(2004) Solubility of gases and vapors in glassy poly-
mer blends. In: Pinnau I, Freeman BD (eds) Advanced
materials for membrane separations, ACS symposium
series, vol 876. ACS, Washington, DC, pp 55–73
Lacombe RH, Sanchez IC (1976) Statistical thermody-
namics of fluid mixtures. J Phys Chem 80:2568–2580
Minelli M, Campagnoli S, De Angelis MG, Doghieri F,
Sarti GC (2011) Predictive model for the solubility of
fluid mixtures in glassy polymers. Macromolecules
44:4852–4862
Prabhakar RS, De Angelis MG, Sarti GC, Freeman BD,
Coughlin MC (2005) Gas and vapor sorption, perme-
ation, and diffusion in poly(tetrafluoroethylene-co-
perfluoromethyl vinyl ether). Macromolecules
38:7043–7055
Rodgers PA, Sanchez IC (1993) Improvement to the
lattice-fluid prediction of gas solubilities in polymer
liquids. J Polym Sci Polym Phys Educ 31:273
Sanchez IC, Lacombe RH (1976) An elementary molecu-
lar theory of classical fluids. Pure fluids. J Phys Chem
80:2352–2362
Sanchez IC, Lacombe RH (1978) Statistical thermody-
namics of polymer solutions. Macromolecules
11:1145
Sarti GC, De Angelis MG (2012) Calculation of the solu-
bility of liquid solutes in glassy polymers. AIChE
J 58:292–301
Sarti GC, Doghieri F (1998) Predictions of the solubility
of gases in glassy polymers based on the NELF model.
Chem Eng Sci 53:3435–3447
N
Neuronal Regeneration
Loredana De Bartolo and Antonietta Messina
Institute on Membrane Technology ITM-CNR,
National Research Council of Italy, Rende(CS),
Italy
Synonyms
Neuronal tissue regeneration
The expression “neuronal regeneration” refers to
all the strategies available for the regrowth,
repair, or the substitution of neuronal cells or
cell products after an injury causing damages
and/or degeneration of the nervous system (NS).
In higher organisms like animals and human
beings, the regenerative ability of the nervous
system is very limited. The NS consists of two
connected sections called central and peripheral
systems. The central nervous system (CNS), in
charge of the behavior control and the informa-
tion processing, includes the brain and the spinal
cord, whereas the peripheral nervous system
(PNS) is made up of cranial, spinal, and auto-
nomic nerves, able to coordinate locomotion,
sensory perception, and homeostasis. Intended
for the transmission and the report of signals
and information between the body and the brain,
the neurons are the main units for both the sys-
tems, but due to the different glial cell composi-
tion, a discrepancy between the regenerative
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_410-1
capabilities in the central nervous system and
the peripheral nervous system is recorded. Glia
is constituted of nonneuronal cells serving to
provide physical and chemical support and pro-
tection to neurons. Schwann cells and oligoden-
drocytes are respectively the main glia
components of the PNS and the CNS. They are
responsible of the axons myelination allowing
rapid and efficient signal transmission and
impulse conduction between the two systems,
whereas the central astrocytes serve the mainte-
nance of the homeostasis and the recycle of the
neurotransmitters. When an injury occurs and the
peripheral axons are severed, leading to the
Wallerian degeneration, macrophages and mono-
cytes migrate in the injured site to remove myelin
and axon debris. Schwann cells proliferate in
order to substitute glial cells lost during injury
and initiate the production and secretion of lam-
inin and fibronectin, which provide the path for
the regeneration. Moreover, they upregulate the
expression of adhesion proteins (NCAMs),
cadherins (N-cadherin), and other neurotrophic
factors (BDNF, CNTF, GDNF) involved in the
axonal regeneration across the area of injury and
lead the formation of growth cones in the proxi-
mal damaged axons. Unlike peripheral glia, oli-
godendrocytes in the CNS are not able to
proliferate, and then cells lost to injury are not
replaceable. Furthermore, the growth-promoting
activity of the central glia is not enough to ensure
the conductive environment for the axonal
regrowth due to the over expression of inhibitor
2 Neuronal Regeneration
factors of the axon growth. After a trauma or an
injury, the production of neuroprotective factors
is quite limited and eventually not enough to
oppose the two main mechanisms occurring in
the central nervous system. First, the apoptotic
phenomena affecting the surrounding of the dam-
aged area over a great distance, due to the secre-
tion of members of the transforming growth
factor family (TGF) that largely promote cell
death. Secondly, the proliferation of glial cells
in quiescent state and the consequent formation
of a glial scar acting as physical barrier for the
axonal regeneration. Astrocytes actually produce
and secrete specific factors, such as NOGO pro-
teins, NI-35, chondroitin sulfate proteoglycans,
and keratan sulfate proteoglycans, known to be
inhibitors of the remyelination and axon repair
(Steward et al. 2013; Allodi et al. 2012). Then,
the modulation of the regenerative process in the
nervous system lies on different approaches
depending on the site and the extension of the
injured area. Independently on the causes, an
injury affects the nervous system with the inabil-
ity of neuronal cells to transmit impulses to spe-
cific regions of the nervous system. In order to
restore the functionalization, one of the three
specific repair mechanisms must occur: the
regrowth of the neuronal damaged axons, the
recovery of the axonal function, or the substitu-
tion of the neurons that have been lost through the
generation of new neuronal cells. Each one of
these regenerative methods stands as alternative
to the gold standard treatments, represented by
the coaptation and the nerve graft implantation.
The first one consists in the surgical reparation of
small nerve gap (<8 mm) resulting after an
injury, and the second one consists in the implan-
tation of grafts regardless the size of the gaps.
Generally autografts, which have no risk of
immune reactions, are the first choice in the
nerve injury treatment, but allografts and xeno-
grafts are also available. Therefore, none of them
allow to reach a full functional recovery and
many drawbacks are possible.
Cell Replacement or Cell Therapy. When a
wide area of the nervous system has been dam-
aged by a trauma or a degenerative pathology, a
replacement of the neuronal cells can be obtained
using stem cells. Neural stem cells (NSC) are
available from the hippocampus, spinal cord,
fetal brain, and neural retina and due to the ability
to self-renew can differentiate in neurons, astro-
cytes, and oligodendrocytes in order to substitute
cells lost in the injury. Amyotrophic lateral scle-
rosis (ALS), spinal muscular atrophy (SMA),
main motor neuron disorders, and Parkinson’s
disease (PD) are the focus of the neural stem
cell strategies. NSC not only can be integrated
into host nervous system but also have been
engineered to act as delivery vehicle for
neuroprotective growth factors like the GDNF
and IGF-1, resulting in an increase of the spinal
motor and the dopaminergic neuron survival
(Tysseling and Kessler 2011). Pluripotent stem
cells have been also successfully used as strategy
for the neuronal regeneration. They represent a
perfect in vitro system for developmental studies
and can be not only differentiated in neurons but
reprogrammed to form stem cells facilitating the
replacement of degenerated neurons from autol-
ogous sources avoiding grafts rejection in the
patients (Steward et al. 2013).
Drug Delivery. Many natural and synthetic
molecules have shown to possess neuroprotective
and neurogenerative properties. The administra-
tion of neurotrophic factors demonstrated an
improvement of the regenerative process in both
the central and the peripheral nervous systems.
The intact blood-spinal cord barrier represents an
obstacle in reaching the brain and the spinal cord,
but generally after injuries or degenerative pro-
cesses, several parts result to be compromised;
therefore, neurotrophins and drugs administered
can overcome the barrier reaching the site of
action. Carrier, microcarrier, microspheres, lipo-
somes, and hydrogels are the devices available
for the controlled release, and synthetic or natural
polymers, extracellular matrix derived biomate-
rials, carbon nanoparticles, and ions complexes
represent only a few of the biomaterials usable
for their preparations (Tysseling and Kessler
2011; Gu et al. 2014). Moreover, not only spinal
cord and nerve regeneration have been achieved,
but due to this strategy central diseases such as
Parkinson’s and Alzheimer’s are possible. In fact,
the controlled release of dopamine and b-amiloid
Neuronal Regeneration
inhibitors represents today the best treatment
available for the neurodegenerative pathologies
in combination with the cell transplantation.
Moreover, in order to avoid multiple drug injec-
tions and to increase the delivery time in the
selected area, mini-pumps are available and sur-
gically implantable in patients for the treatment
of the chronic pain and the degenerative diseases.
Nerve Conduit, Scaffolds, and Channels. The
protection of the injured site from inhibitor fac-
tors and apoptotic/inflammatory phenomena is of
main importance in order to increase the regen-
erative process in the nervous system. This is the
reason why scaffolds, channels, and conduits
have been purposely made to protect the severed
areas during the regeneration and tested in
in vitro and in vivo studies. With the aim of
recreating a permissive environment for the
neurite and axonal growth, these synthetic
devices consisting of polymers and hydrogels in
form of tubes or fibers possess morphological,
chemical-physical, and mechanical specific prop-
erties. Topography, mechanical strength, biodeg-
radation, porosity, and dimensions are necessary
to induce cell adhesion, proliferation and differ-
entiation, to allow the nutrient and growth factor
supply, to remove the metabolites and inhibitors,
and to avoid the device collapsing during the
regenerative process after the implantation
(Sedaghati et al. 2014; Morelli et al. 2010). Col-
lagen, laminin, fibronectin, polycaprolactone,
polylactic acid, and chitosan tubes are allowed
to build high-quality guides for the neural repair.
In addition, in the last decade, the nerve conduits
have been further developed and leveled up
through the combination with supportive cells
and the growth factors incorporation. Alterna-
tively, neural stem cells and pluripotent cells are
seeded in the lumen of the tubes, and they stim-
ulate the release of diffusible growth factors in
3
order to induce the neurite outgrowth and axonal
regeneration in the insulated area. On similar
lines of the drug delivery, growth factors and
neuroprotective agents are encapsulated in the
scaffolds or incorporated in the biomaterials and
then let diffuse towards the severed site. This new
approach increases the neural regeneration guid-
ing the axonal growth in both the central and
peripheral nervous systems.
Despite the autografts still remain the gold
standard for the treatment of the nervous system
injuries, the promising results recorded in the
biomaterials field represent the best alternative
in the development of new regenerative
approaches, based on the controlled drugs and
factors release, the guidance of the axonal
regrowth, and the transplantation of cells in the
selected area.
References
Allodi I, Udina E, Navarro X (2012) Specificity of periph-
eral nerve regeneration- interactions at the axon level.
Prog Neurobiol 98:16–37
Gu X, Ding F, Williams DF (2014) Neural tissue engi-
neering for peripheral nerve regeneration. Biomate-
rials 35:6143–6156
Morelli S, Salerno S, Piscioneri A, Papenburg BJ, Di
Vito A, Giusi G, Canonaco M, Stamatialis D,
Drioli E, De Bartolo L (2010) Influence of
micropatterned PLLA membranes on the outgrowth
and orientation of hippocampal neuritis. Biomaterials
31:7000–7011
Sedaghati T, Jell G, Seifalian M (2014) Nerve regenera-
tion and bioengineering. In: Orlando G -
(ed) Regenerative medicine applications in organ
transplantation. Elsevier, Waltham, pp 799–810
Steward MM, Sridhar A, Meyer JS (2013) Neural regen-
eration. Curr Top Microbiol Immunol 367:163–191
Tysseling VM, Kessler JA (2011) Biomaterials for central
nervous system regeneration. Tissue Eng Neurol
Neurosurg 533:455–466
N
Nichel Recovery by Liquid
Membrane
Argurio Pietro
Department of Environmental and Chemical
Engineering, University of Calabria, Arcavacata
di Rende (CS), Italy
Heavy metal removal from various industrial
wastewaters is a major concern, since they are
often present at significant levels. Among the
numerous industrial sectors that contribute to
environmental pollution with these metals, such
as dyeing, mining, electroplating, nuclear power
operations, aerospace, and battery manufacturing
processes, the metal finishing industry is very
important due to the large number of locations
as their geographical dispersion. Heavy metals
differ from organic substances because they are
not biodegradable (Lothongkum et al. 2009).
Thus, they can accumulate in living tissues, caus-
ing various diseases and disorders, since they are
toxic to human beings and organisms even at very
low concentrations (Hassaine-Sadi et al. 2012).
Among these metals, chromium, nickel, zinc,
copper, and cadmium are the most abundant ones.
The main way of water contamination by
heavy metals is the discharge of liquids effluent
with relatively low but harmful concentration. As
a consequence, the appropriate treatment of high-
volume wastewater containing low concentra-
tions of heavy metals is very important, and in
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_412-6
addition, the discharge regulation is progres-
sively becoming more stringent. The World
Health Organization recommends the toxic limits
of permissible concentration of Ni in wastewaters
at a level of 1 mg/L as insoluble compounds,
0.1 mg/L as soluble compounds, 0.05–012 mg/L
as nickel carbonyl, and 1 mg/L as nickel sulfide.
Many countries have regulations of the maximum
permissible concentration of nickel in industrial
wastewaters with values in the order of 1 mg/L.
Chemical precipitation is extensively used to
treat nickel-bearing wastewater, resulting in the
production of a large amount of toxic chemical
sludge which disposal/treatment is a very costly
affair, and it is not eco-friendly (Molinari
et al. 2009). Other convectional methods, such
as filtration after neutralization, ion exchange,
and adsorption, are not selective, and thus, no
metal recovery is achieved. Besides, they are
expensive methods and not efficient enough to
reduce nickel concentration below the permissi-
ble concentrations.
Transport of metal ions across a liquid mem-
brane (LM) is a powerful technology combining
extraction and stripping into a one-step process
(G€uell et al. 2008; Walkowiak and Kozlowski
2009). LM systems include bulk liquid mem-
brane (BLM), emulsion liquid membrane
(ELM), and supported liquid membrane (SLM).
The lower capital and operating costs, the low
energy and extractant consumed, and the high
selectivity are the main advantages of LM sys-
tems with respect to the traditional separation
2 Nichel Recovery by Liquid Membrane
techniques. Thanks to these characteristic,
LM-based techniques permit to obtain the recov-
ery of heavy metal ions and the production of
water with good quality, resulting into both envi-
ronmental and economic benefits.
The selective separation of nickel from vari-
ous aqueous media containing nickel and cobalt,
that is, an important problem in hydrometallurgy,
can be carried out by using ELM (Longquan
et al. 1997; Kumbasar and Tutkun 2008). Ni and
Co possess aqueous similar chemical behavior,
because they are metal of the transition series
adjacent in the periodic table, but some differ-
ences exist. In ammoniacal environment
(Kumbasar 2009) the complex Co(NH3)2+ is
readily oxidized to Co(NH3)3+ with addition of
hydrogen peroxide, while the nickel complex Ni
(NH3)2+ is not oxidized. In these conditions the
nickel ammine complex can be selectively
extracted using an acidic extractant (e.g.,
5,7-dibromo-8-hydroxyquinoline (DBHQ)) by
the following reversible pH-dependent reaction:
NiðNH3 Þ2þ ðaqÞ þ 2 HRorg ¼ NiðNH3 ÞR2 þ 2 Hþ
The concentration of complexing agent (e.g.,
ammonia) in the feed phase, the pH of the feed
and of the strip aqueous phases, the composition
of the LM phase (extractant concentration, sur-
factant concentration, modifier concentration),
the mixing speed of feed solution, the presence
of complexing agent and its concentration in the
strip phase, and the feed/strip volumetric ratio are
the most important operating variables influenc-
ing the permeation of nickel across a LM and then
membrane selectivity.
The selective recovery of nickel ions from
wastewater of stainless steel manufacturing
plants can be efficiently carried out by hollow
fiber supported liquid membranes (HFSLM).
The type of extractant and its concentration in
the LM phase, the pH of the feed phase, the
stripping solution concentration (i.e., pH), the
flow rates of feed and stripping solution, and the
volumetric ratio of feed to stripping solutions
represent the most important parameters affect-
ing system selectivity (Lothongkum et al. 2009).
Two or more HFSLM modules can be placed in
series, obtaining satisfactory nickel recovery and
an aqueous effluent with concentration within the
common permissible limits.
References
G€
uell R, Anticó E, Salvadó V, Fontàs C (2008) Efficient
hollow fiber supported liquid membrane system for the
removal and preconcentration of Cr(VI) at trace levels.
Sep Purif Technol 62:389–393
Hassaine-Sadi F, Graiche M, Boudaa A, Bouchabou
H (2012) Purification-concentration process of Zn
(II), Ni(II) and Cd(II) using liquid membrane with
different carriers. Proc Eng 33:351–356
Kumbasar RA (2009) Selective extraction of nickel from
ammoniacal solutions containing nickel and cobalt by
emulsion liquid membrane using 5,7-dibromo-8-
hydroxyquinoline (DBHQ) as extractant. Miner Eng
22:530–536
Kumbasar RA, Tutkun O (2008) Separation of cobalt and
nickel from acidic leach solutions by emulsion liquid
membranes using Alamine 300 (TOA) as a mobile
carrier. Desalination 224:201–208
Longquan L, Cheng W, Yadong L (1997) Separation of
cobalt and nickel by emulsion liquid membranes with
the use of EDTA as masking agent. J Membr Sci
135:173–177
Lothongkum AW, Khemglad Y, Usomboon N,
Pancharoen U (2009) Selective recovery of nickel
ions from wastewater of stainless steel industry via
HFSLM. J Alloy Compd 476:940–949
Molinari R, Argurio P, Poerio T (2009) Studies of various
solid membrane supports to prepare stable sandwich
liquid membranes and testing copper (II) removal from
aqueous media. Sep Purif Technol 70:166–172
Walkowiak W, Kozlowski CA (2009) Macrocycle carriers
for separation of metal ions in liquid membrane
processes – a review. Desalination 240:186–197
N
Non Linear Programming
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Problems of nonlinear programming (NLP) arise
in many engineering applications. These involve
(complex) process simulations, optimal experi-
ment design for estimation of parameters, param-
eter estimation, optimal process design, optimal
process control, and so on. In general,
constrained NLP problems can be mathemati-
cally stated as (Bertsekas 1999)
min f ðxÞ (1a)
x and active set methods).
s:t: gðxÞ  0 (1b)
hðxÞ ¼ 0 (1c)
where x represents vector of optimization
(decision) variables, f(x) is optimization crite-
rion, and g(x) and h(x) stand for sets of inequality
and equality constraints, respectively.
If the instance of problem (1a) does not
involve (1b) and (1c), then the problem is referred
to as unconstrained. Minimizer x* must satisfy
the following property (Boyd and Vanderberghe
2004)
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_414-4
∇f ðx⋆ Þ ¼ 0
and thus the problem boils down to solving the set
of nonlinear equations. For solving this type of
problems, one may use well-established algo-
rithms such as steepest descent method and New-
ton or quasi-Newton methods.
However, in practice, any optimization prob-
lem involves constraints naturally. To treat
constrained NLPs analytically, one may exploit
Karush-Kuhn-Tucker (KKT) conditions which
are based on the theory of Lagrange multipliers
(Bazaraa et al. 1993). For practical purposes, one
usually relies on using numerical methods. These
are based on approximation of original problems
into an unconstrained form (penalty, barrier, and
interior point methods) or generating sequences
of simpler but closely related subproblems (SQP
References
Bazaraa MS, Sherali HD, Shetty CM (1993) Nonlinear
programming. Theory and algorithms. Wiley, New
York
Bertsekas DP (1999) Nonlinear programming. Athena
Scientific, Belmont
Boyd S, Vandenberghe L (2004) Convex optimization.
Cambridge University Press, Cambridge
N
Nucleation Stage Crystal Growth
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
Nucleation is the initial stage of crystal growth
and can be either homogeneous nucleation or
heterogeneous, surface-catalyzed nucleation
(Cahn 1960). The nucleation stage can be
surpassed when a seed material is used, on
which crystallization can take place by addition
of new atoms, ions, or polymers. This is typically
applied in reactors for precipitation such as the
pellet reactor for water softening. This is hetero-
geneous precipitation, for which a moderately
supersaturated solution is needed (with stability
index SI = 1–2). Heterogeneous precipitation is
easier than homogeneous precipitation, since
there is no need to create a new surface (and to
supply the energy needed for this). This also
allows a better control of the crystallization.
Homogeneous nucleation sets off with the cre-
ation of a small nucleus, which contains the newly
forming crystal. This stage in the process is rela-
tively slow, because the initial crystal components
have to arrange in the correct orientation and
position to adhere and form the crystal. Therefore,
a larger oversaturation is needed (SI = 3–4).
Once a nucleus is formed, crystals may grow
more rapidly because they contain dislocations
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_417-1
and other defects, which act as growth points
and catalysts for structural transformation and
long-range order formation (Frank 1949).
Nucleation stage crystal growth can be
described by the self-consistent theory of nucle-
ation (Girshick and Chiu 1990). According to the
self-consistent theory, the Gibbs free energy DG
needed for nucleation can be written as:


DG ¼ 4pr 2  s s  ðn  1Þ kB Tln S
in which kB is the Boltzmann constant, S is the
supersaturation, and s is the surface area of a
monomer. From this, the nucleation rate can be
calculated as:
 
ss
exp
kB T
I SCT ¼ I
S
in which I is the rate calculated from the classical
nucleation theory. The exponential coefficient in
the equation takes the surface energy of the mono-
mer into account.
Nucleation is an important phenomenon in
membrane synthesis, mainly applied for synthesis
of inorganic membranes. For example, Lin
et al. (2001) prepared silicalite membranes by a
single hydrothermal synthesis on nanoscale-
silicalite-seeded porous tubular supports. An
incompact crystal layer was obtained, especially
on the unseeded support. Silicalite crystals
2 Nucleation Stage Crystal Growth
preferentially grew onto the support tubes seeded
with silicalite powders with size below 4 mm. The
silicalite seed particles mainly provided nucle-
ation sites (heterogeneous nucleation) and
enhanced silicalite crystal growth in all directions
onto the support, resulting in the formation of a
thin and dense crystal layer.
For polymeric membranes, the nucleation
stage is typically fast, and homogeneous nucle-
ation is usually applied.
A direct application of nucleation for crystalli-
zation is encountered in membrane crystallization
(Curcio et al. 2001). In a membrane crystallizer, a
solution is concentrated by, e.g., membrane distil-
lation, so that a supersaturated solution is obtained
(Curcio and Driolo 2005). Subsequently, the
supersaturated solution is crystallized in a second
unit, which yields crystals with extraordinary
purity. The process uses heterogeneous nucleation
due to the presence of a membrane surface acting
as growth points. Thus, the membrane is used as
an active surface to promote heterogeneous nucle-
ation, but also for mass transfer. This allows a
good process control and fast crystallization;
membrane-assisted crystallization is in that sense
superior to other crystallization methods. For
these reasons, membrane crystallization is a
promising process not only for inorganic salts
(Van der Bruggen et al. 2004) but also for proteins
with substantial added value (Di Profio
et al. 2003). A high uniformity in size was
obtained for crystallization of trypsins in a mem-
brane crystallizer (Di Profio et al. 2005), with
crystals produced in forced solution flow found
to be more uniform than those obtained in a qui-
escent membrane system. The crystallization
system was further optimized by increasing solu-
tion velocity to a maximum.
Cross-References
▶ Membrane Crystallization
▶ Membrane Distillation
▶ Membrane Synthesis
▶ Supersaturated Solution
References
Cahn J (1960) Theory of crystal growth and interface
motion in crystalline materials. Acta Metall
8(8):554–562
Curcio E, Drioli E (2005) Membrane distillation and
related operations—a review. Sep Purif Rev
34(1):35–86
Curcio E, Criscuoli A, Drioli E (2001) Membrane crystal-
lizers. Ind Eng Chem Res 40(12):2679–2684
Di Profio G, Curcio E, Cassetta A, Lamba D, Drioli
E (2003) Membrane crystallization of lysozyme:
kinetic aspects. J Cryst Growth 257(3–4):359–369
Di Profio G, Perrone G, Curcio E, Cassetta A, Lamba D,
Drioli E (2005) Preparation of enzyme crystals with
tunable morphology in membrane crystallizers. Ind
Eng Chem Res 44(26):10005–10012
Frank FC (1949) The influence of dislocations on crystal
growth. Discuss Faraday Soc 5:48–54
Girshick SL, Chiu CP (1990) Kinetic nucleation theory: a
new expression for the rate of homogeneous nucleation
from an ideal supersaturated vapor. J Chem Phys
93(2):1273–1277
Lin X, Kita H, Okamoto KI (2001) Silicalite membrane
preparation, characterization, and separation perfor-
mance. Ind Eng Chem Res 40(19):4069–4078
Van der Bruggen b, Curcio E, Drioli E (2004) Process
intensification in the textile industry: the role of mem-
brane technology. J Environ Manag 73(3):267–274
O
O2/N2 Separation
Ahmad Fauzi Ismail
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Advanced
Membrane Technology Research Centre
(AMTEC), Skudai, Johor, Malaysia
Separation of air into oxygen and nitrogen is an
important process, and this separation process has
been applied in an industrial scale such as oxygen
(O2) enrichment from air (medical devices) and
nitrogen (N2) enrichment from air (used as
protecting atmosphere for oxygen-sensitive com-
pounds) (Jeazet et al. 2012). There are three tech-
nologies that currently exist for separating
oxygen and nitrogen from the air including cryo-
genic distillation, pressure swing adsorption
(PSA), and membranes. Among these three tech-
nologies, cryogenic distillation is considered the
most mature technology and allows for the pro-
duction of both high purities (>99 %) and large-
scale productions. However, this technology is
renowned to be complex, expensive, and energy
intensive, which consumes about 15 % of the
electrical output of the power station (Hashim
et al. 2011).
PSA is a technology that used to separate some
gas species from a mixture of gases under pres-
sure based on the molecular characteristics of the
species and affinity for an adsorbent material.
Under high pressure, gases tend to be attracted
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_418-4
to solid surfaces (adsorbed), and different gases
tend to be attracted to different solid surfaces. For
example, in air mixture, carbon molecular sieves
(CMS) as the adsorbent bed will adsorb oxygen
and water vapor molecules under high pressure
while allowing N2 gas to pass through. Rufford
et al. (2012) claimed that the preferential adsorp-
tion of components from a gas mixture can be
achieved by one, or a combination, of the follow-
ing mechanisms:
1. Differences in the adsorbate-surface interac-
tions and/or adsorbate packing interactions
when the system reaches equilibrium
2. Differences in the size and/or shape of gas
molecules
3. Differences in the diffusion rates of molecules
through the adsorbent pores
Yet, the main disadvantage of PSA occurs
when large flow rates of N2 are needed; therefore,
a large vessel needs to be utilized which conse-
quently increased the installation cost.
The development of membranes for partial air
separation progressed rapidly since the 1980s,
and this technology is attractive compared to the
conventional separation facilities because
membrane-based devices are much smaller and
can be operated at lower temperature. For dense
polymeric membrane, the differences in solubil-
ity and diffusivity of O2 and N2 in and through the
membrane materials will make the separation
between the gases occurred. In solution-diffusion
2 O2/N2 Separation
model, permeants dissolve in the membrane
material and then diffuse through the membrane
down a concentration gradient. Polyimide, poly-
carbonate, polysulfone, polyethersulfone, and
other aromatic polymers are commonly used as
polymeric membrane-based devices for gas sep-
aration. Mixed matrix membrane (MMM) is a
combination of polymer matrix with molecular
sieve materials. Separation of gases through
molecular sieving materials depends on the dif-
ferences in molecular size of the gases. By com-
bining the polymer matrix and molecular sieve
materials, MMM with enhanced performance,
heat, and chemical resistance can be developed.
Other types of membranes that foreseen as the
promising technology to replace cryogenic sepa-
ration for high purity and bulky supply of O2 from
air separation are ion transfer membranes. Ion
transfer membranes are solid inorganic oxide
ceramic materials with complex crystalline struc-
tures. These dense membranes allow oxygen ions
to diffuse in the direction of decreasing O2 partial
pressure given an adequate electronic conductiv-
ity that allows the counter migration of electrons
(Steeneveldt et al. 2006). The movement of O2
ions down the membrane is charge compensated
by the opposite movement of electrons. Then, the
oxygen ions release their electrons and recom-
bine to form molecular oxygen at the low partial
pressure end. Therefore, the separation of oxygen
via ion transfer membrane concept is achieved
with the ability of the oxide membrane to conduct
both ions and electrons (Leo et al. 2009).
Oxygen-enriched air at various concentrations
can be achieved in polymeric membrane,
whereas ion transfer membranes can give purities
of close to 100 %. However, until now both
membranes have not been built for large-scale
gas separations (Burdyny and Struchtrup 2010).
References
Burdyny T, Struchtrup H (2010) Hybrid membrane/cryo-
genic separation of oxygen from air for use in the
oxy-fuel process. Energy 35:1884–1897
Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep-
aration from air using ceramic-based membrane tech-
nology for sustainable fuel production and power
generation. Renew Sust Energ Rev 15:1284–1293
Jeazet HBT, Staudt C, Janiak C (2012) A method for
increasing permeability in O2/N2 separation with
mixed-matrix membranes made of water-stable
MIL-101 and polysulfone. Chem Commun
48:2140–2142
Leo A, Liu S, Diniz da Costa JC (2009) Development of
mixed conducting membranes for clean coal energy
delivery. Int J Greenh Gas Control 3:357–367
Rufford TE, Smart S, Watson GCY, Graham BF, Boxall J,
Diniz da Costa JC, May EF (2012) The removal of
CO2 and N2 from natural gas: a review of conven-
tional and emerging process technologies. J Pet Sci
Eng 94–95:123–154
Steeneveldt R, Berger B, Torp TA (2006) CO2 capture and
storage: closing the knowing-doing gap. Chem Eng
Res Des 84(A9):739–763
O
Off-Gas from Catalytic Reforming
A. Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
The largest source of hydrogen in the refinery is
the off-gas of the catalytic reforming unit. Cata-
lytic reforming is a reaction using precious metal
(platinum or rhenium)-based catalysts that con-
verts alkane-containing naphta into two main
products: aromatics and hydrogen. The produced
hydrogen generally contains from 10 % to 30 %
of cracked hydrocarbons ranging from C1 to C6+
as well as traces (at the ppmv level) of HCl and
aromatics (Yampulski and Freeman 2010).
As a general rule the hydrogen produced in the
catalytic reforming is purified via a PSA
(pressure-swing adsorption) unit prior to being
reintroduced in other hydrogen-consuming units
of the refinery such as hydrotreatments or hydro-
cracking units. PSA proves to be a very profitable
unit for such an application, as this technology
allows to reach very high purities in hydrogen
(>99 % molar) and high yield as the tail gas
flow of the adsorber, mainly composed of the
hydrocarbon part of the reformer off-gas, is very
small compared to the feed gas flow. Membrane-
based gas permeation unit is sometimes used to
purify the hydrogen contained in the off-gas of
the catalytic reformer; especially it is necessary
to regenerate the catalyst. In this case, when small
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_419-1
hydrogen feed flows (up to 1000 Nm3 ∙ h 1) and
medium hydrogen purities (between 90 % and
98 % molar) are required, gas permeation proves
economically viable at the industrial scale.
Nowadays, three main membrane providers
offer hydrogen purification permeators:
– Air Products with the Prism ® silicon-coated
polysulfone membranes (issued from
Monsanto). Air Products claims that the life-
time of the Prism ® modules can be more than
15 years.
– Ube Industries with polyimide hollow fiber
membranes.
– Air Liquide with the MEDAL polyimide and
high-selectivity polyaramide membranes.
All those membranes are based on glassy
polymers and offer a diffusion-based hydrogen
selectivity. Today’s membranes have high H2/
CH4 selectivities (from 35 to 200 at 80  C
(Roman et al. 1991)). For instance, Air Products
claims that a single-stage array of Prism ® mod-
ules is able to raise the concentration of gases
from 10 % to 30 % up to 70–90 % (Air Products
website), while Medal membranes are able to
raise the concentration of a gas at 51 bar from
86 % in hydrogen up to 98 % with a permeate
pressure at 30 bar and a residue containing 52 %
of hydrogen at 50 bar (Medal Internet website).
2 Off-Gas from Catalytic Reforming

References Monereau C (2003) Perméation hydrogène: de la

Air Products website. http://www.airproducts.com/Prod
ucts/Equipment/PRISMMembranes/page08.htm
Medal Internet website. www.medal.airliquide.com
périphérie des procédé vers le coeur des procédés.
Intégration des membranes dans les procédés
2(89):275–282
Yampulski Y, Freeman BD (2010) Membrane gas separa-
tion. Wiley, New-York
O
Optimal Process Control
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Efficient automatic control system is an essential
part of every plant being operated in chemical
industry. It may be implemented for various rea-
sons: plant and environmental safety, fulfillment
of varying process demands, rejection of input
disturbances, optimal production desire, etc.
Process control is usually achieved via feed-
back policy. By measuring time-varying process
outputs y(t) (controlled variables), such as tem-
perature or concentration, one decides about pro-
cess inputs u(t) (manipulated variables), such as
input power to heating cell or valve position, to
attain some or all of the abovementioned goals.
Classical control theory defines a fashion in
which obtained measurements are used to iden-
tify values of inputs as a control law (Skogestad
and Postlethwaite 2005). Its basic form can be
stated as
uðtÞ ¼ f ðyðtÞÞ
uðtÞ ¼ f ðyðtÞÞ where f() represents a function
which can take various forms and can be designed
using analytical or numerical methods in order to
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_422-7
establish optimal, adaptive, robust, stochastic, or
any other type of process control.
Optimality of the process is measured in terms
of performance criterion J(y,u). Optimal control
of the process should be then set such that it
minimizes this criterion. Classical problems of
optimal control involve problems such as refer-
ence tracking or optimal change over control.
The most common reference tracking problem
is expressed by
ð1
 T  
min y  yref Q y  yref þ uT Ru dt
u 0
where yref represents output reference (trajectory)
and Q and R are so-called weighing matrices
(Mikles and Fikar 2007). If this problem is con-
sidered and the controlled process is described by
linear model (e.g., transfer function), function f()
takes the form of a matrix-vector product, Ky.
Matrix K can be found easily using the tools of
linear algebra. However, if the controlled system
exhibits nonlinear behavior, more complicated
techniques (e.g., dynamic optimization) are
required.
Cross-References
▶ Process Control in Membrane Operations
2 Optimal Process Control

References Skogestad S, Postlethwaite I (2005) Multivariable feed-

back control – analysis and design. Multivariable
Mikles J, Fikar M (2007) Process modelling, identifica- Feedback Control: Analysis and Design John Wiley
tion, and control. Springer Verlag, Berlin & Sons. ISBN:0470011688
O

Orthogonal Collocation Method
 XNp

Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
This method represents an approximation tech-
nique which is successfully used to solve
multipoint boundary value problems. Such prob-
lems arise in engineering applications frequently
when it is desired to simulate processes described
by partial differential equations (Kaldis
et al. 2000; Sousa and Mendes 2004), to model
complex processes (Ganguly and Bhattacharya
(1994); Sousa et al. 2002) or to compute optimal
process control (Fikar et al. 2010).
The principle is to approximate the behavior
of any nonlinear function f(x) by the sum of basis
functions (most preferably polynomials) on some
chosen number of intervals. Approximation func-
tion on the kth interval, Yk, can be written as
Yk yk , x ¼ yki fki ðxÞ
i¼0
where yk is a vector of Npþ1 collocation points
which represent weighting factors (coefficients)
for vector of functions fk. If polynomial approx-
imation is considered, function fik is an Np th
order polynomial. To guarantee the orthogonality
of resulting approximation and to achieve other
useful properties, orthogonal polynomials (such
as Chebyshev, Lagrange, and other types) are
used. For the case of Lagrange polynomials,
function fik can be written as follows:
Np x  xkj
fki ðxÞ ¼ ∏ :
j¼0, j6¼i xi  xj
k k
This is illustrated in Fig. 1 which shows three
consecutive intervals of approximation.

# Springer-Verlag Berlin Heidelberg 2012

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_428-2
2 Orthogonal Collocation Method

yk +1
Np
yk1+1
yk yk
0 1 yk yk0+1
ykN–1 2 ykN
yk0–1 p p

yk1–1

x k1 –1 x k2 –1 x kN–1 x k1 x k2 x kN x 1k +1 x k2+1 x kN+1

p p p

Δx k –1 Δx k Δx k +1
x k0 –1 x k0 x k0 +1 x k0 +2

Orthogonal Collocation Method, Fig. 1 Schematic representation of orthogonal collocation method

References collocation – hydrogen recovery from refinery gases.

Fikar M, Kovács Z, Czermak P (2010) Dynamic optimi-
zation of batch diafiltration processes. J Membr Sci
355(1–2):168–174. doi:10.1016/j.
memsci.2010.03.019
Ganguly S, Bhattacharya PK (1994) Development of con-
centration profile and prediction of flux for ultrafiltra-
tion in a radial cross-flow cell. J Membr Sci
97:185–198. doi:10.1016/0376-7388(94)00161-Q.
ISSN 0376-7388
Kaldis SP, Kapantaidakis GC, Sakellaropoulos GP
(2000) Simulation of multi-component gas separation
in a hollow fiber membrane by orthogonal
J Membr Sci 173(1):61–71. doi:10.1016/S0376-
7388(00)00353-7. ISSN 0376-7388
Sousa JM, Mendes A (2004) Simulating catalytic mem-
brane reactors using orthogonal collocation with spa-
tial coordinates transformation. J Membr Sci
243(1–2):283–292. doi:10.1016/j.
memsci.2004.06.031. ISSN 0376-7388
Sousa JM, Cruz P, Magalhaes FD, Mendes A (2002)
Modeling catalytic membrane reactors using an adap-
tive wavelet-based collocation method. J Membr Sci
208(1–2):57–68. doi:10.1016/S0376-7388(02)00175-
8. ISSN 0376-7388
O
Oxidative Steam Reforming
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
Autothermal reforming or oxidative steam
reforming is a combination of conventional
steam reforming of the fuel (endothermic reac-
tion) with the partial oxidation of a small amount
of the fuel (exothermic reaction) in order to
achieve an autothermal reaction that proceeds
without external input of energy.
The most studied autothermal reforming is the
conversion of methane to hydrogen. The overall
chemical reactions taking place in the
autothermal reforming of methane include
steam reforming (Eq. 1), water-gas shift (Eq. 2),
and total oxidation (Eq. 3). The energy generated
by the oxidation reaction and WGS is used for the
SMR:
CH4 þ H2 O ¼ CO þ 3H2
CO þ H2 O ¼ CO2 þ H2
CH4 þ 2O2 ¼> CO2 þ 2H2 O
This reaction system can be carried out efficiently
in a membrane reactor as the extraction of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_433-3
hydrogen during the reaction shifts the equilib-
rium reactions toward completion at moderate
temperatures, and thus the extent of oxidation
reaction to achieve autothermal reforming is
moderate.
One of the problems of autothermal reforming
carried out in membrane reactors is the mismatch
between the oxidation reaction rate and the
reforming reaction rate. The oxidation is often
much faster than the reforming, and for this rea-
son, in packed bed membrane reactors, a high
temperature region is obtained at the beginning
of the bed followed by a low temperature region
at the end of the bed. This could cause problems
to the membranes that could be damaged by high
temperatures while does not work properly (low
flux – see Richardson equation) at lower
temperatures.
To circumvent these problems, fluidized bed
membrane reactors are often proposed for this
kind of reaction system, as the solid circulation
inside the reactor allows a virtually isothermal
condition even in case of highly exothermic
reactions.
(1) Examples of autothermal reforming (ATR)
(or oxidative steam reforming) reactions also
(2) include the ATR of ethanol and methanol or the
ATR of naphtha. All these reactions have been
(3) successfully tested in membrane reactors for pure
hydrogen production.
O

Oxyfuel electricity generation by the oxyfuel process is

more expensive than in a traditional air-fired
Juergen Caro plant. The main cost factor of the oxyfuel process
Institut of Physical Chemistry and is the production of almost pure oxygen.
Electrochemistry, Leibniz University, Perovskite-type mixed conducting ceramics can
Hannover, Germany theoretically separate oxygen with 100 % purity
from air. Some of the CO2 is in a loop used for
sweeping the oxygen from the membrane separator
Synonyms to the combustion chamber thus reducing the
oxygen partial pressure on the permeate side of
Oxyfuel combustion the membrane to have a constant high driving
force for oxygen permeation. This sweeping tech-
The name is derived from the process: a mixture
nique with some of the CO2 in a loop requires CO2-
of oxygen and a gaseous, liquid, or solid fuel is
stable oxygen-conducting membranes. Since most
burnt in a nitrogen-free atmosphere which con-
of the mixed conducting perovskite-type ceramics
sists of oxygen and an easy to separate second
contain alkaline earth metal cations, these mate-
gas, usually carbon dioxide. If fuels like natural
rials are not suitable since they form carbonates
gas, oil, or coal are combusted with pure oxygen
(for thermodynamic reasons also at high tempera-
instead of air as oxidant, nitrogen as an inert
tures because of the high CO2 partial pressure).
component is not heated. Therefore, the burning
Therefore, new CO2-stable mixed conducting or
unit can be smaller, the flame temperatures are
dual-phase materials have to be developed.
higher, and the fuel consumption is reduced.
Since the fuel is combusted in an O2/CO2 atm,
Depending on the fuel, the flue gas consists of
this combustion with diluted oxygen reduces the
CO2 and H2O only. After condensation of H2O,
flame temperature which reduces the costs for
the flue gas consists of only CO2 which can be
special high temperature-resistant materials. The
sequestrated or used in chemical processes. But
amount of the second inert gas can control the
not only the mass and volume of the flue gas
flame temperature of the combustion: Without
become smaller, due to the absence of nitrogen,
any dilution gas, the combustion temperature
also no NOx is formed.
can become too high. On the other hand, if the
The oxyfuel combustion process is one of
CO2 concentration is much less than 80 %
several possible technologies to separate and
(nitrogen content of air), higher flame tempera-
sequestrate CO2 from fossil fuel burning espe-
tures can be reached which is desired.
cially in electric power stations. However,

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_434-1
2 Oxyfuel
However, the few pilot plants evaluating the
feasibility of the oxyfuel concept use oxygen
production by cryogenic air separation after
Linde (Callide Oxyfuel Project; Callide Oxyfuel
Pilot Project; CCS Vattenfall Pilot Oxyfuel Pro-
ject). In 2006 in the Schwarze Pumpe industrial
area in East Germany, construction work started
on the world’s first “carbon-dioxide free” power
station testing the oxyfuel concept on a pilote
scale. However, the owner Vattenfall stopped
carbon capture R&D at the plant in 2014 because
“its costs and the energy it requires makes the
technology unviable” (http:www.thelocal.se/
20140507/vattenfall-abondons-research-on-co2-
storage). In the Callide oxyfuel project, carbon
dioxide capture started in Dec. 2012. In March
2015, the Callide Oxyfuel Project demonstration
phase comes to a close after 2 years and 9 months
successfully proving 10,000 h of oxyfuel
combustion, and 5,500 h of carbon dioxide plant
operation. Since the usual oxygen purity of
99.5 % as obtained in the Linde technique is not
necessary for oxyfuel, the Linde technology can
produce oxygen with 95 % purity in a cost-
effective way which is competing with the
ceramic membrane technology. Organic polymer
membrane permeation is not competitive since it
cannot produce the necessary oxygen purity of
95 % purity in a single step.
References
Callide Oxyfuel pilot project, Cubillos del Sil, Spain
Callide Oxyfuel project, Queensland, Australia
CCS Vattenfall pilot Oxyfuel project, Schwarze Pumpe,
Germany
O
Oxygen Separation
Juergen Caro
Universität Hannover, Institut of Physical
Chemistry and Electrochemistry, Leibniz
University Hannover, Hannover, Germany
Synonyms
Air separation
Oxygen can by separated from air by different
separation techniques such as cryogenic air dis-
tillation after Linde, pressure swing adsorption
using coals for kinetic separation (the slightly
smaller oxygen diffuses faster than nitrogen into
the pores of the coal), or Li-exchanged zeolites
like Li-LTA/Li-FAU for thermodynamically
controlled separation (the more polar nitrogen is
strongly adsorbed by the zeolite than the less
polar oxygen). Also organic polymer hollow
fiber membranes are used for oxygen/nitrogen
separation, but they produce in general lower
gas purity. The amount and purity of the oxygen
to be produced decides about the economy of the
separation techniques to be applied.
Perovskite membranes allow principally a
new route for oxygen separation from air, how-
ever, at elevated temperatures of 750  C to
900  C. The high temperatures are necessary for
a high-oxygen ion mobility and to avoid mem-
brane damage (if CO2 is present in low
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_435-1
concentrations, carbonates do not form at high
temperatures, see Ellingham diagram). As long
as there is a sufficient gradient of the oxygen
partial pressure (better: activity) over the mem-
brane, oxygen will enter the perovskite material
on the high-oxygen partial pressure side (feed
side) and leave the membrane on the
low-oxygen partial pressure side (permeate
side). The low-oxygen partial pressure can be
achieved by continuous vacuum pumping as the
most effective and economic technique but also
with sweep gases. In the latter case, the sweep
gases and oxygen must be separated again
(if steam is used, the membrane can be damaged
at the high permeation temperature). Another
option to reduce the oxygen partial pressure on
the permeate side is the consumption of the per-
meated oxygen in a catalytic partial oxidation
(e.g., by consuming oxygen in a methane partial
oxidation to synthesis gas).
Figure 1 shows a three-tube perovskite mem-
brane module with 1 cm (outer diameter)
Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF) tubes purchased
from Fraunhofer IKTS (Fraunhofer Institute for
Ceramic Technologies and Systems, Dresden-
Hermsdorf, Germany). The permeator has been
erected during November 2012–April 2013 at
Leibniz University of Hannover copying a proto-
type oxygen separation permeator developed by
Dr. R. Kriegel (Fraunhofer IKTS, Hermsdorf)
(Kriegel et al. 2010; Schulz et al. 2011). The
permeator is gastight up to an operation
2 Oxygen Separation
Oxygen Separation, Fig. 1 Photo and scheme of the
three-tube oxygen production demonstration unit at Leib-
niz University of Hannover (copyright Caro, Univ. Han-
nover). Oxygen from surrounding air enters the BCFZ
material on the shell side, diffuses via vacancies in the
temperature of 950  C, membrane area 400 cm2,
and dead-end BSCF tubes.
oxygen lattice to the core side of the one-end-sealed BSCF
tubes where it is released into the gas phase. To have a
high-oxygen partial pressure difference over the mem-
brane, the permeated oxygen is removed by vacuum
pumping
References
Kriegel R, Kirchheim R, Töpfer J (2010) Oxygen stoichi-
ometry and expansion behaviour of
Ba0.5Sr0.5Co0.8Fe0.2O3-d. Solid State Ionics 181:64–70
Schulz M, Kriegel R, Kämpfer A (2011) Assessment of
CO2 stability and oxygen flux of oxygen permeable
membranes. J Membr Sci 378:10–17
P
Packed Bed Membrane Reactor
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
The fixed bed (or packed bed) membrane reactor
configuration is the first and most studied config-
uration for membrane reactors. This is because
the first studies on membrane reactors focused on
the effect of the gas permeation through mem-
branes on the reaction system (which is often a
conventional packed bed reactor).
In a packed bed membrane reactor, the cata-
lyst is confined in fixed bed configuration, and it
is in contact with a permselective membrane. The
most used packed bed configuration is the tubular
one where the catalyst may be packed either in
the membrane tube or in the shell side, while the
permeation stream is collected in the other side of
the membrane (in case of hydrogen-selective
membranes) or one reactant is feed on the other
side of the membrane (in case of oxygen-
selective membrane).
For multi-tubular membrane reactor configu-
rations, the catalyst in tube configuration can be
preferred especially for construction reason and
for the extent of bed-to-wall mass and heat trans-
fer limitations which can be very detrimental in
the catalyst in shell configuration.
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_436-1
Often, a sweep gas can be used in the perme-
ation side of the membrane in order to keep the
permeation hydrogen partial pressure as low as
possible for minimizing the membrane area
required for the hydrogen separation. This prac-
tice is, for example, very useful if hydrogen for
ammonia plant is being produced, in which case
an amount of nitrogen can be used for sweeping
the permeation side producing a synthesis stream
(N2/H2 = 1/3) ready for the final reaction step. If
a sweep gas is used in the permeation side, then a
packed bed membrane reactor can be used in both
cocurrent or countercurrent modes.
An interesting feature of packed bed mem-
brane reactors is the possibility to operate them
in a reverse flow mode, integrating the reaction
and separation with the recuperative heat
exchange inside the reactor. This operational
mode is quite interesting for partial oxidation of
methane (POM) (Smit et al. 2005). In normal
POM systems, air and CH4 feed streams have to
be preheated to the reaction temperature, while
POM reaction being only slightly exothermic, the
external heat transfer between feed and exhaust is
very expensive. Therefore, recuperative heat
exchange is preferably carried out inside the
reactor.
Although the tube in tube configuration is
quite useful to work in lab scale and for proof of
principle of membrane reactors, for industrial
scale some other configurations need to be used
in order to increase the membrane area per vol-
ume of vessel used. In fact, the amount of
2 Packed Bed Membrane Reactor
hydrogen produced is directly related to the
amount of membrane area installed in the reactor.
Starting for the tube in tube configuration, a
straightforward way to increase the membrane
area in packed bed is the tube in shell configura-
tion (Buxbaum 2002; Tosti et al. 2008).
Although the packed bed configuration is very
advantageous and easy to operate, the production
of thin membranes brought under the spotlight
one of the disadvantages of fixed bed membrane
reactors: the influence of bed-to-wall mass trans-
fer limitations on the membrane area required.
Briefly, as long as the hydrogen flux through the
membrane is a limiting step, the effect of external
mass transfer limitations such as the limitations
to hydrogen transport between the bulk of the
catalytic bed (where hydrogen is produced) and
the membrane wall (where hydrogen is recov-
ered) can be neglected. However, by increasing
the membrane flux, the external mass transfer
limitations became limiting and determine the
extent of membrane area. This has been demon-
strated both experimentally (Peters et al. 2008)
and numerically (Gallucci et al. 2010). This
important drawback has driven the research
toward new reactor concepts such as
micromembrane reactors or fluidized bed mem-
brane reactors.
References
Buxbaum RE (2002) Patent US 6,461,408
Gallucci F, Van Sint Annaland M, Kuipers JAM
(2010) Theoretical comparison of packed bed and flu-
idized bed membrane reactors for methane reforming.
Int J Hydrog Energy 35:7142–7150
Peters TA, Stange M, Klette H, Bredesen R (2008) High
pressure performance of thin Pd-23%Ag/stainless steel
composite membranes in water gas shift gas mixtures;
influence of dilution, mass transfer and surface effects
on the hydrogen flux. J Membrane Sci
316(1–2):119–127
Smit J, Bekink GJ, Van Sint Annaland M, Kuipers JAM
(2005) A reverse flow catalytic membrane reactor for
the production of syngas: an experimental study. Int
J Chem React Eng 3:1
Tosti S, Basile A, Bettinali L, Borgognoni F, Gallucci F,
Rizzello C (2008) Design and process study of Pd
membrane reactors. Int J Hydrog Energy
33(19):5098–5105
P
Pd-Based Tubular Membrane
Reactor
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
A Pd-based tubular membrane reactor consists
of two concentric tubes where the internal one is
the metallic membrane separating the two reactor
sides, that is, the reaction and permeate volumes.
The reaction side can be the core of the inner tube
or the annular volume between the two tubes. The
Pd-based membranes are used since they are per-
meable only to hydrogen. Therefore, such a reac-
tor will be mainly evaluated on two performance
parameters: feed conversion and hydrogen recov-
ery on permeate side.
A reactor having a prevalent geometrical
development along a specific direction is known
as tubular reactor. Its most common cross section
is the circular one even though other sections
such as square, rectangular, etc., are possible.
Thus, a cylindrical surface mostly delimits such
a reactor and two circles define the entrance and
exit surfaces.
Such a tubular reactor with a circular cross
section is commonly used both industrially and
at a lab scale. This configuration allows the pres-
sure on the reactor surface to be uniformly dis-
tributed, a very important issue for industrial
application where the pressure can be really
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_439-1
high; in some cases (see ammonia synthesis),
the reaction pressure reaches 600–1000 bar.
This reactor is commonly used in the laboratory
for its cylindrical symmetry which allows to
reducing the complexity of the equation set for
mass and energy balance. Often, in a first approx-
imation, radial and axial diffusions of mass and
energy are neglected, and the resulting mathe-
matical model consists in an ODE (ordinary dif-
ferential equation) system of the first order whose
resolution is much simpler than that of PDE
(partial differential equations) system of the sec-
ond order necessary for the mathematical
description in the absence of cylindrical symme-
try and radial and axial diffusions. This reactor
model, known as plug flow reactor (PFR), is the
most common experimental investigated since its
mathematical description consisting in a first-
order ODE set, as above said, is the simplest
one from a fluidodynamics point of view after
the continuous stirred tank reactor.
The reactor diameter ranges from a few centi-
meters to meters also depending on the exother-
micity/endothermicity of the reaction, in other
words on the necessity of heat exchange/provi-
sion. Often, industrial reactors operate in adia-
batic conditions, but in some cases the heat
request by reaction is so high that energy has to
be provided in order for the reaction to precede;
in these cases small diameter is preferred to the
higher one.
The simplest Pd-based tubular membrane
reactor utilized the various advantages
2 Pd-Based Tubular Membrane Reactor
Q Feed
Permeating
JH2
Q Permeate
P Permeation Membrane
P Reaction Catalyst
Pd-Based Tubular Membrane Reactor, Fig. 1
(cylindrical symmetry, no radial and axial diffu-
sions) of a plug flow reactor on reaction side; this
condition is also valid for the permeate volume.
This membrane reactor (MR) model is mathemat-
ically described by a first-order ODE set. The two
streams in the reaction and permeate volumes can
be in co- or, as shown in the next figure, counter-
current configurations. The permeation driving
force, the difference between the square root of
hydrogen partial pressure on reaction and perme-
ation sides, of a co-current tubular MR is the
highest at the entrance and it reduces along the
reactor length; if the reactor is really long, this
difference becomes null. The permeation driving
force of a countercurrent tubular MR is more
distributed along the reactor length (Barbieri
and Di Maio 1997). Therefore, countercurrent
flow configuration results in a higher perfor-
mance in terms of, e.g., reaction conversion and
hydrogen recovery. The countercurrent configu-
ration requires a shooting method for the numer-
ical solution of the ODEs set. Equation 1 shows
an example of an ODE system for an MR oper-
ating in steady state (Fig. 1):
dFi

þ ½Generation by reaction
dz

½Permeation through the membrane
¼0 (1)
The choice about the reaction volume as the one
inside the core of the membrane or in the annular
space between the two tubes depends on several
factors, e.g., contact between the catalyst and
membrane (can damage the membrane since
this is a few microns thin) and heat transfer
from the energy source and reaction. The heat
Q Retentate
Q Sweep
SS-Shell
transfer is more efficient (Marigliano
et al. 2001) if the reaction takes place in the
annular space since the resistance in this case is
concentrated in the external tube and in the gas
films around it. In the other case, the overall heat
transfer coefficient is lower since the energy has
to be transported through the permeation
volume too.
Different reactor configurations and geome-
tries also including radial and axial diffusions
are often operated also at lab scale for analyzing
the effect related to the mass and energy diffusive
transport. The following Eq. 2 shows the com-
plexity of PDE set of a two-dimensional second-
order mathematical model written down for a
tubular MR operating in steady state:
@ 2 PReactionSide
i
Diffusivityi, z
@z2
@ 2 PReactionSide
þDiffusivityi, r i
þ Rgas T ReactionSide
r, z
@r2
!
@N ReactionSide
i, z
þ ½Generation by reactionr, z ¼0
@z
(2)
Models for more complex reactor configurations
and geometries also including radial and axial
diffusions are reported in (Barbieri et al. 2008a)
and characterized by first- and second-order
PDE set.
Two more aspects have to be discussed for an
MR: the concentration gradients, more known as
concentration polarization, and the permeation
reduction owing to the presence of some gases
since both reduce the membrane performance.
Pd-Based Tubular Membrane Reactor
The permeation is a mass transport happening
at a surface – the one delimited by the
membrane – and when it is selective creates a
variation in the composition of species in the film
close to the membrane itself. This variation will
spread with a finite – not infinite – velocity; this
means a concentration profile is created in the
orthogonal direction at the membrane surface.
The concentration profile is physiological in any
membrane separation and its breadth depends on
membrane selectivity and permeance. The higher
the selectivity and permeance, the higher the
concentration profile (Caravella et al. 2008,
2009; Boeltken et al. 2013). The presence of a
concentration gradient reduces significantly the
driving force for the permeation, that is, function
of the partial pressure at the membrane surface
and not the one in the bulk of the reaction and
permeation phases.
The adsorption of some species such as CO
and H2S (Gade et al. 2011; Morreale et al. 2004;
Kulprathipanja et al. 2005; Braun et al. 2012;
Kajiwara et al. 1999; Gabitto and Tsouris 2009;
Chen and Ma 2010; Iyoha et al. 2007) on the
membrane surface causing the reduction in the
number of metal surface sites for hydrogen
adsorption is a fundamental step for hydrogen
permeation. This phenomenon, known in cataly-
sis as poisoning of catalysts, follows the same
adsorption laws, e.g., the Langmuir one
(Barbieri et al. 2008b). It results in a significant
increase of permeation resistance and similar
permeance reduction (Caravella et al. 2010).
Both concentration gradients and inhibition by
chemical species have to be taken into account
for a proper evaluation of hydrogen permeation
(Caravella et al. 2010, 2011; Barbieri et al. 2011)
and hence membrane reactors performance.
References
Barbieri G, Di Maio FP (1997) Simulation of methane
steam reforming process in a catalytic Pd–membrane
reactor. Ind Eng Chem Res 36(6):2121–2127.
doi:10.1021/ie9601615
Barbieri G, Scura F, Brunetti A (2008a)
Chapter 9 – Mathematical modelling of Pd-alloy mem-
brane reactors. In: Mallada R, Menendez M (eds)
3
Inorganic membranes: synthesis, characterization and
applications, vol 13 Series membrane science and
technology. Elsevier B.V., Amsterdam/The Nether-
lands, pp 325–400. ISBN 978 0 444 53070
7. doi:10.1016/S0927-5193(07)13009-6
Barbieri G, Scura F, Lentini F, De Luca G, Drioli
E (2008b) A novel model equation for the permeation
of hydrogen in mixture with carbon-monoxide through
Pd-Ag membranes. Sep Purif Technol 61(2):217–224.
doi:10.1016/j.seppur.2007.10.010
Barbieri G, Caravella A, Drioli E (2011) Polarization and
CO inhibition in Pd-based membranes, Chapter 14. In:
Drioli E, Barbieri,G (eds) Membrane engineering for
the treatment of gases, vol 2 Gas-separation problems
combined with membrane reactors. The Royal Society
of Chemistry, Cambridge, MA, pp 137–161. ISBN
978-1-84973-239-0. http://pubs.rsc.org/en/content/
ebook/978-1-84973-239-0; doi:10.1039/
9781849733489-00137
Boeltken T, Belimov M, Pfeifer P, Peters TA, Bredesen R,
Dittmeyer R (2013) Fabrication and testing of a planar
microstructured concept module with integrated palla-
dium membranes. Chem Eng Process 67:136–147
Braun F, Miller JB, Gellman AJ, Tarditi AM, Fleutot B,
Kondratyuk P, Cornaglia LM (2012) PdAgAu alloy
with high resistance to corrosion H2S. Int J Hydrog
Energy 37:18547–18555
Caravella A, Barbieri G, Drioli E (2008) Modelling and
simulation of hydrogen permeation through supported
Pd-alloy membranes with a multicomponent approach.
Chem Eng Sci 63(8):2149–2160. doi:10.1016/j.
ces.2008.01.009
Caravella A, Barbieri G, Drioli E (2009) Concentration
polarization analysis in self-supported Pd-based mem-
branes. Sep Purif Technol 66:613–624. doi:10.1016/j.
seppur.2009.01.008
Caravella A, Scura F, Barbieri G, Drioli E (2010) Inhibi-
tion by CO and polarization in Pd-based membranes: a
novel permeance reduction coefficient. J Phys Chem
B 114:12264–12276. doi:10.1021/jp104767q
Caravella A, Scura F, Barbieri G, Drioli E, Hara S (2011)
On the role of the coupled effect of inhibition by CO
and concentration polarization on hydrogen perme-
ation through Pd-based membranes. Trans Mater Res
Soc Jpn 36:225–228. doi:10.14723/tmrsj.36.225
Chen C-H, Ma YH (2010) The effect of H2S on the
performance of Pd and Pd/Au composite membrane.
J Membr Sci 362:535–544
Gabitto JF, Tsouris C (2009) Sulfur poisoning of metal
membranes for hydrogen separation. Int Rew Chem
Eng 1(5):394–411
Gade SK, De Voss SJ, Coulter KE, Paglieri SN, Alptekin
GO, Way JD (2011) Palladium–gold membranes in
mixed gas streams with hydrogen sulfide: effect of
alloy content and fabrication technique. J Membr Sci
378(1–2):35–41
Iyoha O, Enrik R, Killmeyer R, Morreale B (2007) The
influence of hydrogen sulfide-to-hydrogen partial
4 Pd-Based Tubular Membrane Reactor
pressure ratio on the sulfidization of Pd and 70 mol%
Pd–Cu membranes. J Membr Sci 305:77–92
Kajiwara M, Uemiya S, Kojima T (1999) Stability and
hydrogen permeation behavior of supported platinum
membranes in presence of hydrogen sulfide. Int
J Hydrog Energy 24:839–844
Kulprathipanja A, Alptekin GO, Falconer JL, Way JD
(2005) Pd and Pd–Cu membranes: inhibition of H2
permeation by H2S. J Membr Sci 254:49–62
Marigliano G, Barbieri G, Drioli E (2001) Effect of energy
transport in a palladium based membrane reactor for
methane steam reforming process. Catal Today
67(1–3):85–99. doi:10.1016/S0920-5861(01)00268-1
Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
Cugini AV, Enick RM (2004) Effect of hydrogen-
sulfide on the hydrogen permeance of
palladium–copper alloys at elevated temperatures.
J Membr Sci 241:219–224
P
PEGylation
Andrew Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
PEGylation refers to the covalent attachment of
one or more polyethylene glycol (PEG) chains to
another molecule, typically a small therapeutic
protein (Veronese and Harris 2002). The attach-
ment of the PEG increases the hydrodynamic size
of the protein, reducing the clearance by the kid-
ney and significantly increasing the half-life of
the protein thereby reducing the dosage level and
frequency. PEGylation can also reduce the anti-
genicity of the protein, significantly reducing any
adverse immune response (Veronese 2009).
A variety of commercial PEGylated proteins are
currently on the market (Table 1).
PEGylation is typically accomplished by
reacting an activated form of the polyethylene
glycol with available reactive groups on the sur-
face of the therapeutic molecule. This includes
the free amino groups on the amino acid lysine as
well as the free sulfhydryl group on the amino
acid cysteine. The N-terminal amino group and
the C-terminal carboxylic acid can also be used
for site-specific PEGylation.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_441-4
One of the challenges in producing PEGylated
therapeutics is the need to remove the unreacted
protein and PEG, as well as any multiply
PEGylated species, from the desired (typically
singly) PEGylated product (Fee and Van Alstine
2006). A variety of chromatographic methods
have been developed for the purification of
PEGylated proteins including size exclusion
chromatography, ion exchange chromatography,
and hydrophobic interaction chromatography
(Fee 2009).
There is also considerable interest in the
development of ultrafiltration systems for the
purification of PEGylated proteins. Molek and
Zydney (2007) demonstrated the use of ultrafil-
tration to remove the unreacted protein, reaction
by-products, and unreacted PEG from a desired
PEGylated protein using a two-stage diafiltration
process. The first stage used an electrically neu-
tral membrane to remove the small unreacted
protein, with the neutral PEG removed in a sec-
ond stage using an electrically charged mem-
brane that provided high retention of the
charged PEGylated protein. Ruanjaikaen and
Zydney (2011) used a charged ultrafiltration
membrane to remove multiply PEGylated species
from singly PEGylated a-lactalbumin, with the
more heavily PEGylated species retained by the
charged ultrafiltration membrane using a combi-
nation of size and electrostatic interactions.
2 PEGylation

PEGylation, Table 1 Examples of commercial PEGylated products

Commercial
name Protein Manufacturer Indication
Adagen Bovine adenosine deaminase Enzon Severe combined
immunodeficiency
Oncaspar L-asparaginase Enzon Acute lymphoblastic leukemia
Peglntron Interferon alpha-2b Schering-Plough Hepatitis C, hepatitis B
Neulasta Granulocyte colony-stimulating factor Amgen Neutropenia
Pegasys Interferon alpha-2a Hoffman- Hepatitis C, hepatitis B
LaRoche
Somavert Modified human growth hormone Pharmacia- Acromegaly
Upjohn
Macugen Pegaptanib sodium Osi Wet macular degeneration
Pharmaceuticals
Cimzia Monoclonal antibody (TNF-alpha UCB, Inc. Crohn’s disease, rheumatoid
blocker) arthritis
Pegloticase Uricase Savient Chronic gout

References byproducts using ultrafiltration. Biotechnol Prog

Fee CJ (2009) Protein conjugates purification and charac-
terization. In: Veronese FM (ed) PEGylated protein
drugs: basic science and clinical applications.
Birkhauser Publishing, Basel, pp 113–125
Fee CJ, Van Alstine JM (2006) PEG-proteins: reaction
engineering and separation issues. Chem Eng Sci
61:924–939
Molek JR, Zydney AL (2007) Separation of PEGylated
a-lactalbumin from unreacted precursors and
23:1417–1424
Ruanjaikaen K, Zydney AL (2011) Purification of singly
PEGylated a-lactalbumin using charged ultrafiltration
membranes. Biotechnol Bioeng 108:822–829
Veronese FM (2009) PEGylated protein drugs: basic sci-
ence and clinical applications. Birkhauser Publishing,
Basel
Veronese FM, Harris JM (2002) Introduction and over-
view of peptide and protein pegylation. Adv Drug
Deliv Rev 54:453–456
P
Permeance
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, University of
Calabria, Rende (CS), Italy
Synonyms
Gas permeance
The permeance is a characteristic of a membrane
expressing the ability of a species to penetrate
and permeate a membrane of a specific thickness.
It is an overall coefficient to be used in the eval-
uation of the flux of any species permeating the
membrane as well membrane selectivity.
The driving force at the basis of mass transport
through the membrane, in most of the membrane
operations such as reverse osmosis,
nanofiltration, ultrafiltration, microfiltration, gas
separation, membrane distillation, membrane
contactors, etc., is a difference of feed and per-
meate pressures or species partial pressures. This
is valid for both dense membranes used in reverse
osmosis and gas separation and porous ones uti-
lized in the other operations. In addition, the
permeance most often does not depend on the
permeation driving force; thus, the following
equation defines the flux of each permeating spe-
cies (ith) as the product of permeance and driving
force:
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_445-1
Fluxi ¼ Permeancei  driving forcei
The reverse of this equation allows the
permeance to be calculated; thus, the membrane
permeance is evaluated for each species as the
ratio between the own flux and the related driving
force.
The driving force is calculated as function of
the pressure values in the bulks of the feed and
permeate streams or volumes for continuous or
batch systems, respectively. This means, the
permeance has to take into account all the mass
transfer resistance encountered by the molecules
along the path followed for their permeation from
the bulk of the feed side to the bulk of the perme-
ation side. These resistances are those in the film
on the feed side, in the separating membrane
layer, in the supporting membrane layer, in the
support eventually present, in the film on perme-
ation side, and in the fouling as well.
The units of the permeance depend on the
permeation mechanism at the basis of mass trans-
port through the membrane. In most of the mem-
brane operations as those before reported for
which the driving force is a difference of feed
and permeate pressures, the permeance units are:
mol m2 s1 Pa1
or m m s Pa1 , or m3 m2 h1 bar1 ,
3 2 1
or L m2 s1 Pa1 , or etc:Þ
2 Permeance
However, the driving force of the permeation in
inorganic membranes, such as the Pd-based and
perovskite ones, is the difference of the square
root of the pressures on both membrane sides
since the hydrogen (see Sieverts’ law) or oxygen
molecules permeating these membranes are dis-
sociated in atoms before their permeation in the
selective membrane layer. Consequently, the
permeance units are:
mol m2 s1 Pa0:5
or m m2 s1 Pa0:5 , or m3 m2 h1 bar0:5 ,
3 A Pd-based membrane operating at 5 and 1 bar
or L m2 s1 Pa0:5 , or etc:Þ
Power different from 0.5 is also utilized for the
feed-permeate pressure difference when the dif-
fusion in the separating layer is not the only rate-
determining step but surface phenomena are
significant.
Examples
The permeance of a reverse osmosis membrane,
operating under a feed-permeate pressure differ-
ence of 50 bar with a water flux of 60 m3 m2 h1,
is 60/50=1.2 m3 m2 h1 bar1.
The permeance of a gas separation membrane
having a CO2 flux of 5 m3 m2 h1 and operating
under a feed-permeate partial pressure difference
of 10 bar is 500 dm3(STP) m2 h1 bar1
(ca. 62 nmol m2 s1 Pa1).
as feed and permeate hydrogen pressures, respec-
tively, shows a hydrogen flux of 300 nmol m2
s1. Thus, hydrogen permeance is ca. 243 nmol
m2 s1 Pa-0.5.
P

Permeate membrane side with respect to the feed, it is

Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
The permeate is the whole mass permeated of the
membrane containing the different species which
permeated the membrane itself. On the other
collected in a volume or as a stream, leaving the
membrane module in a batch or continuous oper-
ations, respectively.
Together with the retentate, the permeate is
one of the two outlets of a membrane unit. The
other two streams are the feed and, optionally, the
sweep.

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_446-1
P
Permeate Gap Membrane
Distillation (PGMD)
Daniel Winter
Fraunhofer Institute for Solar Energy Systems
(ISE), Freiburg, Germany
Permeate gap membrane distillation (PGMD)
represents a specific configuration of the mem-
brane distillation (MD) process.
In a MD process, a hydrophobic highly porous
membrane separates an aqueous feed solution
from the distillate. The hydrophobic membrane
property prevents the liquid phase from entering
the membrane structure; thus, liquid-vapor inter-
faces are established on both sides of the mem-
brane. By applying a temperature difference,
evaporation takes place on the feed
(or evaporator) side; the vapor penetrates the
membrane pores and condenses on the permeate
(or condenser) side. The separation is based on
the phase change; thus, the product quality is
usually very high and does not depend on feed
concentration or the membrane structural proper-
ties. The coupled heat and mass transfer through
the membrane includes vapor flux, latent heat of
evaporation, and conductive heat transfer.
In conventional direct contact membrane dis-
tillation (DCMD) process, the heat of evapora-
tion is supplied by the hot feed stream, and the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_447-4
cooling is maintained by the cold stream,
respectively.
In permeate gap membrane distillation
(PGMD) process, a third channel is introduced
by an additional non-permeable foil, similar to air
gap membrane distillation (AGMD). The basic
PGMD channel arrangement is given in Fig. 1.
In PGMD, usually this channel is filled with
permeate during operation. One significant
advantage of this arrangement is the separation
of permeate from the cooling fluid. Therefore, the
coolant can be any other liquid, such as cold feed.
The presence of the permeate gap and the
non-permeable foil introduce additional heat
transfer resistances, which lead to a reduction of
the effective temperature difference across the
membrane. This heat transfer resistance is to be
minimized, by designing a very thin permeate
gap and using thin foils.
For special applications this concept can even
be further developed, e.g., by introducing a sec-
ond foil at the feed side. Here, the heating func-
tion can be decoupled from the feed solution as
well (Hausmann et al. 2011).
In module design, the PGMD concept pro-
vides the opportunity for internal heat recovery.
Modules are usually designed based on plate and
frame or spiral wound concepts.
Figure 2 shows the channel arrangement for a
PGMD module with integrated heat recovery.
2 Permeate Gap Membrane Distillation (PGMD)
Permeate Gap
Membrane Distillation
(PGMD), Fig. 1 Basic
channel arrangement and
temperature profile for
PGMD (Winter et al. 2011)
Permeate Gap Membrane Distillation (PGMD), Fig. 2 Principle channel arrangement of a spiral wound PGMD
module (Winter et al. 2011)
The PGMD channel arrangement is transferred
into a compact spiral package. Full-scale mod-
ules of this type were developed and fabricated at
Fraunhofer ISE (Winter et al. 2011). The total
membrane area is 5–15 m2. The module concept
goes back to a patent of W. L. Gore from 1985
(Gore et al. 1985).
This type of module is quite suitable to follow
the transient behavior of thermal energy input
from renewable sources. Thus, an integration to
solar thermal collectors or waste heat is easily
applicable. Various demonstration plants for
desalination using PGMD spiral wound modules
have already been tested in the field (Raluy
et al. 2012).
References
Gore WL et al. (1985) US Patent 4,545,862, United States,
Patent and trademark office
Hausmann A, Sanciolo P, Vasiljevic T, Weeks M, Duke
M (2011) Membrane distillation in the dairy industry:
process integration and membrane performance. In:
Proceedings of the international workshop on mem-
brane distillation and related technologies, Ravello
Raluy RG, Schwantes R, Subiela VJ, Peñate B, Melián G,
Betancort JR (2012) Operational experience of a solar
membrane distillation demonstration plant in Pozo
Izquierdo-Gran Canaria Island (Spain). Desalination
290:1–13
Winter D, Koschikowski J, Wieghaus M (2011) Desalina-
tion using membrane distillation: experimental studies
on full scale spiral wound modules. J Membr Sci
375:104–112
Further Reading
Cipollina A, Micale G, Rizzuti L (2009) Seawater desali-
nation. Springer, Heidelberg
Khayet M, Matsuura T (eds) (2011) Membrane distilla-
tion. Elsevier, Amersterdam
Koschikowski J (2011) Entwicklung von Energieautark
arbeitenden Wasserentsalzungsanlagen auf Basis der
Membrandestillation. PhD thesis, Fraunhofer ISE,
Fraunhofer, Universität Kassel
P
Permeating Flux
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
All the species permeating a membrane generate
a stream passing through the membrane, a stream
characterized by a flow rate according to the
actual operating conditions. A permeating flux
is defined for this stream as the ratio of the per-
meating flow rate and the membrane area.
Permeating Flow Rate
Permeating Flux ¼
Membrane Area
The permeating flux can be defined as well for ith
species as the ratio of the flow rate of the referred
species and the membrane area.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_448-1
Permeating Flow Ratei
Permeating Fluxi ¼
Membrane Area
It is a fraction of the total permeating flux and can
be expressed as product of the molar fraction of
the ith species and the permeating flux of all the
species.
Permeating Fluxi ¼ Molar Fractioni Permeating Flux
The permeating flux can be defined for each ele-
mentary membrane area element or for the whole
membrane area. In the first case, it is a function of
the spatial coordinates such as, for instance, the
membrane length. In the latter case, the permeat-
ing flux corresponds to the integration of the
permeating flow rate on the whole membrane
area of the elementary one divided for the whole
membrane area.
P

Permeation Number (ratio) between two main transport mechanisms

Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
involved in a membrane separation unit:
1. The mass transport through the membrane
2. The convective mass transport for feeding the
membrane unit

The permeation number expresses (Brunetti For the ith species, it is given by the equation
et al. 2010), for each species, a comparison

Permeancei Membrane Area Feed Pressure

Permeation Numberi ¼
Feed Molar Fractioni Feed Flow Rate Pressure Ratio

It is a dimensionless number to be used in sizing The pressure ratio is the ratio of the feed to the
the permeation unit. A low value means a low permeate pressures.
fraction of the referred ith species can pass
through the membrane; vice versa, a high value
means a large fraction of i will be in the permeate
References
stream.
A value of zero means no membrane separa- Brunetti A, Scura F, Barbieri G, Drioli E (2010) Mem-
tion, that is, permeance equals to zero or equiva- brane technologies for CO2 separation. J Membr Sci
lently no membrane area available for 359:115–125. doi:10.1016/j.memsci.2009.11.040
permeation.

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_449-1
P
Pervaporation (PV)
Bart Van der Bruggen
Department of Chemical Engineering,
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
Pervaporation is a membrane separation process,
in which components from a liquid mixture are
selectively transported through a dense or micro-
porous membrane. Pervaporation was mentioned
for the first time in 1917 by Kober in a publication
reporting on the selective permeation of water
from aqueous solutions of albumin and toluene
through cellulose nitrate films. “Pervaporation”
is a contraction of “permselective evaporation.”
The permselectivity originates from the mem-
brane itself, which selectively transports compo-
nents from the feed mixture, due to differences in
(mainly) hydrophilicity and molar size. Evapora-
tion is obtained by a low partial pressure at the
permeate side of the membrane, either by using a
vacuum or a sweep gas stream. The heat of vapor-
ization of the permeating components has been
supplied to the feed. In an industrial setup, this
heat is supplied by intermediate heat exchangers
installed between a number of pervaporation
modules in series. This is shown in the figure
below (Fig. 1).
Permeation through the membrane in
pervaporation can be described in two different
ways. The first is the use of pore flow model (and
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_451-1
derived models), developed by Okada and
Matsuura (1991). The basic assumption of such
models is that the membrane is considered to be a
bundle of straight, cylindrical pores distributed
across the surface layer of the membrane. Trans-
port (and thus, separation) is achieved by liquid
permeation followed by vapor permeation
through nanometer-scale pores, due to a pressure
difference over the membrane. Convective trans-
port is assumed within the pores with an interme-
diate phase change due to the vacuum at the
permeate side or the use of a sweep gas (Shieh
and Huang 1998a, b; Lipnizki and Trägårdh
2001). The second approach is the solution-
diffusion model, developed by Graham and intro-
duced to pervaporation by Binning et al. (1961).
In this model, the membrane is considered to be
nonporous so that transport occurs only by diffu-
sion and not by convection. Transport of a com-
ponent from the feed solution through the
membrane occurs by (1) sorption onto the mem-
brane, (2) diffusion through the membrane, and
(3) desorption from the membrane. The driving
force is a difference in chemical potential (due to
a partial pressure or activity difference) between
feed and permeate side (Lipnizki and Trägårdh
2001).
Three types of separations should be distin-
guished for pervaporation. In hydrophilic
pervaporation, small fractions of water (typical
range 1–10 %) are removed from organic sol-
vents, using hydrophilic polymers (typically
polyvinyl alcohol (PVA), but also other polymers
2 Pervaporation (PV)
Pervaporation (PV), Retentate
Fig. 1 Pervaporation
modules in series with
intermediate heat
exchangers
Feed
can be used) or ceramic membranes. Hydropho-
bic pervaporation makes use of polymeric mem-
branes (hydrophobic, such as
polydimethylsiloxane or PDMS) with preferen-
tial transport of nonpolar solvents, which can be
used to remove organics from an aqueous matrix.
The third type of applications is organic-organic
separations, which require special membranes
allowing to distinguish between different organic
solvents; an example is PTMSP (Claes
et al. 2011). The most important industrial appli-
cation is the dehydration of alcohols, although
research efforts also indicate a great potential in
the water and wastewater treatment sector, in the
food and biotechnology industry, and in the
chemical industry.
With regard to large-scale industrial applica-
tion, the earliest mention of an operating pilot
plant dates back to 1982 as a demonstration unit
for alcohol dehydration was designed to produce
1,200 l per day of 99.2 wt.% ethanol. This unit
clearly demonstrated the low energy consump-
tion of pervaporation compared with that of con-
ventional dehydration of ternary azeotropic
distillation after addition of benzene (Feng and
Huang 1997; Kujawski 2000; Jonquières
et al. 2002).
A membrane separation process closely
related to pervaporation is vapor permeation.
The only difference concerns the feed, which is
a mixture of vapors or vapors and gases in vapor
Vacuum pump
Permeate
Condensor
permeation, in contrast to the liquid feed in
pervaporation.
Cross-References
▶ Dense Membrane
▶ Microporous Membrane
▶ Polymeric Membrane
▶ Solution-Diffusion
▶ Vapor Permeation
References
Binning RC, Lee RJ, Jennings JF, Martin EC (1961) Sep-
aration of liquid mixtures by permeation. Ind Eng
Chem 53:45–50
Claes S, Vandezande P, Mullens S, Van Bael MK, Maurer
FHJ (2011) Enhanced performance in pervaporation of
supercritical carbon dioxide treated poly1-
(trimethylsilyl)-1-propyne pervaporation membranes.
J Membr Sci 382:177–185
Feng X, Huang RYM (1997) Liquid separation by mem-
brane pervaporation: a review. Ind Eng Chem Res
36:1048–1066
Jonquières A, Clément R, Lochon P, Néel J, Dresch M,
Chrétien B (2002) Industrial state-of-the-art of
pervaporation and vapour permeation in the western
countries. J Membr Sci 206:87–117
Kujawski W (2000) Application of pervaporation and
vapour permeation in environmental protection.
J Environ Study 9:13–26
Lipnizki F, Trägårdh G (2001) Modelling of
pervaporation: models to analyze and predict the
mass transport in pervaporation. Sep Purif Method
30(1):49–125
Pervaporation (PV) 3

Okada T, Matsuura T (1991) A new transport model for component permeation. Sep Sci Technol
pervaporation. J Membr Sci 59:133–149 33(6):767–785
Shieh JJ, Huang RYM (1998a) A pseudophase-change Shieh JJ, Huang RYM (1998b) A pseudophase-change
solution-diffusion model for pervaporation. I. Single solution-diffusion model for pervaporation. II. Binary
mixture permeation. Sep Sci Technol 33(7):933–957
P

Pervaporation-Assisted Reactor much attention for the reaction with butanol

(Bitterlich et al. 1991). Other esterifications that
Bart Van der Bruggen have been studied include the reaction of
Department of Chemical Engineering, Process propanol with propionic acid, the reaction of
Engineering for Sustainable Systems (ProcESS), oleic acid with ethanol, the reaction of tartaric
KU Leuven, Leuven, Belgium acid with ethanol, and the reaction of erucic acid
with cetyl alcohol, among many others (Van der
Bruggen 2010).
Synonyms One important feature to optimize the design
of pervaporation-assisted reactors (pervaporation
Pervaporation membrane reactor membrane reactors) is the integration of catalysts
into the membrane structure. Catalytically active
Reactors coupled with membrane separation,
pervaporation membranes are also called
such as pervaporation, can help to enhance the
“bifunctional” membranes, i.e., catalytic and sep-
conversion of reactants for thermodynamically or
arative. The fixation of the catalyst to a mem-
kinetically limited reactions via selective
brane was proposed by Shah and Ritchie (2005),
removal of one or more product species from
but the membranes originally proposed were
the reaction mixture (Benedict et al. 2006). A -
microfiltration membranes (Van der Bruggen
pervaporation-assisted reactor is more frequently
2010). The membrane is then used both as cata-
denoted as a pervaporation membrane reactor,
lyst and as a separator. Bernal et al. (2002) used a
and both terms are usually considered as syno-
catalytically active inorganic pervaporation
nyms. Pervaporation-assisted reactors are always
membrane for the same purpose, instead of a
described as chemical reactors, in which a side
microfiltration membrane. An acid zeolite,
product is removed to shift the reaction equilib-
H-ZSM-5, was used as a catalyst for esterification
rium, and more specifically in the context of
reactions (ethanol and acetic acid to produce
esterification reactions. In these reactors, a hydro-
ethyl acetate) in what was called an “active zeo-
philic pervaporation membrane is used to selec-
lite membrane reactor (AZMR).” De la Iglesia
tively remove water, which is a non-desired side
et al. (2006) followed the same approach and
product of any esterification reaction (Datta and
synthesized two-layered mordenite-ZSM-5
Tsai 1995). For example, ethanol and acetic acid
membranes for the same esterification reaction.
react to ethyl acetate, with water as the side
Using a two-layered membrane, the catalytic
product to be removed. Esterification of acetic
activity and the hydrophilicity necessary to
acid is also studied with other alcohols, with

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_452-1
2 Pervaporation-Assisted Reactor
obtain a high flux are combined in a single
structure.
Going beyond the classical esterification reac-
tor, a pervaporation-assisted reactor for
transesterification is an interesting but challeng-
ing extension. In a transesterification reaction, the
side product is not water, but methanol; this
implies that methanol is to be separated from
the reaction mixture. This is a much more diffi-
cult separation to achieve with regular
pervaporation membranes. A new generation of
organophilic membranes is appearing, which is
thought to stimulate a wider scope of applications
of pervaporation-assisted reactors/pervaporation
membrane reactors, also for non-hydrophilic
pervaporation separations.
A possible application of non-esterification
pervaporation membrane reactors is the dehydra-
tion reaction of butanediol to form tetrahydrofu-
ran (THF), catalyzed by H3PW12O40 (Liu and Li
2002). Numerous other reactions are of potential
interest for enhancement in a pervaporation-
assisted reactor. Several are described in the lit-
erature; for an overview, the reader is referred to
Van der Bruggen (2010). The requirements are as
follows: (a) it concerns an equilibrium reaction
and (b) the by-product formed in the reaction can
be selectively removed by a pervaporation
membrane.
Cross-References
▶ Pervaporation
▶ Pervaporation Membrane
▶ Pervaporation Membrane Reactor
References
Benedict DJ, Parulekar SJ, Tsai SP (2006) Pervaporation-
assisted esterification of lactic and succinic acids with
downstream ester recovery. J Membr Sci 281:435–445
Bernal MP, Coronas J, Menendez M, Santamaria J (2002)
Coupling of reaction and separation at the microscopic
level: esterification processes in a H-ZSM-5 mem-
brane reactor. Chem Eng Sci 57:1557–1562
Bitterlich S, Meissner H, Hefner W (1991) Enhancement
of the conversion of esterification reactions by
non-porous membranes. In: Bakish R (ed) Proceedings
of the fifth international conference on pervaporation
processes in the chemical industry. Bakish Material
Corporation, Englewood, pp 273–281
Datta R, Tsai S (1995) Esterification of fermentation-
derived acids via pervaporation. US Patent 5,723,639
De la Iglesia O, Irusta S, Mallada R, Menendez M,
Coronas J, Santamaria J (2006) Preparation and char-
acterization of two-layered mordenite-ZSM-5
bi-functional membranes. Microporous Mesoporous
Mater 93:318–324
Liu QL, Li QB (2002) Membrane of PVA coated on
porous catalytic ceramic disks supported by
H3PW12O40. J Membr Sci 202:89–95
Shah TN, Ritchie SMC (2005) Esterification catalysis
using functionalized membranes. Appl Catal A Gen
296:12–20
Van der Bruggen B (2010) Pervaporation membrane reac-
tors. In: Drioli E, Giorno L (eds) Comprehensive mem-
brane science and engineering, vol 3. Academic,
Oxford, pp 135–163
P
Pervaporation Hybrid System
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
Synonyms
Pervaporation-based hybrid system
A hybrid system based on pervaporation refers to
an integrated entity comprising a pervaporation
unit for separation and a second unit in which
either a reaction is carried out or a separation with
a different method than pervaporation. The inte-
gration by recycling one stream from the
pervaporation unit and another stream from the
second unit to the pervaporation unit is an essen-
tial aspect of the hybridization (without a recycle
stream, the system would rather be a separation-
separation or reaction-separation sequence) (Van
der Bruggen 2010). A hybrid system should have
a performance superior to the performance of the
sum of the individual processes, which should not
be able to carry out the overall process as a stand-
alone system (although this is usually understood
in the sense that none of the individual processes
is able to carry out the overall process in an
economical way).
Lipnizki et al. (1999) categorize pervaporation
hybrid systems into two types, i.e., separation-
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_453-1
type and reaction-type hybrid processes. The lat-
ter are denoted as R-type hybrid systems; the
pervaporation unit can remove either the desired
reaction product from the reactor or from a recy-
cle loop (R1-type hybrid system) or a side prod-
uct (R2-type hybrid system), which is often
water. This is shown in Fig. 1 (Lipnizki
et al. 1999). R-type hybrid systems with a
pervaporation unit for separation are also referred
to as pervaporation membrane reactors. R1-type
hybrid systems are typical (but not exclusive) for
bioconversions, in which the conversion can be
enhanced by removal of the conversion product.
For example, in the production of bioethanol, the
product ethanol acts as an inhibitor for bacterial
activity when the concentration becomes too
high. Removal of ethanol allows for continuous
biological activity, which enhances the yield of
ethanol significantly. R2-type pervaporation
hybrid systems are typical for equilibrium reac-
tions, in which the yield is enhanced by the
removal of a by-product of the reaction.
According to the principle of Le Ch^atelier-
Braun, the reaction equilibrium would then shift
toward a higher conversion; the net result is that
the yield of the desired product is substantially
higher, allowing even for full conversion. The
most studied examples are esterification reac-
tions, in which an ester is produced from the
reaction of an acid with an alcohol. The side
product in these reactions is water, which can be
easily removed from the reaction medium by a
hydrophilic pervaporation membrane.
2 Pervaporation Hybrid System
Pervaporation Hybrid a b
System, Fig. 1 R-type
(reaction) hybrid processes:
(a) type R1 (removal of
reactor product) and (b)
type R2 (removal of
by-product) (Lipnizki
et al. 1999)
Pervaporation Hybrid System, Fig. 2 Integration of pervaporation and distillation in different hybrid configurations
Esterification reactions are often carried out with
acetic acid (Van der Bruggen 2010).
Pervaporation-assisted esterification of ethanol
and acetic acid is often studied, but many other
reactions are similar. The principle was patented
in 1995 (Datta and Tsai 1995) for the esterifica-
tion of lactic acid, propionic acid, butyric acid,
acetic acid, and succinic acid (and combinations
thereof) with an alcohol, including the reaction of
acetic acid and ethanol, aided by the use of a
pervaporation membrane.
The separation-type hybrid systems based on
pervaporation typically combine pervaporation
with distillation. Both processes can in principle
be used for the same kind of separations, but the
separation mechanisms are totally different
(based on a difference in volatility for distillation
and on a difference in membrane affinity for
pervaporation), so that a combination is logical
to overcome difficult points in the individual
processes. Different configurations based on
reactor reactor
PV PV
Product By-Product
integration of pervaporation with a distillation
column are shown in Fig. 2 (Van der Bruggen
2010).
The most common difficulties in separations
are azeotropic points in distillation, which require
complex and energy-intensive solutions when
using distillation alone, but are easy in a hybrid
setup in which pervaporation is used to overcome
the azeotrope. A typical example is the produc-
tion of ethanol from ethanol-water mixtures. The
azeotrope at a concentration of ethanol of
ca. 96 % can be overcome by distilling to, e.g.,
90 % and continuing with pervaporation for puri-
fication of the distillate (and recycling the water-
richer retentate back to the distillation column).
Various hybrid pervaporation systems can be
developed, with a (smaller) distillation column
for the final ethanol purification, or a second,
more selective pervaporation membrane
separation.
Pervaporation Hybrid System 3

Cross-References Lipnizki F, Field RW, Ten PK (1999) Pervaporation-

based hybrid process: a review of process design,
applications and economics. J Membr Sci
▶ Pervaporation 153:183–210
▶ Pervaporation Membrane Reactor Van der Bruggen B (2010) Pervaporation membrane reac-
tors. In: Drioli E, Giorno L (eds) Comprehensive mem-
brane science and engineering, vol 3. Academic,
Oxford, pp 135–163
References

Datta R, Tsai S (1995) Esterification of fermentation-

derived acids via pervaporation. US Patent 5,723,639
P
Pervaporation Membrane
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
A membrane for pervaporation is a microporous
or dense membrane, which selectively transports
components from a liquid mixture due to differ-
ences in sorption in the membrane matrix and in
diffusion through the membrane to the permeate
side. Dense membranes have in principle no
pores, whereas microporous membranes have
pores in the order of magnitude of 1 nm. The
difference, however, is small since the free vol-
ume in dense membranes can yield pathways
with sizes in the same range as microporous
channels.
In general, three types of membranes can be
distinguished: (1) hydrophilic membranes, which
preferentially transport polar solvents, in partic-
ular water, (2) hydrophobic membranes, which
preferentially transport nonpolar solvents, and
(3) organophilic membranes, which allow sepa-
ration of one solvent from another. The separa-
tion is based on properties of the membrane
material, dominated by polarity interactions but
extending to size effects in nanoscale channels.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_454-1
An overview of hydrophilic membrane mate-
rials for pervaporation is given in Table 1. Hydro-
philic membranes have a water contact angle
below 90 and are either made of polymeric or
ceramic materials. They are successfully used for
dehydration of solvents. Polymers are often based
on polyvinyl alcohol (PVA) or polyimide (PI).
Ceramic membranes can be made of silica or
zirconia. Zeolites are also used; zeolite A is
used as a molecular sieve for pervaporation.
Because of the well-defined structure of the zeo-
lites, very high separation factors can be obtained
with zeolite membranes. The separation is then
based on size effects rather than polarity effects.
Hydrophobic membranes are summarized in
Table 2. They have a contact angle between 90
and 120 . The typical polymer for hydrophobic
pervaporation membranes is polydimethyl-
siloxane (PDMS). A typical application of hydro-
phobic pervaporation is the recovery of ethanol
from a fermentation broth. Given the low con-
centrations of ethanol usually encountered, this
requires a multistep approach.
Organophilic pervaporation is in an earlier
stage of development because the separation is
more challenging, and membranes for specific
solvent separations are still scarce. Nevertheless,
this is a highly promising membrane type in view
of many applications, ranging from solvent
recycling to solvent exchange in e.g., pharmaceu-
tical production (Table 3).
2 Pervaporation Membrane

Pervaporation Membrane, Table 1 Hydrophilic pervaporation membranes and their applications

Membrane
Application type Membrane Reference Specific target
Dehydration Polymeric Polyvinylalcohol Kujawski 2000; Van Baelen et al. 2004; Methanol,
of organic (PVA) Huang and Jarvis 1970 ethanol,
solvents n-propanol, IPA
dehydration
Polyimide (PI) Kim et al. 2000 Ethanol
dewatering
Cellulose and Huang and Jarvis 1970 Methanol,
derivatives ethanol,
n-propanol, IPA
dewatering
Sodium aliginate Uragami and Saito 1989; Mochizuki Ethanol
et al. 1990; Kanti et al. 2004 dehydration
chitosan Feng and Huang 1996; Goto et al. 1994 Ethanol, IPA, and
ethylene glycol
dewatering
Inorganic Microporous Van Veen et al. 2001 Dewatering of
silica IPA and 2-butanol
Titania Sekulic et al. 2002 Dehydration of
IPA and 2-butanol
Zirconia Sekulic et al. 2002 Dehydration of
IPA and 2-butanol
ZSM-5 Bowen et al. 2004 Ethanol and IPA
dehydration
Mordenite Bowen et al. 2004 Methanol,
propanol, and IPA
dehydration
A-, X-, Y-, and Bowen et al. 2004; Sommer and Melin Ethanol
T-type zeolite 2005; Ying et al. 2004; Okamoto dehydration
membranes et al. 2001; Morigami et al. 2001
Organic/ PDMS with Vankelecom et al. 1995 Ethanol
inorganic zeolite filler dehydration
Chitosan- Liu et al. 2005 Dehydration of
trimethoxysilane IPA

A general problem for the stability of a mem-
brane in pervaporation is the effect of the vacuum
applied at the permeate side. The vacuum is
needed to obtain a sufficient difference in partial
pressure. In such conditions, the membrane is not
swollen. In contrast, the membrane is in contact
with the liquid feed mixture at the feed side,
which causes swelling by uptake of solvent. The
more flexible the polymeric chains are (e.g.,
linear polymers), the more the membrane swells
at the feed side. This causes an asymmetric struc-
ture (swollen/unswollen), which causes mechan-
ical stress that might lead to cracking. Swelling
can be avoided by crosslinking of the polymer,
but a balance is needed because crosslinking usu-
ally has a negative impact on fluxes.
Pervaporation Membrane 3

Pervaporation Membrane, Table 2 Overview of membranes for hydrophobic pervaporation

Membrane
Application type Membrane References Specific target
Removal Polymeric Poly(dimethyl Lipnizki et al. 1999; Removal of chloroform, toluene,
of diluted siloxane) (PDMS) Mohammadi methylene chloride, trichloroethane,
organics et al. 2005 benzene, styrene, cyclohexane
Polyurethane (PU) Ji et al. 1994 Removal of toluene, trichloroethane
Poly(ether-block- Djebar et al. 1998; Ji Removal of trichloroethane, methyl
amide) (PEBA) et al. 1994; and Peng chloride
et al. 2003
Nitrile-butadiene Brun et al. 1985 Removal of chloroform and toluene
rubber (NBR)
Styrene-butadiene Brun et al. 1985 Removal of chloroform and toluene
rubber (SBR)
Supported ionic Izák et al. 2003 Removal of toluene from toluene/
liquid membranes alcohol mixtures
(SILMs)
poly Claes et al. 2011 Ethanol/water
[1-(trimethylsilyl)-
1-propyne]
(PTMSP)
Inorganic Silicalite Bowen et al. 2004 Ethanol removal from water
membranes

Pervaporation Membrane, Table 3 Overview of membranes for organophilic pervaporation

Organic- Polymeric Polyimide copolymer membranes Ho et al. 1998 Separation of aromatic/
organic saturated mixtures
separations Polyetherimide segmented Tanihara Separation of benzene/
compolymer et al. 1994, cyclohexane, benzene/
1995 heptane, acetone/cyclohexane
Polyimide-co- Tanihara Separation of benzene/
polyphenylenediamine et al. 1994, cyclohexane, benzene/
1995 heptane, acetone/cyclohexane
Blended cellulose acetate and Cabasso 1983 Separation of benzene/
polyphosphonates cyclohexane
Blended cellulose acetate and Acharya Separation of benzane/
polybromophenylene oxide et al. 1988 cyclohexane
dimethylphosphonate ester
Polypropylene PP Villaluenga Separation of benzene/
and cyclohexane
Mohammadi
2000
Polyvinylidene fluoride (PVDF) Villaluenga Separation of benzene/
and cyclohexane
Mohammadi
2000
Polymethyl methacrylate (PMMA) Villaluenga Separation of benzene/
and cyclohexane
Mohammadi
2000
Organic/ Aluminia supported PVA Yoshida and Separation of methanol/
inorganic Cohen 2003 MTBE
4 Pervaporation Membrane
Cross-References
▶ Crosslinking
▶ Dense Membrane
▶ Microporous Membrane
▶ Pervaporation
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tion and pervaporation of dilute aqueous solutions of
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Cabasso I (1983) Organic liquid mixtures separation by
permselective polymer membranes, I selection and
characteristics of dense isotropic membrane employed
in the pervaporation process. Ind Eng Chem Prod Res
Dev 22:313–319
Claes S, Vandezande P, Mullens S, Van Bael MK, Maurer
FHJ (2011) Enhanced performance in pervaporation of
supercritical carbon dioxide treated poly1-
(trimethylsilyl)-1-propyne pervaporation membranes.
J Membr Sci 382:177–185
Djebar MK, Nguyen QT, Clément R, Germain Y (1998)
Pervaporation of aqueous ester solutions through
hydrophobic poly(ether-block-amide) copolymer
membranes. J Membr Sci 146:125–133
Feng X, Huang RYM (1996) Pervaporation with chitosan
membranes, I. Separation of water from ethylene gly-
col by a chitosan/polysulfone composite membrane.
J Membr Sci 116:67–76
Goto M, Shiosaki A, Hirose T (1994) Separation of water/
ethanol vapor mixtures through chitosan and
crosslinked chitosan membranes. Sep Sci Technol
29:1915–1923
Ho WSW, Sartori G, Thaler WA, Dalrymple DA
(1998) Polyimide copolymers containing polycarbon-
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(vinyl alcohol). J Appl Polym Sci 14:2341–2356
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Description of binary liquid mixtures transport
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Stefan equations. J Membr Sci 214(2):293–309
Ji W. Sikdar SK, Hwang ST (1994) Modeling of
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Kanti P, Srigowri K, Madhuri J, Smitha B, Sridhar
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Kim JH, Lee KH, Kim SY (2000) Pervaporation separa-
tion of water from ethanol through polyimide compos-
ite membranes. J Membr Sci 169:81–93
Kujawski W (2000) Application of pervaporation and
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Lipnizki F, Hausmanns S, Ten PK, Field RW, Laufenberg
G (1999) Organophilic pervaporation: prospects and
performance. Chem Eng J 73(2):113–129
Liu YL, Su YH, Lee KR, Lai JY (2005) Crosslinked
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Pervaporation of dilute alcoholic mixtures using
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The first large-scale pervaporation plant using tubular-
type module with zeolites NA membrane. Sep Purif
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Okamoto K, Kita H, Horii K, Tanaka K, Kondo M (2001)
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40(1):163–175
Peng M, Vane LM, Liu SX (2003) Recent advances in
VOCs removal from water by pervaporation. J Hazard
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K (2002) Microporous silica and doped silica mem-
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of industrial solvents. Chem Eng Proc
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Pervaporation of organic liquid mixtures through
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substituted phenylenediamine moieties. J Membr Sci
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Pervaporation Membrane
and new technique for separation of aqueous alcoholic
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Vandecasteele C, Degrève J (2004) Pervaporation of
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organic mixtures. J Membr Sci 213:145–157
P
Pervaporation Membrane Reactor
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Celestijnenlaan 200F, Leuven,
Belgium
A pervaporation membrane reactor (PMR) is an
integrated reaction-separation system, in which
one or more components from a reaction medium
is selectively removed in order to increase the
yield of the reaction (Van der Bruggen 2010).
The component removed by pervaporation can
be the product (type 1 PMR) or a by-product
(type 2 PMR). This is schematically shown in
Fig. 1 (Lipnizki et al. 1999).
Pervaporation membrane reactors can be used
for bioconversions (type 1 PMR), such as the
production of bioethanol and bio-butanol, and
for the extraction of aroma components from a
fermentation broth. Vane (2005) describes a
pervaporation-bioreactor hybrid process for eth-
anol fermentation and further ethanol purification
by dehydration (Fig. 2). A hydrophobic mem-
brane is needed for ethanol extraction
(polydimethylsiloxane membranes are typical
for this application), followed by a hydrophilic
membrane for obtaining a sufficient ethanol
purity.
Another type of applications is in conversion
reactions limited by the chemical equilibrium.
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_455-1
According to the principle of Le Ch^atelier-
Braun, selective removal of a by-product in the
reaction shifts the reaction equilibrium to a
higher product yield (type 2 PMR). A typical
class of reactions in which this is applied is
esterification:
RCOOH þ R0 OH $ RCOOR0 þ H2 O
The most simple esterification reaction is the
reaction of ethanol with acetic acid to yield
ethyl acetate and water. To enhance the yield of
RCOOR’ (ethyl acetate in the example), H2O can
be removed by a hydrophilic pervaporation mem-
brane (Datta and Tsai 1995; Waldburger and
Widmer 1996). The membrane to be used should
be hydrophilic, often based on polyvinyl alcohol
(PVA). Other materials include polyvinylacohol/
polyacrylonitrile (PVA/PAN), polyetherimide
(PEI), and 4,40 -oxydiphenylene pyromellitimide
(POPMI) (Van der Bruggen 2010). Ceramic
pervaporation membranes have specific advan-
tages (more robust and higher fluxes, although
more expensive). For this application, a
pervaporation membrane reactor is an alternative
to the more conventional (and more energy-
consuming) reactive distillation.
Pervaporation membrane reactors can be even
more integrated by using a catalytically active
inorganic pervaporation membrane, which acts
both as catalyst and separator. An acid zeolite,
H-ZSM-5, was used in what was called an “active
zeolite membrane reactor (AZMR).” Gao
2 Pervaporation Membrane Reactor

Pervaporation a b
Membrane Reactor,
Fig. 1 (a) Type R1 PMR
(removal of reactor
product) and (b) type R2 reactor reactor
PMR (removal of
by-product) (Lipnizki
et al. 1999)

PV PV

Product By-Product

CO2 Retentate Hydrophilic PV

(dehydrated
Bleed ethanol)

Water enriched
Retentate Ethanol permeate
feed
enriched
microfiltration permeate

fermentation Hydrophobic PV

Pervaporation Membrane Reactor, pretreatment, and dehydration with hydrophilic

Fig. 2 Fermentation reactor coupled to hydrophobic pervaporation (Adapted with permission from Vane
pervaporation for ethanol extraction, with microfiltration (2005))

et al. (1996) and Tanaka et al. (2001) studied the conditions (in particular with methanol selectiv-
esterification of acetic acid and alcohol, catalyzed ity) have been reported and can be used (Bhat and
by an exchange resin, using a zeolite A-PVA Pangarkar 2000; Ray et al. 1999). The use of
composite membrane, and a zeolite pervaporation membrane reactors for transester-
T membrane, respectively. ifications in comparison with reactive distillation
In spite of many applications already studied, has also been described by Brinkmann
transesterification reactions have not yet been et al. (2009).
extensively considered. Many esters are made
using transesterification, because the milder con-
ditions prevailing permit the reaction of compo-
Cross-References
nents containing additional functional groups. In
alcoholysis, a complex alcohol is reacted with a
▶ Pervaporation
methyl ester, forming a complex ester and meth-
▶ Pervaporation Membrane
anol. These reactions are all equilibrium limited
and are therefore candidates for use in a
pervaporation membrane reactor. However,
pervaporation membranes needed for this type References
of PMR should be organophilic, which is more
challenging than classical solvent-water separa- Bhat AA, Pangarkar VG (2000) Methanol-selective mem-
branes for the pervaporative separation of
tions. Nevertheless, membranes for specific
Pervaporation Membrane Reactor
methanol–toluene mixtures. J Membr Sci
167(2):187–201
Brinkmann T, Pingel H, Wolff Th, Döker M, Gmehling J
(2009) Separation of organic product streams from
reactive distillation columns: membrane material
selection and process integration studies. Presented at
Euromembrane, 6–10 Sept 2009, Montpellier, France
Datta R, Tsai S (1995) Esterification of fermentation-
derived acids via pervaporation. US Patent 5,723,639
Gao Z, Yue Y, Li W (1996) Application of zeolite-filled
pervaporation membrane. Zeolites 16(1):70–74
Lipnizki F, Field RW, Ten PK (1999) Pervaporation-
based hybrid process: a review of process design,
applications and economics. J Membr Sci
153:183–210
Ray SK, Sawant SB, Joshi JB, Pangarkar VG (1999) Meth-
anol selective membranes for separation of
3
methanol–ethylene glycol mixtures by pervaporation.
J Membr Sci 154:1–13
Tanaka K, Yoshikawa R, Ying C, Kita H, Okamoto
K (2001) Application of zeolite membranes to esteri-
fication reactions. Catal Today 67(1–3):121–125
Van der Bruggen B (2010) Pervaporation membrane reac-
tors. In: Drioli E, Giorno L (eds) Comprehensive mem-
brane science and engineering, vol 3. Academic,
Oxford, pp 135–163
Vane L (2005) A review of pervaporation for product
recovery from biomass fermentation processes.
J Chem Technol Biotechnol 80:603–629
Waldburger RM, Widmer F (1996) Membrane reactors in
chemical production processes and the application to
the pervaporation-assisted esterification. Chem Eng
Technol 19(2):117–126
P
Pervaporation Separation Factor
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
The selectivity of a pervaporation membrane in a
given separation is usually calculated by the
dimensionless separation factor a. For a binary
mixture consisting of components A and B, the
separation factor a is given by the following
equation, in which yA and yB are the permeate
compositions and xA and xB are the feed or
retentate compositions:
yA =yB
aAB ¼
xA =xB
These compositions can be described by means of
mole fractions, mass fractions, or volume frac-
tions (Mulder 1996).
The separation factor is chosen in such a way
that its value is greater than unity and so that
component A permeates preferentially. If
a = 1, no separation can be achieved
(composition of the feed is identical to the
feed composition).
The separation factor in pervaporation is cal-
culated in the same way as the relative volatility
in distillation applications (vapor-liquid
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_456-1
equilibrium). Because the separation in
pervaporation is not obtained by effects of vola-
tilization, however, the selectivity in
pervaporation is very different than for distilla-
tion for the same binary system. In the figure
below, the McCabe-Thiele diagram showing the
vapor-liquid equilibrium and the feed-permeate
relation in pervaporation for the ethanol-water
system is shown (Kujawski 2000). The composi-
tion of the feed mixture is shown on the x-axis;
the y-axis gives the composition of the vapor in
equilibrium with the respective liquid (for distil-
lation) or the composition of the permeate (for
pervaporation). The pervaporation membrane in
the figure is a hydrophilic membrane through
which water is passing preferentially (for any
concentration of water) and is enriched in the
permeate. The highest separation factor can be
observed at low water content. Thus,
pervaporation is ideal for removal of water from
the feed mixture at low concentrations of water,
in the case of water-ethanol mixtures. In distilla-
tion, on the other hand, the more volatile ethanol
is enriched in the vapor phase at high water con-
centrations (below the azeotropic point). With
decreasing water in the feed, the vapor-liquid
equilibrium shows azeotropic behavior, which
means that the composition of vapor and liquid
are identical; (ordinary) distillation cannot be
used to cross the azeotropic point (Fig. 1).
An alternative way to quantify selectivity is by
the dimensionless enrichment factor b, which is
defined as the ratio of the fraction (molar or mass)
2 Pervaporation Separation Factor

Pervaporation 100 100

Separation Factor,
Fig. 1 Comparison pervaporation
between selectivity in
pervaporation (upper 80 80
curve) and distillation
(lower curve) (Kujawski

Permeate [wt.% H2O]

Distillate [wt.% H2O]

2000)
60 60

α=1

40 40

20 20
distillation

azeotropic point
0 0
0 20 40 60 80 100
Feed [wt.% H2O]

of component A in the permeate to the fraction of
component A in the feed:
yA
bA ¼
xA
Usually, there is a trade-off between the perme-
ation flux and selectivity; i.e., when one factor
increases, the other decreases. As both of them
are important numbers in the separation process,
a pervaporation separation index (PSI) can be
defined as a measure of the separation ability of
a membrane (Sommer and Melin 2005):
the highest reported separation factors for
ethanol-water separation are in the order of mag-
nitude of 20 (Claes et al. 2011).
Flux and selectivity are strongly influenced by
the specific characteristics of the components in
the feed, the membrane, and the process-
operating parameters. These factors include per-
meate pressure, process temperature, feed com-
position and concentration, feed turbulence,
membrane thickness, concentration polarization,
temperature polarization, and the membrane
material.

PSI ¼ Jtot aAB

Cross-References
in which aAB is the separation factor as defined
▶ Concentration Polarization
above, and Jtot is the total flux through the
▶ Reverse Osmosis
membrane.
▶ Temperature Polarization
Compared to other membrane processes, such
▶ Ultrafiltration
as ultrafiltration and reverse osmosis,
pervaporation generally has low fluxes
(<10 kg/m2h). Nevertheless, its selectivity can
be extremely high, with a often exceeding 1,000 References
for separation of components with a large differ-
ence in polarity. This is not the case for more Claes S, Vandezande P, Mullens S, Van Bael MK, Maurer
FHJ (2011) Enhanced performance in pervaporation of
difficult separations such as ethanol-water, for supercritical carbon dioxide treated poly1-
which separation factors are typically below ten; (trimethylsilyl)-1-propyne pervaporation membranes.
J Membr Sci 382:177–185
Pervaporation Separation Factor 3

Kujawski W (2000) Application of pervaporation and Sommer S, Melin T (2005) Performance evaluation of
vapour permeation in environmental protection. microporous inorganic membranes in the dehydration
J Environ Stud 9:13–26 of industrial solvents. Chem Eng Proc
Mulder MHV (1996) Basic principles of membrane tech- 44(10):1138–1156
nology, 2nd edn. Kluwer, Dordrecht
P
Pervaporation Through Supported
Liquid Membrane
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Celestijnenlaan 200F, Leuven,
Belgium
Supported liquid membrane pervaporation is a
process for separating volatile organic com-
pounds (VOCs) from their dilute aqueous solu-
tions through a supported liquid membrane (Qin
et al. 2002), often in a fermentation broth. It
integrates simultaneous extraction of the VOCs
from the aqueous solution with vacuum stripping
of the VOCs from the organic phase in one mem-
brane module. The separation occurs by
pervaporation, in which components selectively
evaporate through a membrane. The membrane
used in this case is a liquid membrane supported
with a hydrophobic porous membrane
(Matsumura and Kataoka 2004). The selectivity
is thus determined by the choice of the liquid and
its properties, and the selection of a proper liquid
is a key factor for a successful separation. For
example, oleyl alcohol was found to be the most
suitable liquid for separating volatile products in
ABE (aceton-butanol-ethanol) fermentation
(Matsumura and Kataoka 2004). Oleyl alcohol
is a preferred compound, since it is nontoxic to
the microorganisms used in fermentation
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_457-1
(Matsumura et al. 1992). The use of decanol
(100 % pure) instead of oleyl alcohol (85 %
pure) as the membrane solvent increased the
flux and improved the stability without signifi-
cant loss of performance up to about 70 h
(Clement and Hossain 1997). Ionic liquids are a
logical alternative in view of the stability of the
membrane. Among the ionic liquids that have
been considered are 1-ethenyl-3-ethyl-
imidazolium hexafluorophosphate and
tetrapropyl-ammonium tetracyanoborate (Izak
et al. 2009) and tetracyanoborate and tris
(pentafluoroethyl)trifluorophosphate (Heitmann
et al. 2012), but the range of ionic liquids that
can be used for this purpose is very wide. For
example, Matsumoto et al. (2011) studied
pervaporation of 1-butanol and isopropyl alcohol
(IPA) through a poly vinyl chloride membrane
(PVC) as the active layer and a porous hydropho-
bic polyvinyldene fluoride membrane as the sup-
port layer for a series of ionic liquids, including
Aliquat 336, Cyphos 101, 102, and 104. It has
been shown that the sorption step mainly affected
the separation factor depending on the hydrophi-
licity of the ionic liquid (Matsumoto et al. 2009).
Applications of pervaporation through
supported liquid membranes are in the field of
bioconversions. For example, an oleyl alcohol
supported liquid membrane was successfully
applied to diacetyl fermentation by immobilized
lactic acid bacteria by Ishii et al. (1995). Diacetyl
productivity was about 10 g per m3and per h,
while the productivity during batch fermentation
2 Pervaporation Through Supported Liquid Membrane
was about 6 g per m3and per h. The diacetyl yield
from consumed glucose was about four times as
large as that of batch fermentation. No fouling
effects were encountered by using the actual fer-
mentation broth: the flux of the permeate and the
diacetyl separation factor for the pervaporation
were maintained at almost constant levels during
fermentation. The diacetyl concentration in the
permeate, which was about 2 kg/m3, was found
sufficiently high for commercial use.
A closely related process is vapor permeation
through supported liquid membranes, which is
applied in, for example, the separation of benzene
and cyclohexane (Matsumoto et al. 2009). The
difference is in the feed solution, which is a liquid
for pervaporation and a vapor for vapor perme-
ation. The choice between both processes is not a
fundamental difference but usually depends on
the feed mixture to be separated.
A general challenge for supported liquid
membranes is their stability during application.
For aqueous applications, it was shown that the
loss of the ionic liquid from the supporting mem-
brane towards the contacting aqueous phases is
not negligible (Fortunato et al. 2004). Matsumoto
et al. (2009), however, obtained a steady flux and
separation factor and suggest that the membrane
was extremely stable in the application that was
considered.
Cross-References
▶ Pervaporation
▶ Supported Liquid Membrane
▶ Vapor Permeation
References
Clement C, Hossain MM (1997) Stability of a supported
liquid membrane for removing hydrophobic solutes
from casein hydrolysate solution. Sep Sci Technol
32(16):2685–2703
Fortunato R, Afonso CAM, Reis MAM, Crespo JG
(2004) Supported liquid membranes using ionic liq-
uids: study of stability and transport mechanisms.
J Membr Sci 242:197–209
Heitmann S, Krings J, Kreis P, Lennert A, Pitner WR,
Gorak A, Schulte MM (2012) Recovery of n-butanol
using ionic liquid-based pervaporation membranes.
Sep Purif Technol 97:108–114
Ishii N, Matsumura M, Kataoka H, Tanaka H, Araki
K (1995) Diacetyl fermentation coupled with
pervaporation using oleyl alcohol supported liquid
membrane. Bioprocess Biosyst Eng 13(3):119–123
Izak P, Friess K, Hynek V, Ruth W, Fei Z, Dyson JP, Kragl
U (2009) Separation properties of supported ionic
liquid-polydimethylsiloxane membrane in
pervaporation process. Desalination 241:182–187
Matsumoto M, Ueba K, Kondo K (2009) Vapor perme-
ation of hydrocarbons through supported liquid mem-
branes based on ionic liquids. Desalination
241:365–371
Matsumoto M, Murakami Y, Kondo K (2011) Separation
of 1-butanol by pervaporation using polymer inclusion
membranes containing ionic liquids. Solvent Extr Res
Dev Jpn 18:75–83
Matsumura M, Kataoka H (2004) Separation of dilute
aqueous butanol and acetone solutions by
pervaporation through liquid membranes. Biotechnol
Bioeng 30(7):887–895
Matsumura M, Takehara S, Kataoka H (1992) Continuous
butanol isopropanol fermentation in down-flow col-
umn reactor coupled with pervaporation using
supported liquid membrane. Biotechnol Bioeng
39(2):148–156
Qin Y, Sheth JP, Sirkar KK (2002) Supported liquid
membrane-based pervaporation for VOC removal
from water. Ind Eng Chem Res 41(14):3413–3428
P
Phenolic Compound
Beatriz Mello
UFSCar, Federal University of Sao Carlos, Buri,
SP, Brazil
Phenolic compounds are a chemical class
consisting by at least one aromatic ring
(C6) bearing one or more hydroxyl groups. The
hydrogen of the phenolic hydroxil groups is labile
thanks to the aromatic ring, which is responsible
for the weak acid characteristic of phenols
(Wermerris and Nicholson 2007). They are
found in the natural world, being one of the
most important groups occurring in the plant
kingdom where they are the most abundant sec-
ondary metabolites in plants – usually found as
esters or glycosides and not as free compounds.
They are responsible for several functional activ-
ities in plant’s life cycle including defense, attrac-
tants for pollinators, and protection against
ultraviolet light (Jaganath and Crozier 2010).
These characteristics explain their wide use com-
mercially as flavoring agents, natural drugs, anti-
oxidants, etc., acting as natural additives.
Phenol (C6H5OH) is the simplest compound
of the class (also called carbolic acid), and its
structure is represented in Fig. 1. Polyphenols
are compounds that have more than one hydroxyl
group attached to one or more benzene rings.
It is possible to divide the phenols in several
different groups according to the number of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_458-4
carbons in conjunction with the structure of the
basic phenolic skeleton – simple phenols, pheno-
lic acids, coumarins, phenylopropanoids, flavo-
noids, antocyanins, catechins, terpenoids, to
highly polymerized compounds, such as con-
densed tannins. Their molecular weight is in the
range of 90–350 g/mol. Flavonoids constitute the
most important polyphenolic class, with more
than 500 compounds already described.
These compounds are reported to exhibit
anticarcinogenic, antiinflammatory, antioxidant,
and antimicrobial activities, among others. Sev-
eral studies were carried out in order to correlate
the consumption of foods with high concentra-
tions of polyphenols and the reduced risk of
degenerative diseases, mostly with very positive
results. For example, they can prevent
neurodegeneration by trapping radicals, working
as a preventive action. So, phenolic compounds
presented a potential protective role through
ingestion of fruits and vegetables, working
against oxidative damage diseases (coronary
heart disease, stroke, and cancers) (Jaganath and
Crozier 2010).
Their antioxidant activities and the possibility
of use in processed foods as a natural antioxidant
are the explanation for the increased interest in
phenolic acids. Their antioxidant properties come
from their redox potential, which can act as free
radical scavengers, hydrogen donators, metal
chelators, and singlet oxygen quenchers. The
effectiveness in food depends on not only the
number and location of hydroxyl groups but
2 Phenolic Compound
Phenolic Compound, OH
Fig. 1 Basic structure of a
phenol
also on factors such as physical location, interac-
tion with other food components, environmental
conditions (e.g., pH), and the degree of
glycosylation – aglycons of quercetin and
myricetin are more active than their glycosides
(Marchand 2002). The most well-known physio-
logical phenolic antioxidant is vitamin E.
Antimicrobial activity of phenolic compounds
is related to the principle of inactivation of cell
enzymes, what explains the different activities
between Gram-negative and Gram-positive spe-
cies once they have variations in their cell struc-
tures. The antimicrobial effect related with
phenolic compounds contents in several natural
products, as olive (Pereira et al. 2007), wine
(Cueva et al. 2012), mushroom (Barros
et al. 2007), propolis extracts (Hendi
et al. 2011), and green tea (Kristanti and
Punbusayakul 2009).
As every natural product, phenolic com-
pounds have a great utilization potential in sev-
eral processes in order to aggregate their main
properties. It is important to know their action
mechanisms and utilization forms to produce bet-
ter products with functional properties.
The use of membrane operations to separate,
purify, and produce phenolic compounds from
natural sources is very attractive due to the
clean, safe, and low energy input of the
technology
References
Barros L, Calhelha RC, Vaz JA, Ferreira ICFR, Baptista P,
Estevinho LM (2007) Antimicrobial activity and bio-
active compounds of Portuguese wild edible mush-
rooms methanolic extracts. Eur Food Res Technol
225:151–156
Cueva C, Mingo S, Muñoz-González I, Bustos I,
Requena T, Del Campo R, Martín-Álvarez PJ,
Bartolomé B, Moreno-Arribas MV
(2012) Antibacterial activity of wine phenolic com-
pounds and oenological extracts against potential
respiratory pathogens. Lett Appl Microbiol
54:557–563
Hendi NKK, Naher HS, Al-Charrakh AH (2011) In vitro
antibacterial and antifungal activity of Iraqi propolis.
J Med Plant Res 5:5058–5066
Jaganath IB, Crozier A (2010) Dietary flavonoids and
phenolic compounds. In: Fraga CG (ed) Plant pheno-
lics and human health. Wiley, New Jersey, pp 1–50
Kristanti RA, Punbusayakul N (2009) Antioxidant and
antimicrobial activity of commercial green tea in
Chiang Rai. Acta Horticult 837:53–58
Marchand LL (2002) Cancer preventive effects of flavo-
noids a review. Biomed Pharmacother 56:296–301
Pereira AP, Ferreira ICFR, Marcelino F, Valentão P,
Andrade PB, Seabra R, Estevinho L, Bento AÇ,
Pereira JA (2007) Phenolic compounds and antimicro-
bial activity of olive (Olea europaea L. Cv.
Cobrançosa) leaves. Molecules 12:1153–1162
P
Photocatalysis with Membrane
Distillation
Palmisano Leonardo
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Università di Palermo, Palermo, Italy
Photocatalysis by polycrystalline semiconductor
oxides is being successfully applied to the abate-
ment of organic and inorganic pollutants both in
gas and in liquid phases. In order to increase the
efficiency of this method, the coupling of this
technology with the membrane separation pro-
cess has been the object of investigation. In this
combination, the membrane may act in different
ways: to confine the photocatalytic powder in the
reacting suspension, to selectively separate the
photoreaction products, or to be the support of
photocatalyst. Recent studies in which different
types of membranes (such as distillation, dialysis,
nanofiltration, pervaporation, and osmosis mem-
branes) were used in hybrid systems have been
reviewed by Loddo et al. (2009) describing per-
spectives and future possible application of the
synergy between membranes and photocatalytic
reactors. An additional advantage of coupling is
that the photocatalyst prevents the microbial
fouling offering a strong potential for the use of
new types of thin-film-composite membrane.
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_460-2
In the following, some studies concerning in
details the application of photocatalysis and
membrane distillation are reported.
To solve problems concerning separation of
photocatalyst as well as products and byproducts
of photodecomposition from the reaction mix-
ture, the application of photocatalytic membrane
reactors (PMRs) is a promising method. The
PMRs described in literature combine
photocatalysis with pressure-driven membrane
techniques, such as nanofiltration (NF), ultrafil-
tration (UF), and microfiltration (MF). A serious
problem with application of these membrane
techniques can be membrane fouling, which is
especially observable with MF and UF. The
results of the investigation on the possibility of
coupling photocatalysis and membrane distilla-
tion (MD) for degradation of organic pollutants in
aqueous solution were described by Mozia
et al. (2005). Acid Red 18 was applied as model
dye and titanium dioxide Aeroxide (R) P25
(Degussa, Germany) was used as photocatalyst.
In the first step of the research, the effect of the
presence of TiO2 in a feed on the permeate flux
was investigated. It was found that the addition of
TiO2 P25 did not affect the distillate flux, regard-
less of the catalyst concentration applied. In order
to select the best process conditions in terms of
photocatalyst concentration and temperature of
feed solution batch tests were performed. On the
basis of these experiments, TiO2 concentration
and feed temperature in the reactor were set at
0.3 g/dm3 and 333 K, respectively. The hybrid
2 Photocatalysis with Membrane Distillation
process photocatalysis -MD was conducted in a
simultaneous mode. After 5 L of permeate the
model dye was removed completely, whereas
total organic carbon (TOC) concentration was
lowered down to 20 % of the initial value.
Mozia et al. (2007) investigated on the possi-
bility of coupling photocatalysis and direct con-
tact membrane distillation (DCMD, MD) for
degradation of azo dyes (Acid Red 18, Acid Yel-
low 36, and Direct Green 99) in aqueous solution.
TiO2 Aeroxide (R) P25 (Degussa, Germany) was
used as the photocatalyst. It was found that the
addition of TiO2 P25 to the feed did not affect the
distillate flux, regardless of the catalyst concen-
tration applied. The MD process was very effec-
tive in separation of photocatalyst particles. After
5 h of the experiment, the turbidity of distillate
was similar to that measured for ultrapure water,
regardless of the TiO2 loading used. The highest
effectiveness of photodecomposition was
obtained in case of Acid Red 18, whereas Acid
Yellow 36, which has the lowest molecular
weight among the dyes used, was degraded with
high difficulty. The composition of the feed solu-
tion slightly influenced the quality of distillate.
Among the volatile compounds that passed
through the membrane, some organic compounds
were present as indicated by the measurements of
TOC concentration.
An anatase-phase TiO2 was applied for degra-
dation of Acid Yellow 36 (AY36) in the PMR
coupling photocatalysis and direct contact mem-
brane distillation (DCMD) by Mozia
et al. (2009). The effect of different process
parameters such as dye concentration, reaction
temperature, and photocatalyst loading on the
effectiveness of degradation of AY36 was inves-
tigated. Moreover, in order to compare the effec-
tiveness of AY36 photodegradation during
photocatalysis alone and the hybrid process,
additional experiments without application of
the membrane distillation (MD) were conducted.
The addition of TiO2 to a feed did not affect the
permeate flux, regardless of the process condi-
tions applied. The latter remained constant during
about 400 h of experiments. The highest decolor-
ization of AY36 solution during hybrid process
was observed at the highest photocatalyst loading
applied (0.5 g TiO2/dm3). The increase of the
reaction temperature from 313 to 333 K resulted
in an increase of the photodegradation rate of
AY36. After 5 h of the hybrid process, the effec-
tiveness of dye degradation calculated on a basis
of AY36 mass in a feed solution amounted to
31 %, 36 %, and 42 % at reaction temperatures
313–333 K. Similar results were obtained when
photocatalysis was conducted in the MD installa-
tion but with the MD module disconnected. An
improvement of AY36 photodegradation was
achieved by decreasing the initial dye concentra-
tion. The best configuration seemed to be the
PMR one by taking into account the rate of azo
dye degradation and the quality of the product.
The investigations on the photodegradation of
a nonsteroidal anti-inflammatory drug ibuprofen
sodium salt (IBU) in a photocatalytic membrane
reactor (PMR) coupling photocatalysis using
suspended TiO2 and direct contact membrane
distillation was also described by Mozia
et al. (2012). The influence of solution composi-
tion in terms of (i) pH (pH 3, pH 6.5, and pH 10),
(ii) presence of inorganic salts (NaCl, Na2SO4,
NaHCO3, NaNO3, and Na3PO4), and (iii) turbid-
ity (bentonite, 13.5–103 NTU) on the effective-
ness of IBU removal was especially investigated.
The highest effectiveness of IBU
photodegradation was obtained at pH 6.5. No
influence of the presence of NaCl, NaNO3, and
Na2SO4 on the effectiveness of degradation and
mineralization of IBU was found. NaHCO3 and
Na3PO4 did not affect the effectiveness of degra-
dation of IBU; however, the efficiency of miner-
alization decreased significantly. The increased
turbidity of feed solution did not affect IBU
removal in the PMR.
References
Loddo V, Augugliaro V, Palmisano L (2009)
Photocatalytic membrane reactors: case studies and
perspectives. Asia Pac J Chem Eng 4:380–384
Mozia S, Tomaszewska M, Morawski AW (2005) A new
photocatalytic membrane reactor (PMR) for removal
of azo-dye Acid Red 18 from water. Appl Catal
B Environ 59:131–137
Photocatalysis with Membrane Distillation
Mozia S, Tomaszewska M, Morawski AW
(2007) Photocatalytic membrane reactor (PMR) cou-
pling photocatalysis and membrane
distillation – effectiveness of removal of three azo
dyes from water. Catal Today 129:3–8
Mozia S, Morawski AW, Toyoda M, Tsumura T (2009)
Effect of process parameters on photodegradation of
3
Acid Yellow 36 in a hybrid photocatalysis-membrane
distillation system. Chem Eng J 150:152–159
Mozia S, Morawski AW, Toyoda M (2012) The influence
of solution composition on the effectiveness of degra-
dation of ibuprofen sodium salt in a hybrid
photocatalysis – membrane distillation system. J Adv
Oxid Technol 15:21–29
P
Photocatalyst
Palmisano Leonardo
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Università di Palermo, Palermo, Italy
Photocatalyst can be defined as a substance that is
able to produce, by absorption of ultraviolet,
infrared, or visible light, chemical transforma-
tions of reaction partners, repeatedly coming
with them into various chemical interactions
without the occurrence of a permanent modifica-
tion of its chemical composition. After each cycle
of interaction between the reagent(s) and the
photocatalyst, the chemical composition of the
last is regenerated. The presence of a
photocatalyst gives rise to an enhancement of
the rate of a chemical reaction or its initiation
under ultraviolet, infrared, or visible light illumi-
nation, and the role of light is to photo-excite the
solid that works as the photocatalyst (Braslavsky
et al. 2011). Notably, in some cases, light can be
absorbed by the adsorbed reacting species that
can be transformed and the solid photocatalyst
works only as an adsorbent.
The materials that are generally used as
photocatalysts are semiconductor solids with a
band gap energy that is defined as the energy
difference between the nonconductive and the
conductive state of the material. The band gap
energy can be also defined as the energy
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_461-2
difference between the top of the valence band
and the bottom of the conduction band. The
photo-excitation of the solid occurs when light
of suitable energy (higher than the value of the
bandgap energy) induces the separation of elec-
tron and hole pairs by migration of electrons from
the valence to the conduction band:
Photocatalyst

þ hn ! Photocatalyst e ðcbÞ þ hþ ðvbÞ
The photo-produced electrons and holes can give
rise to reduction and oxidation reactions, respec-
tively, with adsorbed reacting species (Voı̈nov
and Augustynski 1997).
The semiconductor photocatalyst is more fre-
quently used both as powders (micro- or nano-
crystalline samples) and films is bare
polycrystalline TiO2 in the anatase phase
(Augugliaro et al. 2010) but also the other poly-
morphic rutile and brookite phases have been
used. Moreover, the formation of nanorods,
nanotubes, and nanowires under particular exper-
imental conditions has been reported (Augugliaro
et al. 2010). TiO2 can be also doped with various
transitional or rare earth metal species and non-
metal species of N, C, S, and F. Sensitization with
(metal) phthalocyanines and porphyrins to extend
the light absorption in the visible region and/or to
increase the lifetime of the photo-produced
electron–hole pairs has been also proposed
(Wang et al. 2010). Metallization with Pt or
other noble metals has proved to be beneficial to
2 Photocatalyst
induce some photo-reduction reactions, as for
instance H2 production from H2O (Chiarello
et al. 2011). Other oxides as for instance ZnO,
WO3, MoO3, Fe2O3, ZrO2, sulfides as ZnS, CdS,
MoS2, or polyoxometalates as the heteropolyacid
H3PW12O40 have been also successfully tested as
photocatalysts (Di Paola et al. 2012). They have
been also mixed with or supported on SiO2 or
Al2O3 with the aim to increase the surface area
and to have the possibility to improve adsorption
of the reacting species before their chemical
transformation on photoactive sites of adjacent
particles of the semiconductor photocatalyst.
They have been also used in combination with
membranes forming devices called
“photocatalytic membrane reactors” (Molinari
et al. 2010).
Some photocatalysts are not (photo)stable in
liquid–solid systems, especially in aqueous envi-
ronments and the extent of this instability
strongly depends on the pH conditions. For
instance, (i) anodic photocorrosion is observed
for ZnO and various sulfides and (ii) the recovery
of polyoxometalates from the reacting medium is
problematic, due to their high solubility. The
above phenomena generally are not observed
when the photoreactions are carried out in
gas-solid systems, although in the latter system
deactivation of photocatalyst has been sometimes
observed, depending on the type of reagent
molecules and on the experimental conditions
used, as for instance the presence of water vapor.
References
Augugliaro V, Loddo V, Palmisano G, Palmisano L,
Pagliaro M (2010) Clean by light irradiation. Practical
applications of supported TiO2. RSC Publishing,
Cambridge
Braslavsky SA, Braun AM, Cassano AE, Emeline AV,
Litter M, Palmisano L, Parmon VN, Serpone N (2011)
Glossary of terms used in photocatalysis and radiation
catalysis (IUPAC recommendations 2011). Pure Appl
Chem 83:931–1014
Chiarello GL, Di Paola A, Palmisano L, Selli E (2011)
Effect of titanium dioxide crystalline structure on the
photocatalytic production of hydrogen. Photochem
Photobiol Sci 10:355–360
Di Paola A, García-López E, Marcı̀ G, Palmisano L (2012)
A survey of photocatalytic materials for environmental
remediation. J Hazard Mater 211–212:3–29
Molinari R, Caruso A, Palmisano L (2010) Photocatalytic
processes in membrane reactors. In: Drioli E, Giorno
L (eds) Comprehensive membrane science and engi-
neering, vol 3. Elsevier-AP, Amsterdam, pp 165–193
Voı̈nov M, Augustynski J (1997) Introduction to the phys-
ics of semiconductor photocatalyst. In: Schiavello M -
(ed) Heterogeneous photocatalysis, vol 3, Wiley series
in photoscience and photoengineering. Wiley, Baffin
Lane, pp 1–34
Wang C, Li J, Mele G, Duan M, L€ u X, Palmisano L,
Vasapollo G, Zhang F (2010) The photocatalytic activ-
ity of novel, substituted porphyrin/TiO2-based com-
posites. Dyes Pigments 84:183–189
P
Photocatalytic Membrane
Palmisano Leonardo
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Università di Palermo, Palermo, Italy
A photocatalytic membrane can be defined as a
combination between a photocatalyst and a mem-
brane. The photocatalyst is able to produce, by
absorption of ultraviolet, infrared, or visible light,
chemical transformations of reaction partners,
repeatedly coming with them into various chem-
ical interactions without the occurrence of a per-
manent modification of its chemical composition.
After each cycle of interaction between the
reagent(s) and the photocatalyst, the chemical
composition of the last is regenerated. The pres-
ence of a photocatalyst gives rise to an enhance-
ment of the rate of a chemical reaction or its
initiation under ultraviolet, infrared, or visible
light illumination and the role of light is to
photoexcite the solid that works as the
photocatalyst (Braslavsky et al. 2011). The mem-
brane has the task to immobilize the
photocatalyst and to act as a molecular separation
barrier for the reagents and/or reaction products
(Molinari et al. 2002). A thin layer of a
photocatalyst can be considered in principle a
photocatalytic membrane, although the perfor-
mance of some of them has not been reported.
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_462-2
Some photocatalytic polysulfone membranes
with the photocatalyst deposited and entrapped in
the membrane were prepared and characterized
by Molinari et al. (2002). It was found that
adsorption of the pollutant on the membrane
and membrane rejection play an important role
in the global membrane performance showing
interesting perspectives and synergy for coupling
photocatalysis and membranes.
Albu et al. (2007) showed a simple and robust
fabrication process of a dense and free-standing
membrane consisting of vertically oriented, both-
side-open TiO2 nanotubes. This membrane struc-
ture allows direct, size-selective, flow-through
photocatalytic reactions with a very high
efficiency.
A semitransparent TiO2 film with extraordi-
narily high photocatalytic activity was prepared
by Sopyan et al. (1996) on a glass substrate by
sintering a TiO2 sol at 450  C. Crystallographic
analysis by X-ray diffraction and Raman spec-
troscopy showed that the film was purely anatase.
The photocatalytic properties of the film were
investigated by measuring the photodegradative
oxidation of gaseous acetaldehyde at various con-
centrations under strong and weak UV light irra-
diation conditions. The photocatalytic activity of
the film was higher than that of one of the most
active commercial TiO2 powders, Degussa P-25.
The kinetics of acetaldehyde degradation as cat-
alyzed by the TiO2 film as well as by P-25 powder
were analyzed in terms of the Langmuir-
Hinshelwood model.
2 Photocatalytic Membrane
TiO2 and Ag-TiO2 catalysts were supported in
the form of thin layers by a dip-coating procedure
on quartz substrate by Herrmann et al. (1997).
The resulting materials were characterized by
SEM/EDX, XRD, XPS, and UV–Vis absorption
spectroscopy. The immobilized catalysts were
tested in the photocatalytic degradation of malic
acid and the increase of the photocatalytic activ-
ity can be explained by the enhanced
electron–hole pair separation efficiency due to
trapping of electrons by metallic Ag.
A novel chemistry method for the fabrication
of robust nanostructured TiO2 photocatalysts was
developed by Choi et al. (2006). Such materials
can be applied for developing efficient
photocatalytic systems to be used for water treat-
ment. The mesoporous photocatalytic TiO2 mem-
branes were synthesized via a simple method that
involves dip-coating of appropriate substrates
into an organic/inorganic sol composed of
isopropanol, acetic acid, titanium tetraiso-
propoxide, and polyoxyethylene sorbitan
monooleate surfactant (Tween 80) followed by
calcination of the coating at 500  C. Controlled
hydrolysis and condensation reactions were
achieved through in-taking of water molecules
released from the esterification reaction of acetic
acid with isopropanol. The subsequent stable
incorporation of Ti-O-Ti network onto self-
assembled surfactants resulted in TiO2
photocatalysts with enhanced structural and cat-
alytic properties. The properties included high
surface area (147 m2/g) and porosity (46 %), nar-
row pore size distribution ranging from 2 to 8 nm,
homogeneity without cracks and pinholes, active
anatase crystal phase, and small crystallite size
(9 nm). These TiO2 photocatalysts were highly
efficient for the destruction of methylene blue
and creatinine in water. High water permeability
and sharp polyethylene glycol retention of the
prepared photocatalytic TiO2/Al2O3 composite
membranes evidenced the good structural prop-
erties of TiO2 films. In addition, the multi-coating
procedure enabled to control the physical prop-
erties of TiO2 layer such as the coating thickness,
amount of TiO2, photocatalytic activity, water
permeability, and organic retention.
TiO2 dispersed in polyester acrylate mem-
branes was tested as a photocatalyst in the phenol
mineralization reaction in the presence of O2 by
D’Arienzo et al. (2010). A kinetic study indicated
that the embedded oxide maintains significant
catalytic activity, and the result was first attrib-
uted to the homogeneous dispersion inside the
polymeric host of TiO2 nanocrystals. Further-
more, an investigation of the photogenerated
charge carriers in the photocatalyst indicated
that electrons are trapped on Ti3+ centers, while
holes are trapped on C-centered species of the
polymer matrix. In the presence of O2, the
C-centered radicals of the polymer transform
into peroxy radicals, improving the charge sepa-
ration in the polymer-embedded oxide with
respect to the powder. The positive interference
of the polymer matrix is responsible for the
enhanced photoactivity of the embedded TiO2.
Kim et al. (2003) proposed a hybrid thin-film-
composite (TFC) membrane consisting of self-
assembly of TiO2 nanoparticles with
photocatalytic destructive capability on microor-
ganisms as a novel mean to reduce membrane
biofouling. Microbial biofouling does not allow
to realize high permeability over a prolonged
period of reverse osmosis operation. The anti-
fouling and fouling mitigation on the actual com-
mercialized TFC was verified. TiO2 anatase
nanoparticles (10 nm) were prepared from the
controlled hydrolysis of titanium tetraiso-
propoxide and characterized by X-ray diffraction
(XRD) analysis and transmission electron
microscopy (TEM). TFC membrane was pre-
pared by self-assembly of the TiO2 nanoparticles
through coordination and H-bonding interaction
with the COOH functional group of aromatic
polyamide thin-film layer. The hybrid membrane
was shown to possess photobactericidal effect on
Escherichia coli (E. coli) under UV light illumi-
nation. Introduction of TiO2 nanoparticles on the
actual commercial TFC membrane and applica-
tion of reverse osmosis field test after exposure to
microbial cells indicated the occurrence of a sub-
stantial prevention against the microbial fouling
showing a less loss of reverse osmosis
permeability.
Photocatalytic Membrane
References
Albu SP, Ghicov A, Macak JM, Hahn R, Schmuki
P (2007) Self-organized, free-standing TiO2 nanotube
membrane for flow-through photocatalytic applica-
tions. Nano Lett 7:1286–1289
Braslavsky SA, Braun AM, Cassano AE, Emeline AV,
Litter M, Palmisano L, Parmon VN, Serpone N (2011)
Glossary of terms used in photocatalysis and radiation
catalysis (IUPAC recommendations 2011). Pure Appl
Chem 83:931–1014
Choi H, Stathatos E, Dionysiou DD (2006) Sol–gel prep-
aration of mesoporous photocatalytic TiO2 films and
TiO2/Al2O3 composite membranes for environmental
applications. Appl Catal B Environ 63:60–67
D’Arienzo M, Crippa M, Essawy AA, Scotti R, Wahba L,
Morazzoni F, Gentile P, Bellobono IR, Polizzi
S (2010) Membrane-assisted charge separation and
photocatalytic activity in embedded TiO2: a kinetic
and mechanistic study. J Phys Chem
C 114:15755–15762
3
Herrmann JM, Tahiri H, Aitichou Y, Lassaletta G,
Gonzalez Elipe AR, Fernandez A (1997) Characteri-
zation and photocatalytic activity in aqueous medium
of TiO2 and Ag-TiO2 coatings on quartz. Appl Catal
B Environ 13:219–228
Kim SH, Kwak SY, Sohn BH, Park TH (2003) Design of
TiO2 nanoparticle self-assembled aromatic polyamide
thin-film-composite (TFC) membrane as an approach
to solve biofouling problem. J Membr Sci
211:157–165
Molinari R, Palmisano L, Drioli E, Schiavello M (2002)
Studies on various reactor configurations for coupling
photocatalysis and membrane processes in water puri-
fication. J Membr Sci 206:399–415
Sopyan I, Watanabe M, Murasawa S, Hashimoto K,
Fujishima A (1996) An efficient TiO2 thin-film
photocatalyst: photocatalytic properties in gas-phase
acetaldehyde degradation. J Photochem Photobiol
A Chem 98:79–86
P
Photocatalytic Membrane Reactor
Leonardo Palmisano
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Università di Palermo, Palermo, Italy
A photocatalytic membrane reactor can be
defined as a device existing in various configura-
tions which combine a photocatalyst and a mem-
brane to produce chemical transformations.
Some experimental results obtained by using
various configurations of photocatalytic mem-
brane reactors (PMRs) have been discussed by
Molinari et al. (2002). The configurations studied
were (i) irradiation of the cell containing the
membrane, with three sub-cases: (i(1)) catalyst
deposited on the membrane; (i(2)) catalyst in
suspension, confined by means of the membrane;
(i(3)) entrapment of the photocatalyst in a PSF
membrane; and (ii) irradiation of the
recirculation tank and catalyst in suspension con-
fined by means of the membrane. In the case of
“(i),” a preliminary investigation of membrane
stability under UV irradiation was carried out.
PMR characterization in photodegradation tests
was mainly carried out in a recycle batch mem-
brane reactor and, in some cases, in a continuous
membrane reactor. The comparison between the
first set of results, where the membrane was used
only as a support for the photocatalyst, and the
newest ones, where the adsorption of the
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_463-2
pollutant on the membrane and membrane rejec-
tion play an important role in the global reactor
performance, showed interesting perspectives
and synergy for coupling photocatalysis and
membranes. Furthermore, the configuration
where the recirculation tank was irradiated and
the catalyst was used in suspension appeared to
be the most interesting for industrial applications.
For example, in reactor optimization, high irradi-
ation efficiency, high membrane permeate flow
rate, and selectivity can be obtained by sizing
separately the “photocatalytic system” and the
“membrane system” and taking advantage of all
the best research results for each system.
A photocatalytic membrane reactor was tested
for degradation of toxic organic species dissolved
in water (Molinari et al. 2000). The catalyst, TiO2
P25 Degussa, was immobilized by means of a flat
sheet polymeric membrane and 4-nitrophenol
(4-NP) was used as a model molecule to evaluate
the reactor performance. A preliminary investi-
gation of the stability, under UV irradiation, of
some eligible polymeric membranes was carried
out by using scanning electron microscopy
(SEM), optical microscopy (OM), determinations
of water permeation flux (WPF), and total
organic carbon (TOC). These tests showed that
commercial membranes made of fluoride + PP
(FS 50 PP-Dow), polysulfone + PP (GR 51
PP-TechSep), and polyacrylonitrile
(PAN-TechSep) seemed to be quite stable to
UV light over a 24 h period of irradiation. Immo-
bilization of TiO2 onto membranes by
2 Photocatalytic Membrane Reactor
ultrafiltrating TiO2 suspensions showed an opti-
mal layer density slightly >2.04 mg TiO2 per
square cm of membrane surface area. Results
obtained from membrane reactor studies indi-
cated that the observed initial rate constants for
the degradation of 4-NP were almost independent
on the amount of TiO2 employed over the range
0.76–4.08 mg/cm2. A 50 % weight degradation of
4-NP after 5 h of irradiation in the presence of air
was obtained. Instead, an almost complete deg-
radation of 4-NP was observed in the presence of
TiO2 suspended in the solution and pure oxygen.
The permeate deriving from the membrane
photoreactor was clear, and 4-NP concentration
was approximately equal to that found in the
retentate. The possibility of the continuous reuse
of the photocatalyst and the continuous separa-
tion of products from the reaction medium gives
some advantages over traditional approaches.
The ability of cross-flow ultrafiltration
(UF) combined with photocatalytic reactions to
separate TiO2 photocatalysts from treated water
in photocatalytic drinking water treatment was
studied by Lee et al. (2001). The effect of natural
organic matter (i.e., humic acids) and cross-flow
velocities on UF fluxes and organic removal was
explored with and without UV irradiation in the
photocatalytic reactor. The interaction between
the two solutes in the system, humic acids and
TiO2 photocatalysts, played a significant role in
the formation of dense cake layers at the mem-
brane surface, leading to a greater flux decline
during ultrafiltration of TiO2 particles. According
to visual observations of the used membranes and
the estimation of back-transport velocities of the
solutes, a substantial amount of TiO2 deposited
on the membrane induces more humic acids to
accumulate at the membrane through the adsorp-
tion of humic acids onto TiO2 particles. The
humic acid-laden TiO2 particles offered more
than four times higher specific cake resistance
with a substantially increased compressibility
coefficient than TiO2 particles alone. The higher
the cross-flow velocities, the greater the UV254
removal achieved. This was because the rise of
cross-flow velocities contributed to the reduction
of concentration polarization at the membrane
surface, thereby resulting in a decrease of the
driving force for humic acids to pass through
the membrane. When photocatalytic reactions
took place with UV illumination, UV254
removal efficiencies of the permeate were
improved markedly, and also the permeate flux
was kept at a constant level without any sign of
fouling. Although humic acids were not
completely mineralized by photocatalysis, the
degradation of the humic acids helped to enhance
the UF flux, as they were transformed into less
absorbable compounds.
The photodegradation of different pharmaceu-
ticals [furosemide, ranitidine (hydrochloride),
ofloxacin, phenazone, naproxen, carbamazepine,
and clofibric acid] in aqueous medium at various
pHs by using a batch photoreactor and a
photocatalytic membrane reactor working in
recirculation regime was carried out by Molinari
et al. (2006). Polycrystalline TiO2 was used as the
photocatalyst, and different membranes (NTR
7410, PAN GKSS HV3/T, N 30 F, NF PES 10)
were tested. A different adsorption of the sub-
strates onto the catalyst surface was observed
owing to the hydrophilic/hydrophobic character
of the catalyst, depending on the pH. The
photodegradation of the seven molecules in the
batch reactor was successfully carried out, and
the behavior was in accordance with pseudo-first-
order kinetics. Furosemide and ranitidine were
selected to carry out the study of rejection and
photodegradation in the hybrid membrane sys-
tem. The permeate flux of the treated water was
in the 31.5–60.0 L/(h m2) range for NTR 7410
membrane, whereas rejection values in the range
10–60 % for furosemide and 5–30 % for raniti-
dine in the dark (without photoreaction) were
found. The degradation in the hybrid membrane
photoreactor showed that the photocatalyst was
retained by the membrane in the reaction ambi-
ent, while the membrane rejection toward the
pollutants was not very satisfactory. A net
decrease of the rejection down to 0 was observed
in the contemporary presence of light,
photocatalyst, and oxygen.
A batch-recirculated photoreactor was com-
bined with a hollow fiber membrane ultrafiltra-
tion (UF) unit for heterogeneous photocatalysis
applications (Sopajaree et al. 1999). The
Photocatalytic Membrane Reactor
operation and modeling of the UF process com-
ponent and the performance of the integrated
photoreactor-UF process assembly were studied.
Methylene blue and titanium dioxide (Degussa
P-25) were used as the test pollutant and
photocatalyst, respectively. The influence of
cross-flow velocity, transmembrane pressure,
and TiO2 dose on the permeate flux through the
hollow fiber membrane was described. These
data are modeled on the basis of concentration
polarization and gel layer formation at the mem-
brane surface/feed slurry boundary. The opera-
tion of the integrated photoreactor-UF assembly
over ten repeated cycles was experimented.
Photocatalyst separation was complete as gauged
by nephelometric turbidity measurements. How-
ever, a systematic degradation in the
photocatalyst performance was noted with each
repeated cycle. Dynamic laser light-scattering
data were consistent with agglomeration of the
TiO2 particles as a result of the UF process and
suggest a possible factor in the degraded
photocatalytic activity.
A photocatalytic reactor membrane pilot sys-
tem, employing UV/TiO2 photocatalysis, was
evaluated by Benotti et al. (2009) for its ability
to remove 32 pharmaceuticals, endocrine-
disrupting compounds, and estrogenic activity
from water. Twenty-nine of the targeted com-
pounds in addition to total estrogenic activity
were greater than 70 % removed, while only
three compounds were less than 50 % removed
following the highest level of treatment
(4.24 kWh/m3). No estrogenically active
3
transformation products were formed during
treatment. Additionally, the unit was operated in
photolytic mode (UV only) and photolytic plus
H2O2 mode (UV/H2O2) to determine the relative
amount of energy required. Based on the electri-
cal energy per order (EEO), the unit achieved the
greatest efficiency when operated in photolytic
plus H2O2 mode for the conditions tested.
References
Benotti MJ, Stanford BD, Wert EC, Snyder SA
(2009) Evaluation of a photocatalytic reactor mem-
brane pilot system for the removal of pharmaceuticals
and endocrine disrupting compounds from water.
Water Res 43:1513–1522
Lee SA, Choo KH, Lee CH, Lee HI, Hyeon T, Choi W,
Kwon HH (2001) Use of ultrafiltration membranes for
the separation of TiO2 photocatalysts in drinking water
treatment. Ind Eng Chem Res 40:1712–1719
Molinari R, Mungari M, Drioli E, Di Paola A, Loddo V,
Palmisano L, Schiavello M (2000) Study on a
photocatalytic membrane reactor for water purifica-
tion. Catal Today 55:71–78
Molinari R, Palmisano L, Drioli E, Schiavello M (2002)
Studies on various reactor configurations for coupling
photocatalysis and membrane processes in water puri-
fication. J Membr Sci 206:399–415
Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
erogeneous photocatalytic degradation of pharmaceu-
ticals in water by using polycrystalline TiO2 and a
nanofiltration membrane reactor. Catal Today
118:205–213
Sopajaree K, Qasim SA, Basak S, Rajeshwar K (1999) An
integrated flow reactor-membrane filtration system for
heterogeneous photocatalysis. Part II: experiments on
the ultrafiltration unit and combined operation. J Appl
Electrochem 29:1111–1118
P
Photocatalytic Process
Palmisano Leonardo
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Università di Palermo, Palermo, Italy
A photocatalytic process is a set of reduction and
oxidation photocatalytic reactions occurring in
the presence of a photocatalyst (see
photocatalyst) that gives rise to one or more
products starting from organic or inorganic sub-
strate(s).
The distinction of the photocatalytic reactions
in oxidation and reduction means that only the
main product(s) derive(s) from oxidation or
reduction, respectively, of the main reagent(s).
Noticeably, in fact, both the oxidative and reduc-
tive pathways are present in heterogeneous
photocatalytic processes. Sometimes the reduc-
tion pathway produces species (e.g., O2• by
trapping electrons in the conduction band of a
semiconductor photocatalyst) whose subsequent
reaction (e.g., with H2O) gives rise to •OH and
•
O2H oxidant radicals.
The photoproduced holes can straightfor-
wardly attack the adsorbed species or solvent
molecules (for instance, H2O) producing oxidant
radical species. The following sketch represents
the possible initial steps of a photocatalytic pro-
cess (Fig. 1).
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_464-4
The heterogeneous photocatalytic oxidations
are generally unselective, and several studies and
applications have been reported, for instance, in
the field of outdoor and indoor environment puri-
fications to abate low concentrations of organic
and inorganic pollutants (Serpone and Emeline
2005). The heterogeneous photocatalytic method
appears to be efficient only in those cases where
low concentrations of pollutants are present
because the presence of high concentrations
slows down the reaction rates. Moreover, it
should be checked, with great care, both the
absence of mass transfer phenomena controlling
the reaction kinetics and the possible
photocatalyst deactivation, due to possible accu-
mulation of by-products and/or intermediates
onto the photocatalyst surface which could
block the (photo)active sites (particularly for
long lasting runs in gas-solid systems). These
problems are not dramatic in the aqueous sys-
tems. A moderate mixing of the reacting suspen-
sion is sufficient to guarantee the absence of a
mass control on the reaction kinetics. The
photocatalyst surface, in fact, is cleaned by pro-
duction of a high number of oxidant radicals that
induce consecutive attacks to the intermediates
giving rise to their complete mineralization by
means of several adsorption-desorption steps. In
addition, the mineralization can proceed through
intermediates that do not desorb into the bulk of
solution, but are subjected to oxidant attacks onto
the surface until the formation of CO2. Indirect
evidence of this behavior in many cases is the
2 Photocatalytic Process
Photocatalytic Process,
Fig. 1 Photocatalytic
Process
hn
detection of CO2 soon after the starting of
irradiation.
Heterogeneous photocatalytic processes have
been more recently addressed also toward the
selective production of high-value molecules in
mild experimental conditions by using suitable
photocatalysts, solvent and starting substrates
(Palmisano et al. 2010; Augugliaro and
Palmisano 2010), and, in some cases, also mem-
branes (Molinari et al. 2009).
References
Augugliaro V, Palmisano L (2010) Green oxidation of
alcohols to carbonyl compounds by heterogeneous
photocatalysis. ChemSusChem 3:1135–1138
Reduction
Conduction band
e− Adsorption
EG
Adsorption
h+
Valence band Oxidation
Molinari R, Caruso A, Palmisano L (2009) Photocatalytic
membrane reactors in the conversion or degradation of
organic compounds. In: Drioli E, Giorno L (eds) Mem-
brane operations, innovative separations and transfor-
mations. Wiley-VCH, Weinheim, pp 335–361
Palmisano G, Garcı́a-López E, Marcı̀ G, Loddo V,
Yurdakal S, Augugliaro V, Palmisano L (2010)
Advances in selective conversion by heterogeneous
photocatalysis. Chem Commun 46:7074–7089
Serpone N, Emeline AV (2005) Modelling heterogeneous
photocatalysis by metal-oxide nanostructured semi-
conductor and insulator materials: factors that affect
the activity and selectivity of photocatalysts. Res
Chem Intermed 31:391–432
P

Plasma Polymers (PPs) the intensity and energy of the species

bombarding the growing film.
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Applications
Pakistan
The advantages of plasma polymer films include
excellent coating adhesion on almost all sub-
The term plasma polymer represents a material
strates (Feddes et al. 2004), chemical and
that is created as a result of a passage of monomer
mechanical stability (Hamerli et al. 2003), ther-
in gaseous form through the glow discharge
mal stability (Zhang et al. 2003), and high barrier
(Odian 2004), or simply one should say that an
effects (Moffitt et al. 2000). Applications of
electric discharge in an organic gas produces
plasma-polymerized films are associated with
plasma polymer. Usually, it is deposited in the
biomaterials, textile industry, electronics (e.g.,
form of a thin film. Plasma polymers are different
semiconductors, insulators, thin-film dielectrics),
from the conventional polymers. In general, con-
optical applications, chemical processing
ventional polymer has regularly repeating units
(reverse osmosis membrane, permselective mem-
(Fig. 1), while in the case of plasma polymers, a
brane), and surface modification (adhesive
great number of free radicals are trapped within
improvement, protective coating). A significant
the network; because of these radicals, the chains
area of research has been on the use of plasma
are short, and in addition they are randomly
polymer films as permeation membranes. The
branched and terminated with a high degree of
permeability characteristics of plasma polymers
cross-linking (Fig. 2).
deposited on porous substrates are different than
The application of plasma causes the genera-
usual polymer films. The characteristics depend
tion of a great number of free radicals which are
on the deposition and polymerization mecha-
trapped within the plasma polymer network.
nism. Plasma polymers as membranes for sepa-
These radicals cannot recombine rapidly, and
ration of oxygen and nitrogen, ethanol and water,
therefore when the plasma polymer is exposed
and water vapor permeation have all been studied
to the open atmosphere, they react with the oxy-
(Inagaki 1996). The application of plasma-
gen and water vapor. These free radicals are the
polymerized thin films as reverse osmosis mem-
cause of often observed aging processes in
branes has received considerable attention as well
plasma polymers. Plasma polymers possess a
(Kim and Kim 2001).
rather disordered structure, and this depends on
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_468-5
2 Plasma Polymers (PPs)

CH2 CH2 CH2 Feddes B, Wolke JGC, Vredenberg AM, Jansen JA

(2004) Initial deposition of calcium phosphate ceramic
on polyethylene and polydimethylsiloxane by rf mag-
netron sputtering deposition: the interface chemistry.
CH2 CH2
Biomaterials 25:633–639
Hamerli P, Weigel T, Groth T, Paul D (2003) Surface
Plasma Polymers (PPs), Fig. 1 High density polyeth- properties of and cell adhesion onto allylamine-
ylene (HDPE), an example of conventional polymer plasma-coated polyethylenterephtalat membranes.
Biomaterials 24:3989–3999
Inagaki N (1996) Plasma surface modification and plasma
CH2 polymerization. Technomic Publishing, Lancaster.
ISBN 1-56676-337-1
Kim HI, Kim SS (2001) Fabrication of reverse osmosis
C
•CH
membrane via low temperature plasma polymeriza-
CH tion. J Membr Sci 190:21–33
CH Moffitt CE, Reddy CM, Yu QS, Wieliczka DM, Yasuda
C C
HK (2000) Selective adsorption of fluorocarbons and
CH2 CH
CH2 CH its effects on the adhesion of plasma polymer protec-
tive coatings. Appl Surf Sci 161:481–496
CH C Odian G (2004) Principles of polymerization, 4th edn.
CH2 CH2 CH2
Wiley, Hoboken, p 227
Zhang J, Feng XF, Xie HK, Shi YC, Pu TS, Guo Y (2003)
Plasma Polymers (PPs), Fig. 2 Hypothetical structure The characterization of structure-tailored plasma films
of a hydrocarbon plasma polymer (Biederman 2004) deposited from the pulsed RF discharge. Thin Solid
Films 435:108–115
References

Biederman H (2004) Plasma polymer films. Imperial Col-

lege Press, London, p 15
T
Track-Etch Membranes as Tools
for Template Synthesis of Nano-/
Microstructures and Devices
S. K. Chakarvarti
Manav Rachna International University,
Faridabad, India
Department of Physics, National Institute of
Technology, Kurukshetra, Haryana, India
Synonyms
Electrochemical deposition; Galvanic replica-
tion; Nuclear track filters
Introduction
In the fast developing technologies era, nanotech-
nology is the one significant technology that has
already taken a big leap. It appears to be all set for
bringing in revolution in the development and
advancement of techniques involved in the syn-
thesis and fabrication of sensors and devices with
great potential. The conventional microelectron-
ics fabrication techniques are facing very harsh
competitions from low dimensional strategies
helping “Moore’s Law” survive and bringing
down the high costs. The conventional tech-
niques for fabrication of very low dimensional
wires – say quantum wires – include wet chem-
istry, electron beam lithography, focused ion
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_473-1
beam techniques, and atomic-beam lithography
(Huixin). That has shown the ways for adopting
newer alternative approaches which are relatively
inexpensive, easier to handle, and synergistically
adorned with high efficacy. Nanotechnology is
one of the fastest growing new areas in science
and engineering and deals with science and tech-
nology associated with dimensions in the range of
0.1–100 nm. The subject arises from the conver-
gence of electronics, physics, chemistry, biology,
and materials science to create new functional
systems of nanoscale dimensions. The ability to
fabricate structures with nanometric precision is
of fundamental importance to any exploitation of
nanotechnology. Nanotechnology is predicted to
have a major impact on the manufacturing tech-
nology in the next few decades from now.
It is now well known that size of the devices
and components dictate many unusual traits and
characteristics where quantum effects become
more predominant. In the recent years, there has
been a tremendous spurt in the potential applica-
tions of metallic as well as nonmetallic nano-/
microstructures and materials. Quasi-one-
dimensional nanostructures and materials like
nanowires, fibers, tubules, etc., having high
aspect ratio, would provide unusual and uncom-
mon properties like strength and hardness
enhancement, dramatic changes in electrical con-
duction, field-ion-emission through tunneling
phenomenon, optical, magnetic, and chemical,
and other important functional attributes which
are found to be enhanced when the size reduction
2 Track-Etch Membranes as Tools for Template Synthesis
comes into play. Materials with nanoscopic
dimensions may exhibit quantized conductance
(Landauer 1989) which not only has potential
technological applications in various areas but
also is of fundamental interest.
It has been approximately five decades since
researchers first began exposing materials like
polymers to ionizing radiation and reporting the
occurrence of cross-linking and other useful
effects. Today, a substantial commercial industry
is in place based on processing of polymers with
radiation. Innovation in this field has by no means
ended; important new products made possible
through radiation technology continue to enter
the marketplace, and exciting new innovations
in the application of radiation to macromolecular
materials are under exploration at research insti-
tutions around the world.
This entry reviews the technique – the “tem-
plate synthesis” (TS) – involving the porous
membranes (specific reference is made to track-
etch membranes) which are spin-off from the
radiation-matter interaction and are used as
tools in the development of nano/micromaterials,
structures, and devices. The recent past has
witnessed the keen interest being generated on
the use of innovative technologies like TS in the
production of nanomaterials’ fabrication involv-
ing materials like metals, nonmetals like semi-
conductors, magnetic multilayered nanowires,
conducting polymers, glasses, nanotubules,
wires, whiskers, etc., reported from various
authors and from our lab (See refs in
(Chakarvarti and Vetter 1998; Martin 1996;
Brumlik et al. 1994; Chakarvarti and Vetter
1993; Kumar et al. 2004a, b, c, d, e, f; Sekhon
et al. 2004; Kumar et al. 2005; Chakarvarti
et al. 2005a; Kumar and Chakarvarti 2005;
Chaudhri et al. 2006a; Singh and Chakarvarti
2008a; Chakarvarti 2007a; Kumar and
Chakarvarti 2007a; Chakarvarti 2007b; Kumar
et al. 2007a, b; Chaudhri and Chakarvarti
2008a; Kumar et al. 2008a)).
Nano Synthesis Approaches
All the conventional and available nanosynthesis
techniques can be categorized into two comple-
mentary approaches:
• The top-down approach – starting with the
bulk material and carving the way down to
the nanoscale, and
• The bottom-up approach – starting at the
molecular level and fabricating up the material
through the small cluster level to the nanopar-
ticle and the assembly of nanoparticles.
Nanotechnology provides the ability to fabri-
cate structures with nanometric precision that is
of fundamental importance. The potential of
combining radiation effects with nanomaterials
has been recognized from the very early stages of
nanoscience research. In the many uses of
nanostructures, and nanoparticles in particular,
from catalysis, bio-sensing, nano-electronics,
magnetic applications including separations,
mechano-chemical conversion, and to molecular
computing radiation can play a significant role.
Many nanostructured systems, like metal sul-
fide semiconductors of nanometric matrices,
PC-controlled biochips for programmed release
systems, nano-ordered hydrogels based on natu-
ral polymers, development of polysaccharides,
emerge out from the use of radiation (UV beam,
electron beam, or focused ion beam) techniques
which offer unmatched reproducibility and very
narrow size distribution. The relative advantages
and deficiencies of each of them are still to be
clarified as the technology advances. However,
whether UV or electron beam will lead to the
highest resolution is still debated.
The studies on natural rubber-clay composites
and thermoplastic natural rubber-clay composites
have given interesting results. Nanomaterials
with high abrasion and high scratch resistance
will find industrial application.
The formation of microporous and
nanoporous membranes having highly uniform
geometry and precisely determined structures is
an exciting example of industrial application of
ionizing radiation. These materials, called track-
etch membranes (TEMs) were first made by irra-
diation of polymeric sheets, micas, and glasses
with fragments from the fission of heavy nuclei
such as californium or uranium (nuclear track-
etch method). This technique presents a great
limitation due to contamination of the foil with
Track-Etch Membranes as Tools for Template Synthesis
radioactive products so that “cooling” of the irra-
diated material, before using, is needed; this usu-
ally takes a few months. The second method
makes use of heavy ion beams, usually of energy
on the order of several MeV, from accelerators
and presents quite a few advantages over the
former one which are: (a) no induced radioactiv-
ity in the irradiated material when ion energy is
below the Coulomb barrier; (b) all tracks show
the same etching properties; (c) deeper penetra-
tion in the material owing to higher energy of
particles; (d) higher density (even >109 cm 2
for smaller pores) track arrays; and (e) easier
control of the impact angle and production of
arrays of parallel tracks. A heavy ion beam with
acceleration energy of more than 1 MeV/n
deposits its energy to a substrate in a region
<10 nm in diameter (an ion track); the depth of
the affected region can be regulated by changing
the energy or replacing species of ion particles.
Widely used polymers for ion track membranes
are polyethylene terephthalate (PET) and poly-
carbonate (PC). By bombarding PET or PC films
with swift heavy ions (e.g., Ar+, N+, or Xe+) latent
radiation damage linear tracks are created
through the samples.
According to the following sensitization and
etching with an alkali solution (NaOH for
instance), uniform cylindrical, conical, tunnel-
like, or cigar-like pores have been obtained.
Pore sizes or dimensions depend upon various
factors, viz., the nature and energy of incident
particles, the target material, etch conditions,
e.g., temperature, nature of etchant, pre-etch stor-
age conditions, etc., and are controllable.
Cylindrical channel 0.02–5.0 mm in diameter
with lengths of 10–50 mm, membranes containing
anywhere from a single pore up to 109 pores/
cm 2 have been produced, and thin film polymer
membranes having highly uniform pore size and
a wide variety of porosities in well-distributed
areas of the template (patterning) are already
commercially available. A number of modifica-
tion methods have been devised for creating
TEMs with special properties and functions.
These isoporous membranes are used as tem-
plate materials for the synthesis of micro- and
nanostructures. The template-base method
3
consists of filling a host porous medium with
one or more desired materials. Three main pro-
cesses are used for the synthesis of various com-
binations of polymers and/or metals:
(a) electrodeposition, where one side of the tem-
plate coated with a metallic layer, or the tem-
plate support itself, is used as a cathode for
electroplating; (b) chemical polymerization
where a solution of the desired monomer and
initiator, in which the template membrane is
dipped, is left to diffuse through the pores of
the templates leading to a polymerization
reaction in these pores; (c) electroless plating
where a catalyst to the pore walls is applied
which facilitates the deposition of metal on the
activated pores of the template. The micro- or
nanomaterials, which are produced in this
way, take the form of wires or tubules. Mag-
netic, conducting, and superconducting
nanowires and nanotubules in array or isolated
mode possessing special properties have been
manufactured in this way.
There are two distinct nano-fabrication pro-
cesses using heavy ion beams; one is nano-hole
formation due to the damage of ion beam path, and
the other is nanowire formation due to cross-
linking of polysilane, which is also caused by
heavy ion beams. Potential applications in devices
such as microwave filters for shielding microwave
ovens and mobile phones, or in chemical detectors
and biosensors with conductive polymer
nanotubules are also being seriously considered.
The fabrication of ion track membranes made
of PET has been reported to develop selective
membranes for the separation of toxic metal
ions, biomolecules, and biological cells because
of the advantages to control the pore size and the
properties of the internal surfaces of the pores.
Methodology
Track-Etch Membranes (TEMs)
The most widely used materials in manufacturing
TEMs are polymers, micas, and rarely this glass
sheets. TEMs, also known as nuclear track filters
4 Track-Etch Membranes as Tools for Template Synthesis
(NTFs), have emerged as spin-off from solid state
nuclear track detectors (SSNTDs) – solid dielec-
tric materials capable of storing damage trails of
energetic heavily ionizing ions which can subse-
quently be chemically amplified for observation
as pores either through, say SEM or optical
microscope. The art and science used in crafting
of TEMs as templates involves two
steps – irradiation of an SSNTD foil or a film by
heavy energetic ion beam creating damage trails,
also called as latent tracks and, followed by a
controlled chemical etching of these latent tracks
so as to produce see-through pores in the host
material. The size and dimensions of the etched
pores can be controlled conveniently through
parametric control over the nature and energy of
the intruding ions, the host material as target to be
developed as template, chemical etch conditions,
viz., nature, concentration, temperature, agita-
tion, etc., besides preirradiation and
postirradiation storage conditions of the target
material. The etched pores can have diameter
ranging from few nm to mm. NTFs have been
put to numerous other applications besides their
use as templates. There exists a wealth of litera-
ture on SSNTDs and related topics. As discussed
already, a large number of materials are used in
manufacturing of NTFs which include mainly
polymeric sheets, micas, glasses, etc. The particle
track-etch technique, therefore, enables the gen-
eration of definite shaped pores which can either
be used individually in the form of single particle
track or collectively in the form of pore arrays
constituting many pores – distributed either sto-
chastically (pore density as high as 1010/cm2), or
in a well-defined spatial geometry through the
control of the drilling particle beam used in
“write mode.” Areal dispersion usually lies
between 2 % and 20 % and a 10 MeV/nucleon
heavy ion (say, for example, various projectiles
used are collimated beam of fission fragments,
heavy energetic ions like U, Pb, Ag, Si, Bi, etc.,
whose range in the target material is far greater
than the thickness of the target) has a range of the
order of 10 mm in many polymers (Williams and
Giordano 1984). The custom made NTFs are
available in a wide variety of pore size and poros-
ities. The crafting of TEM templates through ions
has been discussed in details (see for example,
(Possin 1970; Williams and Giordano 1984;
Klien et al. 1993); etc.). Handled adequately and
properly, these TEMs can enable wires, tubules,
solid cylinders, conical or tapered needles, etc.,
with a well-controlled dimension and shape
besides a large aspect ratio. The dimensional
parameters can vary from 10 nm to several micro-
meters with aspect ratio as high as 10–1000. The
pores can be “drilled” with alignment in any
direction depending upon the angle of incidence
of the beam with the target. The synthesized
members may either be left within the pores as
embedded or can be removed either by dissolving
or removing the host or pulling out mechanically
but carefully of the host matrix. Figure 1 shows
schematically the process of producing TEM and
its use as template, and Fig. 2 shows SEM pho-
tograph of a processed polycarbonate (Makrofol)
NTF with monodisperse pores.
Template Synthesis: A Technique
The template approach has been extensively
investigated in the synthesis of various
nanostructures. For example, mesoporous oxides
with well defined and ordered porous structure
can be readily synthesized using surfactant or
copolymer micelles as templates through sol–gel
processing. However, template-based synthesis is
most commonly and widely used to prepare free
standing, nonoriented and oriented nanowires, or
nanorods or nanotubes; the latter is also referred
to as nanorod or nanowire or nanotube arrays.
The most commonly used and commercially
available templates are anodized alumina mem-
brane (AAM) and radiation track-etched polycar-
bonate (PC) membranes. Other membranes have
also been used, such as nanochannel array on
glass, radiation track-etched mica, mesoporous
materials, porous silicon by electrochemical
etching of silicon wafer, zeolites (Ozin 1992),
and carbon nanotubes. Bio-templates are also
explored for the growth of nanowires and
nanotubes such as Cu, Ni, Co, and Au nanowires.
The commonly used alumina membranes with
uniform and parallel pores are made by anodic
oxidation of aluminum sheet in solutions of sul-
furic, oxalic, or phosphoric acids. The pores can
Track-Etch Membranes as Tools for Template Synthesis
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 1 Schematic diagram showing production of a
TEM as a template for synthesis of low dimensional tem-
plate with monodispersed pores of dia structures. (a).
Polymeric foil being irradiated with heavy and energetic
ion beam, (b) chemically etched foil as template or an
NTF (c), deposited metal ions into the pores, producing
filled pores, (d) free-standing structures after removal of
host template, and (e) mechanical peeling, an alternative
to dissolution or removal of the host for retrieval of syn-
thesized structures
be arranged in a regular hexagonal array, and
densities as high as 1011 pores/cm2 can be
achieved. Pore size ranging from 10 nm to
100 mm can be made. PC membranes are made
by bombarding a nonporous polycarbonate sheet,
typically 6–20 mm in thickness, with nuclear fis-
sion fragments to create damage tracks and then
chemically etching these tracks into pores. In
these radiation track-etched membranes, pores
have a uniform size as small as 10 nm, but they
are randomly distributed. Pore densities can be as
high as 109 pores/cm2. In addition to the desired
pore or channel size, morphology, size distribu-
tion and density of pores, and template materials
5
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 2 A processed TEM with pore dia ca. 1 um
must meet certain requirements. First, the tem-
plate materials must be compatible with the
processing conditions. For example, an electrical
insulator is required for a template to be used in
electrochemical deposition. Except for the
template-directed synthesis, template materials
should be chemically and thermally inert during
the synthesis and following processing steps.
Secondly, depositing materials or solution must
wet the internal pore walls. Thirdly, for the syn-
thesis of nanorods or nanowires, the deposition
should start from the bottom or one end of the
template channels and proceed from one side to
another. However, for the growth of nanotubules,
the deposition should start from the pore wall and
proceed inwardly. Inward growth may result in
the pore blockage, so that should be avoided in
the growth of “solid” nanorods or nanowires.
Kinetically, enough surface relaxation permits
maximal packing density, so a diffusion-limited
process is preferred. Other considerations include
the easiness of release of nanowires or nanorods
from the templates and of handling during the
experiments. AAM and PC membranes are most
commonly used for the synthesis of nanorod or
nanowire arrays. Both the templates are very
convenient to use during the growth of nanorods
by various growth mechanisms, but each type of
template also offers a few disadvantages. The
advantage of using PC as the template is its easy
handling and easy removal by means of pyrolysis
6 Track-Etch Membranes as Tools for Template Synthesis
at elevated temperatures, but the flexibility of PC
is more prone to distortion during the heating
process, and the removal of the template would
occur before complete densification of the
nanorods. These factors would result in broken
and deformed nanorods. The advantage of using
AAM as the template is its rigidity and resistance
to high temperatures, allowing for the nanorods
to densify completely before removal. This
would result in a larger surface area of fairly
free-standing and unidirectionally aligned
nanorod arrays. The problem with AAM is the
complete removal of the template after nanorod
growth, which has so far been unsuccessful using
wet-chemical etching.
The technique of TS (Ozin 1992) may be clas-
sified into three categories depending upon the
mode of use of templates (Huixin): the negative
template method, positive template method, and
surface step-edge template method. The negative
template method which is the most popular and
widely used techniques of TS allows the use of
prefabricated nanopores in solid templates, and
the material is deposited into these pores normally
using electrochemical techniques. After removing
(say by way of dissolving) the host template, free-
standing elements as wires, cylinders, or conical
structures can be obtained. The method has been
regarded as “brute-force” method as the synthe-
sized ensemble structure depicts the true replica-
tion of the morphology of the pores (Foss 2002).
The fabrication of such templates involves many
techniques including heavy ion irradiation of solid
insulating materials like polymeric foils, micas,
glasses, etc., producing so-called TEMs. More
details would follow later. The positive template
methods use wire-like substrates like DNA (size
ca. 2 nm) (Braun et al. 1998), carbon nanotubes
(Fullam et al. 2000), etc., on the outer surface of
which the material is deposited to the desired
dimensions. The removal of templates can pro-
duce wire-like or tube-like structures. Other posi-
tive templates have been discussed by Huixin He
and Nongjian J.Tao (Huixin). The surface step-
edge templates, also known as “step-edges deco-
ration,” use the fact that there is preferential or
selective deposition of many materials initiating
on the defect sites. Zach et al. (Zach et al. 2000)
and Bera et al. (Bera et al. 2004) used this tech-
nique for generating conductive metal oxide
(MoOx) at the step-edges of HOPG, which after
reduction in appropriate environment could yield
metallic Mo nanowires.
When electrodeposition is carried out, the
nucleation of nanostructures on the electrode sub-
strate via template pores during electrodeposition
is influenced by the crystal structure of the sub-
strate, specific free energy, and other factors like
adhesion energy; orientation of the lattice of the
substrate; etc., and the final size distribution of
electrodeposits is strongly dependent upon the
growth and nucleation kinetics (Bera
et al. 2004). Template-assisted electrodeposition
process can be divided into two categories: active
template-assisted process which results from
growth of nuclei that essentially nucleate at the
pores and defects of the substrate, while the other
is known as restrictive template-based electrode-
position used mostly in the synthesis of metallic
nanowires, involves deposition of metal into the
prefabricated and designed pores within an inert,
insulator membrane or template. PTEMs, porous
alumina, conductive polymers, carbon, etc., have
been used as templates which fall under this cat-
egory (Bera et al. 2004).
Negative Template Synthesis
The basic and underlying principle of negative
TS is similar to that of producing materials
through the use of replication, e.g., die-casting
or molding like making ice candies. There are
many methods used in practice for preparing
nanomaterials right from milling to lithographic
techniques (Hhadjipanayis and Siegle 1994).
These techniques suffer from the problems like
little control over the final morphology of the
resulting nanoproducts, ensembles, and mate-
rials. The TS has in turn edge in this regard. It
enables the synthesis of a variety of materials
ranging from micro- to nanodimensions, high
aspect ratio, and of desired morphology and
geometry – the single unique attribute which
makes this route as most acceptable and econom-
ical too. A template, in a general sense, may be
defined as a predesigned structure within which a
network exists, which can be utilized for further
Track-Etch Membranes as Tools for Template Synthesis
use. Thus, for example, a membrane with
prefabricated cavities or pores of known mor-
phology, number, distribution, and configuration
may also act as a template; the pores of which can
facilitate replication by any suitable means.
Removal of the host template would lead to the
presentation of ensembles whose morphological
and stereo-chemical features and traits might rep-
licate the original cavities or pores in the tem-
plate. Here in this technique, materials can be
deposited within the cavities or pores or any
other dimensional structures, by various methods
like electrochemical or chemical reduction
(electroless) of the appropriate ion. Depending
upon the template geometries and the controlling
factors, functional procedure, and related param-
eters, the generated structures can be monodis-
perse homogeneous or heterogeneous,
multilayered, short, squat fibrils, long needles,
hollow tubules, tapered conical (single or double
cones) elements, etc., depending upon the tem-
plate factors stated above. The interesting aspect
is that one can have complete control over the
aspect ratio (length and diameter ratio). Metallic
as well as nonmetallic tubules can be obtained by
chemically derivating the pore/cavity walls by
providing molecular anchors so that the
electrodeposited metal deposits preferentially on
the walls layer by layer, leading to hollow tubules
when the process is terminated at a preestimated
time interval (Martin et al. 1990). The synthe-
sized structures can remain either inside the host
structures in the templates or they can be ren-
dered free, and collected as ensemble. Alterna-
tively, an ensemble of nano-/microstructures that
protrude from a surface like the bristles of a brush
can be produced. The technique is blessed with
simplicity and nano-/microstructures with
extraordinary low dimensions have been reported
to be produced (see refs in Parthasarthy
et al. 1995; Schonenberger et al. 1997; Sima
et al. 2004) which are otherwise difficult to man-
ufacture using lithographic methods.
History and Development of Negative Template
Synthesis
Bean (Bean 1969) first demonstrated the art of
filling the pores of a membrane with silver
7
followed by Possin (Possin 1970) who utilized
electrodeposition technique in the fabrication of
thin wires as small as 400 Å using mica with
etched pores as templates for synthesis of such
elements of the nanostructures. Williams and
Giordano (Williams and Giordano 1984) claimed
to have reduced the size down to 80 Å after
effecting some refinements to the technique.
Penner and Martin (Penner and Martin 1987)
reported on the generation and characterization
of ultra-microelectrodes with radii as small as
1000 Å. Klien et al. (Klien et al. 1993) reported
on the fabrication of graded CdSe/CdTe hetero-
structures and development of chemistry for fab-
ricating II-VI chalcogenide semiconductors
CdSe and CdTe within the template membranes
producing micro-diode arrays consisting of
micro-cylinders retinal rod cells – the photore-
ceptors in the human eye – and having ca. five
times smaller diameter than that of photorecep-
tors. Team led by Prof. Charles Martin at Colo-
rado State University, USA, has been actively
engaged in exploring and exploiting the TS for
its full potential and a large number of reports are
available (see refs in (Huczko 2000)).
Researchers at GSI at Darmstadt, Germany
(where this author has had also his first hands-
on experience with the technique of TS for a short
duration during early 1990s), have also many
reports to their credit for developing the tech-
nique further and generating nano-/
microstructures (see, for example, ref. (Spohr
1990)). A large bulk of literature since then has
been published on the negative TS and its appli-
cations (see refs in (Chakarvarti and Vetter 1998;
Huczko 2000; Martin 1994)). This lab has also
been reporting from time to time on the synthesis
of nano-/microstructures, devices, and tubules
using TEMs as templates (see refs.(Chakarvarti
and Vetter 1998; Martin 1996; Brumlik
et al. 1994; Chakarvarti and Vetter 1993; Kumar
et al. 2004a, b, c, d, e, f; Sekhon et al. 2004;
Kumar et al. 2005; Chakarvarti et al. 2005a;
Kumar and Chakarvarti 2005; Chaudhri
et al. 2006a)). Almost simultaneously, the TS
also included porous alumina (Al2O3) mem-
branes, which are prepared electrochemically
from aluminum (the fabrication method of anodic
8 Track-Etch Membranes as Tools for Template Synthesis
porous alumina started as early as 1950s), and
have usually high pore density (as high as 1011/
cm2) with pores as small as ca.5 nm, arranged in
hexagonal arrays (Despic and Parkhutik 1989).
Here in the present review, detailed discussion
has further been carried only on negative tem-
plate synthesis using TEMs as templates for syn-
thesis of nano-/micromaterials.
Materials
While sieving properties of porous membranes
have been used from as early as some thousands
of years, but it is relatively only recently that a
technological application like TS of nano-/
microstructures has been brought to this
process – almost a by-product having no relation
with sieving properties. Until recently where the
use of positive template synthesis has started,
most of the work had been carried out using
negative template synthesis involving mainly
two types of membranes: TEMs and porous alu-
mina (Al2O3). Others include nanochannel array
glasses, xeolites, proteins, etc. A wide variety of
other nanoporous solids that can be used as tem-
plates are cited elsewhere (see, for example, ref.
Martin 1994).
Template Synthesis of Low Dimensional
Structures and Devices
The strategy for embedding matter of interest
within the etched pores or channels in the tem-
plate is the material’s placement through some
suitable mechanism at the desired places, viz.,
pores. This can be accomplished in four ways.
(Huixin) Using the capillary action of the pores/
channels and enabling the solution of the
dissolved material entering into the pores,
followed by slow evaporation of the solvent.
This will lead to growth of supersaturated struc-
tural elements (Landauer 1989) using electro-
chemical (galvanic) technique which is widely
practiced. Here, electrodeposition of the desired
metal ions is carried out either using
two-electrode or three-electrodes electroplating
cell (Bera et al. 2004;(Chakarvarti and Vetter
1998) using electroless (nongalvanic) deposition
technique (Linkot et al. 1999) and references
therein (Bercu et al. 2004). The underlying prin-
ciple is to create nucleation centers on the pore
walls and then precipitate the desired material on
these nucleation centers. Through controlled
manipulations, one can synthesize hollow as
well as solid tubules. Metals like Cu, Ni, Au,
etc. or chalcogenides are dissolved in suitable
solvents and precipitation can be facilitated on
the pore walls. Martin (1996) using chemical
reactions, say, by permitting two reagents meet
within the pores and react, produced precipitates,
followed by drying process and their retrieval
(Kumar et al. 2004d). The necessary prerequisite
is that the penetrants acting as reactants must be
hydrophilic otherwise one would require to apply
hydrostatic pressure to forcibly inject them into
the pores. In case of two gases (or one as gas and
other participant as liquid) as reactants entering
from both the faces of the template, the reaction
can be accomplished within the pores. For more
details, see references in Ferain and
Legras (2003).
In the proceeding paragraphs, more details of
galvanic synthesis only are being provided. As
mentioned, the technique is based upon the ear-
lier work of Bean (Bean 1969), Possin (Possin
1970), Spohr (1982), Williams and Giordano
(Williams and Giordano 1984) and, Penner and
Martin (1987). The simple underlying concept of
electrodeposition of metals through
electroplating is described as an electrochemical
process in which metallic ions in supporting solu-
tion are reduced to the metallic state at the cath-
ode, which, if closely covered by an NTF as a
template and as an overlay, would lead to the
formation of growth of plated film as the embodi-
ment of micro- or nanostructure. The pores of the
NTF used would act as template (see Fig. 1).
Electrochemical Cells and Electrodeposition
A scientific treatment of galvanic process is in
fact complicated, and development of optimum
plating conditions may be obtained through one’s
personal experience obtained through repeated
trials under the given inputs. The age and condi-
tion of electrolyte, viz., temperature, pH, concen-
tration, agitation rate, purity of solvent as well as
Track-Etch Membranes as Tools for Template Synthesis
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 3 Copper microstructures (Chakarvarti and Vetter
1998)
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 4 Silver conical microstructures (Kumar and
Chakarvarti 2005)
electrolyte solute, additives and their amount,
uneven current distribution, increase of specific
resistivity of electrolyte, formation of gas bub-
bles and gas blankets at electrodes excessive inter
electrode distance, etc. affect the quality of depo-
sition. Plating in small crevices or pores is very
difficult. The solutions should have good micro-
throwing powers – the ability of a solution to
plate into fine cavities or defects on the surface
such as pores, pits, polishing lines, and
scratches – besides the good covering power,
9
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 5 Buds and caps as over-deposition
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 6 Copper hollow tubules
the ability of an electrolyte to deposit metals
into pores where current density is low. Copper,
for example, has poor macro-throwing power but
can possess excellent micro-throwing power.
Electrodeposition of metals such as those which
are more electronegative (e.g., aluminum, molyb-
denum, tungsten, titanium, tantalum, zirconium,
niobium, etc.) is not always possible from aque-
ous solutions. Electrodeposition on metals in cor-
rosive electrolytes or galvanic deposition of
noble metals such as gold and silver on base
metals like copper needs much care as the adhe-
sion of the plated mass is found to be poor. With
microporous membranes, rinsing off the
10 Track-Etch Membranes as Tools for Template Synthesis

Track-Etch Membranes as Tools for Template Synthesis of Nano-/Microstructures and Devices, Fig. 7
(a) Polypyrrole microtubules (Kumar et al. 2004e). (b) Thin walled polypyrrole tubules (Kumar et al. 2004e)

Track-Etch Membranes as Tools for Template Synthesis of Nano-/Microstructures and Devices, Fig. 8
(a) Se microtubules (Chakarvarti and Vetter 1993) (b) Se microtubules (Chakarvarti and Vetter 1993)

membranes with 3 % H2SO4 followed by distilled
water and absolute ethyl alcohol would facilitate
the galvanic process in the case of metals like
zinc, indium, etc. (Possin 1970). Presoaking of
the cleaned and washed template with the given
electrolyte is also helpful (Chakarvarti and Vetter
1991). Many detailed studies of the electrochem-
ical fabrication process for nanostructures have
been reported by many workers (Schonenberger
et al. 1997; Whitney et al. 1993).
For electrodeposition of metals, some special
types of electroplating cells are used (Penner and
Martin 1987; Chakarvarti and Vetter 1991;
Dobrev et al. 1994) which offer a low ohmic
voltage drop across the electrodes even when
the cell is filled with a poorly conducting electro-
lyte. There are various cell designs available: two
electrodes and three electrode cells. The cell
designed by Dobrev et al. (1994) has the provi-
sion for mechanical stirring besides a thermostat
for maintaining the desired temperature of the
water contained in a jacket surrounding the cell
as constant.
Electrodeposition is accomplished by simply
coating one face of the overlaid template with a
metal film (preferably gold) to serve as a working
Track-Etch Membranes as Tools for Template Synthesis 11

Track-Etch Membranes
as Tools for Template
Synthesis of Nano-/
Microstructures
and Devices, Fig. 9 Cu-Se
junctions (Chakarvarti and
Vetter 1993)

Track-Etch Membranes as Tools for Template Syn- Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices, thesis of Nano-/Microstructures and Devices,
Fig. 10 Cu-Se nano-RTDs (Chakarvarti and Vetter 1991) Fig. 11 Zn-Se nano-RTDs
12
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 12 PVDF microtubule
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 13 CdS microflowers (Chakarvarti et al. 2005a)
electrode on which electrodeposition takes place.
The thickness of the film is appreciably large if
the pores in the templates have also larger size.
Alternatively, a metallic tape with conducting
adhesive on the surface may also be used for
fixing up the template membrane while the
pores on the other face act as channel templates
with one end sealed (Chakarvarti and Vetter
1991). In order to make the pore walls conducting
so as to be conducive in convenient electrodepo-
sition by way of providing molecular anchors, the
template may be moistened with solution like
chloroplatinic acid (Penner and Martin 1987)
before electrodeposition is carried out. The use
of electroless plating on the pore walls of
Track-Etch Membranes as Tools for Template Synthesis
polymeric templates might also be useful before
galvanic process is started. This needs etching of
polymer surfaces with chromic-sulfuric acid
solutions followed by activation by immersion
in tin and palladium solutions, or a colloidal
solution containing these ions. This process is
called “conditioning” which is required to
improve the wettability of the polymer surface,
which further facilitates adhesion of the plated
metal. During electrodeposition of the metal at
the cathode, the depletion of the metal ions
increases the absolute value of the deposition
potential and if this exceeds the hydrogen over-
voltage for the given process, hydrogen also
deposits resulting into a loss of plating efficiency
and increase in pH of the elctrodeposited metal,
ultimately causing “burning” of the thin deposi-
tion. In order to avoid the development of over-
potential, factors like increase in bath tempera-
ture and the agitation or the electrolyte are help-
ful. For applying deposition potential and
monitoring the current and potential drop across
the cell, a good constant voltage (potentiostat)
power supply is needed. It is found that while
DC electrodeposition can produce good quality
nanowires, the filling of the pores is partial
ca. 10–20 % (Chakarvarti and Vetter 1991).
A high filling ratio as well as generation of uni-
form array of structures can be achieved by using
AC electrodeposition. Various AC pulse shapes
like saw-tooth waves, triangular, sine waves, but
not square wave (square wave potential pulses
may be used for obtaining multilayered
Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices,
Fig. 14 Copper microrose flower
Track-Etch Membranes as Tools for Template Synthesis
nanowires, see reference Piraux et al. (1994))
with varying frequencies have been used for bet-
ter results, increased crystallinity and homogene-
ity (Yin et al. 2001). Nielsch et al. (2000) used
pulsed electrodeposition method and demon-
strated that it suits for uniform deposition of
porous alumina with almost 100 % (Nielsch
et al. 2000). From our experience, we have
found that initial high voltage for short duration
followed by low values (the process is called
“striking”) produces good results. Chakarvarti
and Vetter (Chakarvarti and Vetter 1998) have
suggested a formula in order to calculate an
approximate optimum current for satisfactory
results. It is of interest to note that the template
synthesized materials (metals as well as semicon-
ductors) in the form of solid cylinders, wires, or
whiskers can be crystalline (Dobrev et al. 1994;
Chakarvarti et al. 1996).
Synthesized Structures and Devices: Some Results
Some of the metallic, nonmetallic homogeneous
and heterogeneous structures and devices synthe-
sized in this lab are shown in the Figs. 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, and 14. The template used in
all cases were TEMs of Makrofol polycarbonate
Track-Etch Membranes
as Tools for Template
Synthesis of Nano-/
Microstructures
and Devices,
Fig. 15 Collective
current–voltage (I–V)
characteristics of Zn-Se
RTDs with average
diameters of 900 nm and
450 nm
−2 −1.5 −1 −0.5
13
having pores with different shapes (some cylin-
drical and others conical). The Makrofol foils
were got irradiated at Gesellschaft fur Schwerio-
nenforschung (GSI), Darmstadt, Germany. Also
some polycarbonate foils were obtained from
Whatman. More details and descriptions can be
found from the references quoted.
Some of the nano-/microdevices synthesized
were resonant tunneling diodes (RTDs) made
from heterojunctions of metal-semiconductors
(Cu-Se,Zn-Se,Cd-Te systems, see refs. (Kumar
et al. 2005, 2008a)) besides field-ion emitters
(Kumar et al. 2004g, 2007b) using metallic
nano/micro-tipped cylinders of copper and silver.
For filling up the template pores, the electrode-
position was carried out from one face and the
process was interrupted when the pores were
filled half-way through. The electrolyte was
replaced by another one with different metal/
semiconductor material composition, and the
deposition was further carried out till the pores
are filled up to the brim. Figure 15 shows typical
I-V characteristics of nano-RTDs synthesized
from Zn-Se deposition in Makrofol PTEMs,
confirming the fact that nature manifests identical
both in small scale and macro scale as well.
Diameter of RTDs = 900
25 nm
20 Diameter of RTDs = 450
nm
15
10
5
0
0 0.5 1 1.5 2
−5
−10
−15
−20
−25
14
Figure 14 shows a floral display as a by-product
of template synthesis process.
More results on the effect of size as well as
temperature of the synthesized RTDs of II-VI
materials, modeling of RTDs, and other aspects
of template synthesis of variety of materials have
been reported (Kumar et al. 2005, 2007a, b, c,
2008a, b, c, d, 2009, 2010a, b, 2011a, b, c, d,
2012a, b, c, d, e, 2013; Chakarvarti 2007a;
Kumar and Chakarvarti 2006, 2007a, b, c, d,
2010, 2012; Chaudhri et al. 2006b, 2010;
Chaudhri and Chakarvarti 2008b, c; Chakarvarti
et al. 2005b; Kaur et al. 2005, 2006, 2007a, b, c, d,
2009a, b, 2011a, b, c; Verma et al. 2005; Singh
et al. 2006, 2008, 2013; Singh and Chakarvarti
2008b; Chakarvarti 2009, 2010; Sekhon
et al. 2011; Gehlawat et al. 2012; Rani
et al. 2013a, b).
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P
Polyetherimide Membrane
S. M. Javaid Zaidi1,2 and Kripal S. Lakhi1
1
Australian Institute for Bioengineering and
Nanotechnology, The University of Queensland,
Brisbane, Australia
2
King Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia
Polyetherimide (PEI hereafter) is one of the
derivatives of a broad class of materials known
as polyimides. PEIs are thermoplastics having
excellent chemical and mechanical stability
with high glass transition temperature and find
its usage in numerous applications. Polyimides
are polymers containing imide group sandwiched
between two aromatic rings as shown in the
Fig. 1. In order words, in polyimides, a nitrogen
atom is shared between two carbonyl functions
(Seifert et al. 2002). PEIs can be prepared by two
different schemes, one of which involves nucle-
ophilic substitution reaction and the other scheme
consists of condensation reaction between
diamines and dianhydrides. The latter method is
more commonly employed than the former
(Sedigh et al. 1999).
Further, PEI, a derivative of polyimide, is
obtained by inserting ether groups within the
polyimide backbone. The presences of ethereal
linkages provide good processability, while aro-
matic groups attribute high performance charac-
teristics. In recent years, there has been a number
# Her Majesty the Queen in Right of Australia 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_478-1
of reports projecting PEI membranes as a suitable
material for biotechnological and biomedical
applications since the requirements for biomedi-
cal applications are rather too stringent to be
satisfied by other polymeric membranes. For
instance, development of biohybrid organ such
as the liver support system would require a mem-
brane material to have biocompatibility with
blood and tissue cells at the same time (Seifert
et al. 2002). A major advantage of the inherent
structure of PEI membranes is the presence of
polarized carbonyl groups that can be easily
functionalized using different ligands and groups
as per the requirement. Surface functionalization
of PEI could produce membranes that are com-
patible with blood on one side and with tissue
cells on the other side. Recent reports have indi-
cated that PEI possesses excellent mechanical
strength and thermal stability and high glass tran-
sition temperature. These properties together
with its ability to allow attachment and growth
of cells and almost insignificant cytotoxicity to
cells make it the most promising biomaterial for
biotechnological and biomedical applications
(Seifert et al. 2002). Further, the PEI polymers
can be used for preparing highly asymmetric
membranes for selective separation of pair of
gases, such as binary mixtures of H2 and CH4,
CO2 and CH4, and CO2 and N2 and ternary of
CO2/H2/CH4 etc. (Shen et al. 2004; Park and Lee
1995; Ahmad et al. 2010; Sedigh et al. 1999).
These are difficult separations, which can only
be achieved by these membrane processes, and
2 Polyetherimide Membrane
Polyetherimide Membrane, Fig. 1 General structure of a polyetherimide (PEI)
are widely used in industry these days. Moreover,
PEI membranes can also be used in ultrafiltration
and microfiltration and in vapor permeation of
water/1-propanol, but its use is limited by the
low hydrophilic nature of PEI membranes (Shen
et al. 2004; Li et al. 2008).
The excellent properties of PEIs have been
utilized by blending it with other well-known
polymers thereby widening the scope of its utili-
zation and application. Reports have indicated
that PEI could be used to reduce the swelling as
well as improve mechanical stability of
sulfonated (ether ether) ketone (SPEEK) mem-
branes when blended in small proportion with
SPEEKs (Bowen et al. 2004). Carbon molecular
sieve (CMS) membranes have been extensively
used for removal of CO2 from natural gas as they
have pores of relatively uniform dimension
which aids in discrimination of molecules of
very similar dimensions (Sedigh et al. 1999).
CMS membranes are prepared by carbonization
of PEI precursors and find extensive application
in solving crucial environmental problems such
as removal of sulfur from gasoline by
pervaporation process (Changewi et al. 2009).
Applications of PEIs abound in the biomedical
domain as evident from a recent report where
PEIs functionalized with groups such as hydroxyl
(-OH), amines (-NHx), carboxylic acids
(-COOH), and sulfate (-SO4) have been reported
to be successful in preventing thrombosis, a
major complication that results from a foreign
surface that comes in contact with blood. Of
these, PEIs functionalized with carboxylic acid
have been reported to possess the best blood-
contacting properties (Tzoneva et al. 2008).
References
Ahmad MA, Rashid NKA, Harun WHFW, Hameed BH
(2010) Effects of polyetherimide pyrolysis tempera-
ture on CMS membranes: study on CO2 permeance
and CO2/CH4 permselectivity. Int J Basic Appl Sci
IJBAS-IJENS 10(06)
Bowen WR, Cheng SR, Doneva TA, Oatley DL
(2004) Manufacture and characterization of
polyetherimide/sulfonated poly(ether ether ketone)
blend membranes. J Membr Sci 250:1–10
Changewi Z, Jiding LI, Jian C, Rongbin QI, Zhaokun
L (2009) Separation of sulfur/gasoline mixture with
polydimethylsiloxane/polyetherimide composite
membranes by pervaporation. Chin J Chem Eng
17(4):707–710
Li L, Yan G, Wu J, YU X, GUO Q (2008) Functiona-
lization of poly(ether imide) membranes via surface-
initiated atom-transfer radical polymerization and
their use in AntiFouling. High Perform Polym
21:455–467
Park Y-I, Lee K-H (1995) The permeation of CO2 and N2
gases through asymmetric polyetherimide membrane.
Energy Convers Manag 36(6–9):423–426
Sedigh MG, Xu L, Tsotsis TT, Sahimi M (1999) Transport
and morphological characteristics of polyetherimide-
based carbon molecular sieve membranes. Ind Eng
Chem Res 38:3367–3380
Seifert B, Mihanetzis G, Groth T, Albrecht W, Richau K,
Missirlis Y, Paul D, Von Sengbusch G (2002)
Polyetherimide: a new membrane-forming polymer
for biomedical applications. Artif Organs
26(2):189–199
Shen L-Q, Xu Z-K, Yang Q, Sun H-L, Wang S-Y, Xu Y-Y
(2004) Preparation and characterization of sulfonated
polyetherimide/polyetherimide blend membranes.
J Appl Polym Sci 92:1709–1715
Tzoneva R, Seifert B, Albrecht W, Richau K, Groth T,
Lendlein A (2008) Hemocompatibility of poly(ether
imide) membranes functionalized with carboxylic
groups. J Mater Sci Mater Med 19:3203–3210
P
Polyethylene Membrane
S. M. Javaid Zaidi1,2 and Kripal S. Lakhi1
1
Australian Institute for Bioengineering and
Nanotechnology, The University of Queensland,
Brisbane, Australia
2
King Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia
Polyethylene (PE) is a polymer obtained by poly-
merization of ethylene. Polyethylene is produced
in three different grades depending on the poly-
merization processes: low-density polyethylene
(LDPE), linear low-density polyethylene
(LLDPE), and high-density polyethylene
(HDPE). Polymerization of ethylene is carried
out in the presence of Ziegler-Natta catalyst,
and the reaction mechanism involves three
steps, namely, initiation, propagation, and termi-
nation. The properties of the polymer depend on
the operating temperature, pressure, and the reac-
tion time. Temperature control is critical in the
polymerization process due to the exothermic
nature of the reaction. PE-based membranes are
highly versatile and have been investigated for
quite some time for numerous applications such
as fuel cell research, biotechnology, and biomed-
ical applications including applications involving
environment monitoring (Amada et al. 1994;
Matsuyama et al. 2003; Sherazi et al. 2013).
Recent reports have shown that surface-
functionalized porous PE membranes have large
# Her Majesty the Queen in Right of Australia 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_479-1
protein adsorption capacity and are preferred
over inorganic materials for binding large quan-
tity of biomolecules. In particular chemically
modified sintered porous PE-based membranes
have been found to have a number of advantages.
These membranes are cost-effective; the textural
parameters such as pore size, pore volume, pore
size distribution, and surface area can be easily
tuned and consequently find applications in sep-
aration and purification of proteins including pep-
tide synthesis (Greene et al. 2005). Another
phenomenal application of nanoporous PE mem-
brane is in the development of glucose sensors
that would detect, quantify, separate, and control
transport of glucose. Such devices are absolutely
essential for people suffering from diabetes
(Uehara et al. 2011). LLDPE membranes are
used in packaging industry because of their excel-
lent mechanical and gas transport properties. It
has been reported that the gas permeability
(P) through these membranes increases according
to the following order P(CO2) > P(He) >
P(O2) > P(N2) in the temperature range 298 to
348K, and the diffusion coefficient for these
gases follows the following order D(He) > D
(O2)  D(CO2)  (N2). The disagreement in the
trend for permeability and diffusion coefficients
highlights that mass transport through the mem-
brane is dependent on the solution process
(Villaluenga and Seoane 2001).
High cost of the proton exchange membranes
coupled with the use of precious metals (such as
platinum and ruthenium) as catalyst has largely
2 Polyethylene Membrane
affected the commercialization of polymer elec-
trolyte membrane fuel cells, and consequently the
focus has shifted toward development of anion
exchange membranes (AEMs) for anion
exchange membrane fuel cells (AEMFCs).
AEMFCs are low cost and use non-noble metal
catalyst as cathode material (Sherazi et al. 2013).
Recent reports have indicated the use of poly
(vinylbenzyl chloride) grafted on ultrahigh
molecular weight polyethylene (UHMWPE)
powder by irradiating with gamma Co radiation.
These polyelectrolyte membranes have been used
in AEMFCs. Ultrahigh molecular weight poly-
ethylene powder is highly stable in alkaline
medium, shows tendency toward cross-linking
when irradiated with gamma radiations, and is a
low-cost material. Surface-modified UHMWPE
membranes have been used as biocompatible
materials for use in many biomedical applica-
tions. Surface modification of UHMWPE is
done using underwater plasma polymerization
technique since olefin polymers do not have any
functional groups which make it relatively easier
to introduce polar groups by plasma processes
thereby attributing biocompatibility (Joshi
et al. 2013). Polyethylene membranes have also
been used in environmental monitoring applica-
tions especially the organochlorine pesticides
such as lindane, aldrin, and dieldrin. It has been
reported that polyethylene membranes have
24–84 times higher chemical uptake capacity as
compared to the cellulose membrane. However, it
is also known that the solvent retention time is
low for polyethylene membranes and the rate of
diffusion of chemicals is dependent not only on
the molecular mass of the chemical species but
also on the solubility in lipids [8].
References
Amada K, Sato T, Takekawa S, Hirata M (1994) Mem-
brane properties of polyethylene films photografted
with hydrophilic monomers. Polym Gels Networks
2:323–331
Greene G, Radhakrishna H, Tannenbaum R (2005) Protein
binding properties of surface-modified porous polyeth-
ylene membranes. Biomaterials 26:5972–5982
Joshi R, Friedrich J, Subaramanian S (2013) Surface mod-
ification of ultra-high molecular weight polyethylene
membranes using underwater plasma polymerization.
Plasma Chem Plasma Process. doi:10.1007/s11090-
013-9476-2
Matsuyama H, Okafuji M, Maki T, Teramoto M, Kubota
N (2003) Preparation of polyethylene hollow fiber
membrane via thermally induced phase separation.
J Membr Sci 223:119–126
Sherazi TA, Sohn JY, Lee YM, Guiver MD (2013) -
Polyethylene-based radiation grafted anion-exchange
membranes for alkaline fuel cells. J Membr Sci
441:148–157
Uehara H, Kakiage M, Sekiya M, Sakuma D,
Yamanobe T, Takano N, Barraud A, Meurville EE,
Ryser P (2011) Nanoporous polyethylene membranes
for glucose sensors. In: 5th European IFMBE confer-
ence, IFMBE proceedings vol 37, pp 987–991
Villaluenga JPG, Seoane B (2001) Experimental estima-
tion of gas-transport properties of liner low-density
polyethylene membranes by an integral permeation
method. J Appl Polym Sci 82:3013–3021
P
Polyethylene Oxide
Anja Car
Department of Chemistry, University of Basel,
Basel, Switzerland
Polyethylene oxide (PEO) is a polymer prepared
by polymerization reaction (polycondensation) of
ethylene oxide and water catalyzed by acidic or
basic catalysts (Hideshi 1995). It has two chemi-
cally synonymous names: poly(ethylene glycol)
(PEG) and poly(oxyethylene) (POE)
(Buchmeister 2003). PEG has tended to refer to
oligomers and polymers with a molecular weight
below 20,000 g/mol, PEO to polymers with a
molecular weight above 20,000 g/mol, and POE
to a polymer of any molecular weight with the
general formula H(OCH2CH2)nOH (Fig. 1), com-
mercially available over a wide range of molecular
weights (http://www.sigmaaldrich.com/materials-
science/material-science-products.html), where n
is the average number of repeating oxyethylene
groups (OCH2CH2) typically from 2 to few 100.
The low molecular weight members from n = 2 to
n = 4 are diethylene glycol, triethylene glycol,
and tetraethylene glycol, respectively, which are
produced as pure compounds (DOW). Increasing
the number of repeating oxyethylene groups leads
to products with different oligomer sizes in a
broadly or narrowly defined molecular weight.
For example, PEG 300 typically denotes a com-
pound that includes a mixture of oligomers having
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_480-2
an average molecular weight of 300 g/mol. Low
molecular weight (<1,000 g/mol) PEGs are vis-
cous and colorless liquids with freezing point from
10  C (diethylene glycol), while higher molecu-
lar weight PEGs (PEOs) are waxy, white solids
with melting points proportional to their molecular
weights up to limit of about 67  C (Bailey and
Koleske 1976). These polymers are amphiphilic
and soluble in water as well as in many organic
solvents (e.g., methylene chloride, ethanol, tolu-
ene, acetone, and chloroform) including aromatic
hydrocarbons (not aliphatic) (Zhao et al. 1998).
Although PEG and PEO with different molecular
weights have different physical properties (e.g.,
viscosity, melting point) due to chain-length
effects, their chemical properties are nearly iden-
tical. Hence, they have multiple applications in
different fields. They provide binding, thickening,
lubricity, water retention, and film formation ben-
efits to deliver excellent performance, such as in
mining, paper, and cleaning products. Due to their
nontoxic and nonirritant properties, they are
broadly used as well in pharmacy, medicine, and
cosmetics (Working et al. 1997; Andersen 1999).
They are also thermoplastic materials that are
readily calendared, extruded, injection molded,
and cast, to provide even greater formulation and
processing flexibility. The different forms of PEG
are also available (Lapienis 2009; Fruijtier-Pölloth
2005; Zalipsky 1995) depending on the used initi-
ator during the polymerization process, the most
common is a monofunctional methyl ether PEG
(methoxypoly(ethylene glycol)), abbreviated as
2 Polyethylene Oxide
Polyethylene Oxide,
Fig. 1 Chemical structure
of polyethylene oxide
MPEG. PEGs are also available with different
microstructure. Branched PEGs have three to ten
PEG chains emanating from a main chain; star
PEGs have 10–100 PEG chains emanating from
a central core group, and Comb PEGs have multi-
ple PEG chains normally grafted to a polymer
backbone.
References
Andersen FA (1999) Special report: reproductive and
developmental toxicity of ethylene glycol and its
ethers. Int J Toxicol 18:53
Bailey FE, Koleske JV (1976) Poly(Ehtylene Oxide).
Academic, New York
Buchmeister MR (ed) (2003) Polymeric materials in
organic synthesis and catalysis. Wiley-VCH Verlag
GmbH &Co. KGaA, Weinheim, p 245
DOW Ethylene glycols: physical properties. http://www.
dow.com/ethyleneglycol/about/properties.htm
Fruijtier-Pölloth C (2005) Safety assessment on polyeth-
ylene glycols (PEGs) and their derivatives as used in
cosmetic products. Toxicology 214:1–38
Hattori H (1995) Heterogeneous basic catalysis. Chem
Rev 95:537–550
Lapienis G (2009) Star-shaped polymers having PEO
arms. Prog Poly Sci 34:852–892
Working PK et al (1997) Safety of poly(ethylene glycol)
and poly(ethylene glycol) derivatives. In: Harris JM,
Zalipsky S (eds) Polyethylene glycol chemistry and
biological applications. American Chemical Society,
Washington, DC, p 45
Zalipsky S (1995) Chemistry of polyethylene glycol con-
jugates with biologically active molecules. Adv Drug
Deliv Rev 16:157–182
Zhao X, Metz WA, Sieber F, Janda KD (1998) Expanding
on the purification methodology of polyethylene gly-
col (PEG) bound molecules: the synthesis of
3,5-pyrazolidinediones. Tetrahedron Lett 39:8433
E
Emulsifier
Emma Piacentini
Institute on Membrane Technology (ITM-CNR),
University of Calabria, Rende CS, Italy
Emulsifiers are a class of molecules with surface
active properties (Dickinson 2009). This behav-
ior is due to their amphiphilic structure which
contains both a polar or hydrophilic head and a
nonpolar or hydrophobic tail (Fig. 1). A measure
of the degree to which an emulsifier is hydro-
philic or lipophilic is given by the hydrophilic-
lipophilic balance (HLB) determined by calculat-
ing values for the different regions of the mole-
cule. Emulsifiers adsorb at interfaces between
two immiscible liquid anchoring its hydrophilic
part into water and its lipophilic part into oil
decreasing the interfacial tension between them
(Fig. 1). This facilitates droplets disruption dur-
ing homogenization and, in the case of mem-
branes, lowering the minimum emulsification
pressure. Emulsifiers have an important role in
emulsion stabilization against droplets coales-
cence and/or aggregation providing electrostatic
repulsion, steric repulsion, and/or strength to the
interfacial layer of the droplets.
Emulsifiers are normally classified according
to the head group type as ionic (anionic and
cationic), nonionic, and amphoterics
(zwitterionics). Anionic emulsifiers contain
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_485-1
anionic functional groups at their head, such as
sulfate (sodium dodecyl sulfate, SDS), sulfonate,
phosphate, and carboxylates. Cationic emulsi-
fiers contain cationic functional groups at their
head, such as pH-dependent primary, secondary,
or tertiary amines and permanently charged qua-
ternary ammonium cation (cetyl trimethy-
lammonium bromide, CTAB). Nonionic
emulsifiers have polar headgroups and they
include glycol and glycerol esters,
polyoxyethylene esters, polyoxyethylene ethers,
polyoxyethylene–polyoxypropylene copolymers,
sorbitan derivatives, and sucrose esters. Zwitter-
ionic (amphoteric) emulsifiers have both cationic
and anionic centers attached to the same mole-
cule. The cationic part is based on primary, sec-
ondary, or tertiary amines or quaternary
ammonium cations. The anionic part can be
more variable and include sulfonates, sultaines,
betaines, and phosphates (lecithin).
A variety of emulsifiers are natural products
derived from plant or animal tissue such as hydro-
colloids (high molecular weight polysaccharides)
and proteins.
References
Dickinson E (2009) Hydrocolloids as emulsifiers and
emulsion stabilizers. Food Hydrocolloids 23:
1473–1482
2 Emulsifier

Emulsifier,
Fig. 1 Emulsifier structure EMULSIFIER
and emulsifier distribution
at water-in-oil and oil-in- Hydrophilic Head
water emulsion interface
Hydrophobic Tail

Water-in-oil emulsion Oil-in-water emulsion

P
Polymer with Intrinsic Microporosity membrane-forming PIM is referred to as PIM-1
(PIM) (Fig. 1).
Peter M. Budd
Organic Materials Innovation Centre, School of
Chemistry, University of Manchester,
Manchester, UK
A polymer of intrinsic microporosity (PIM) is an
amorphous, glassy polymer that contains
interconnected pores of width less than 2 nm,
which arise directly from the shape and rigidity
of the component macromolecules (McKeown
and Budd 2010). This type of polymer behaves
like a microporous material or molecular sieve in
a low-temperature nitrogen adsorption experi-
ment, exhibiting high uptake at very low relative
pressure. It must be emphasized that in this con-
text, the term “microporous” refers to pores with
dimensions on the molecular scale. The term
“intrinsic microporosity” was originally applied
to polyphenylene oxide polymers that showed
evidence of an interconnected system of
microcavities (Illinitch et al. 1999). It was subse-
quently used for polymers with backbones com-
posed of rigid sequences linked by sites of
contortion that force the backbone to twist and
turn (Budd et al. 2005). These polymers possess
high free volume in the solid state, because the
component macromolecules cannot fill space
efficiently. The prime example of a soluble,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_488-3
In PIM-1, there are no single bonds in the
backbone about which rotation can occur, and
so it cannot undergo large-scale conformational
change in the way a conventional polymer can.
The spiro-center (two five-membered rings with a
carbon atom in common) acts as a site of contor-
tion, putting a bend in the chain and making it
difficult for chains to align and pack together. The
intrinsic microporosity, coupled with the organic
nature of its backbone, gives PIM-1 a high affin-
ity for small organic molecules, which are readily
adsorbed from the vapor phase or from aqueous
solution. PIM-1 is soluble in solvents such as
chloroform and tetrahydrofuran and can be
processed from solution to form yellow, fluores-
cent, thermally stable membranes or coatings.
PIM-1 membranes have been investigated for a
variety of liquid, gas, and vapor separations. In
pervaporation, PIM-1 exhibits organophilic char-
acter, being selective for organic species rather
than water (Budd et al. 2004). In organic solvent
nanofiltration, it separates smaller species from
larger species (Fritsch et al. 2012). In gas separa-
tion, it helps to define the 2008 upper bound of
performance for gas pairs such as CO2/CH4, CO2/
N2, and O2/N2 (Robeson 2008). A variety of
chemical modifications have been carried out on
PIM-1 in order to tailor the transport properties.
A wide range of PIMs have been prepared,
including both soluble, membrane-forming poly-
mers and insoluble network polymers (McKeown
2 Polymer with Intrinsic Microporosity (PIM)
Polymer with Intrinsic
Microporosity (PIM),
Fig. 1 Molecular structure
of PIM-1 and molecular
model of a fragment of
PIM-1 showing its
contorted shape
and Budd 2010). In addition to spiro-centers,
units that have been used as sites of contortion
include ethanoanthracene and triptycene. PIMs
are often synthesized by a step-growth polymer-
ization involving a double nucleophilic aromatic
substitution reaction between a monomer bearing
pairs of hydroxyls and a monomer bearing pairs
of fluorines. A recent development is the use of
Tröger’s base formation as a novel polymeriza-
tion method (Carta et al. 2013).
Any polymer that possesses sufficient
interconnected free volume as to allow the
ready uptake and transport of gasses and vapors
may be regarded as having “intrinsic microporos-
ity.” This includes highly permeable, glassy poly-
mers such as poly(1-trimethylsilyl-1-propyne)
(PTMSP), in which it is the bulky trimethylsilyl
side group which restricts flexibility of the back-
bone and forces it into a twisted shape.
References
Budd PM, Elabas ES, Ghanem BS, Makhseed S,
McKeown NB, Msayib KJ, Tattershall CE, Wang
D (2004) Solution-processed, organophilic membrane
from a polymer of intrinsic microporosity. Adv Mater
16:456–459
Budd PM, McKeown NB, Fritsch D (2005) Free volume
and intrinsic microporosity in polymers. J Mater Chem
15:1977–1986
Carta M, Malpass-Evans R, Croad M, Rogan Y, Jansen
JC, Bernardo P, Bazzarelli F, McKeown NB (2013) An
efficient polymer molecular sieve for membrane gas
separations. Science 339:303–307
Fritsch D, Merten P, Heinrich K, Lazar M, Priske
M (2012) High performance organic solvent
nanofiltration membranes. J Membr Sci
401–402:222–231
Illinitch OM, Fenelonov VB, Lapkin AA, Okkel LG,
Terskikh VV, Zamaraev KI (1999) Intrinsic micropo-
rosity and gas transport in polyphenylene oxide poly-
mers. Microporous Mesoporous Mater 31:97–110
McKeown NB, Budd PM (2010) Exploitation of intrinsic
microporosity in polymer-based materials. Macromol-
ecules 43:5163–5176
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320:390–400
P
Polymeric Magnetic Membranes
Anna Strzelewicz
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
Synonym
Magnetically responsive membranes
The polymeric magnetic membranes are poly-
meric membranes with dispersed granules of a
permanent magnet (ferrite, praseodymium, and
neodymium) or with magnetic nanoparticles
(ferroferric oxides), which are intended for sepa-
ration purposes (Rybak et al. 2012). As a polymer
matrix the ethyl cellulose (EC) or poly
(2,6-dimethyl-1,4-phenylene oxide) (PPO) can
be used.
Polymeric membranes filled with neodymium
powder have been successfully used for enrich-
ment of air by oxygen. Membranes of various
polymer matrices (EC and PPO) with different
types of dispersed magnetic powder (ferrite, pra-
seodymium, and neodymium) and granulation
(20–32 mm, 32–50 mm) can be prepared by solu-
tion casting and evaporation. Magnetic mem-
branes are made by casting of 3 % EC solution
in 40:60 ethanol/toluene or 2.5 % PPO solution in
TCE (trichloroethylene) with dispersed magnetic
powders of appropriate amount: 0.5–2 g in exter-
nal field (stable magnetic field with range of
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_490-4
induction 0  40 mT) (Strzelewicz et al. 2007;
Rybak et al. 2009a; Grzywna et al. 2010). In the
next step membranes are removed from Petri dish
and dried in 40  C for at least 2 days before any
further analysis. The membranes were stored in
an exsiccator under the vacuum conditions
(p = 3 mmHg).
The transport of the molecules through the
magnetic membranes can be modeled by a diffu-
sion with a position-dependent diffusion coeffi-
cient. Such a diffusion coefficient reflects the
changes in the membrane composition along the
permeation axis (Rybak et al. 2009b; Borys
et al. 2011). Magnetic membranes are inhomoge-
neous, i.e., on the bottom (permeation side), there
are the magnetic aggregates of the magnetic pow-
der, while on the top (feed side), there is a layer of
pure polymer.
Another group of magnetic membranes are
polymer membranes containing magnetic
nanoparticles, i.e., ferroferric oxide particles.
The membranes can be prepared as described in
Dudek et al. (2012), where ethyl cellulose and
poly(2,6-dimethyl-1,4-phenylene oxide) were
used as polymer matrix. The membranes were
prepared by solution casting and evaporation.
For proper dispersion and homogenization of
magnetic particles in the polymer solution, the
mixture was sonificated using high-intensity
ultrasound radiation. The average thickness of
the obtained membranes was 25 mm. The mem-
branes were examined for nitrogen and oxygen
permeability. Detailed description of preparation
2 Polymeric Magnetic Membranes
and characterization of iron oxides–polymer
composite membranes is given in Dudek
et al. (2012).
References
Borys P, Pawelek K, Grzywna ZJ (2011) On the magnetic
channels in polymer membranes. Phys Chem Chem
Phys 13:17122–17129
Dudek G, Turczyn R, Strzelewicz A, Rybak A,
Krasowska M, Grzywna ZJ (2012) Preparation and
characterization of iron oxides-polymer composite
membranes. Sep Sci Technol 47:1390–1394
Grzywna Z, Rybak A, Strzelewicz A (2010) Air enrich-
ment by polymeric magnetic membrane, chapter in
book. In: Yampolskii Y, Freeman B (eds) Membrane
gas separation. Wiley, Chichester, pp 159–182
Rybak A, Grzywna ZJ, Kaszuwara W (2009a) On the air
enrichment by polymer magnetic membranes.
J Membr Sci 336:79–85
Rybak A, Krasowska M, Strzelewicz A, Grzywna ZJ
(2009b) “ Smoluchowski type” equations for model-
ling of air separation by membranes with various
structure. Acta Phys Pol B 40:1447–1454
Rybak A, Strzelewicz A, Krasowska M, Dudek G,
Grzywna ZJ (2012) On the air separation process by
magnetic membranes influence of various parameters.
Sep Sci Technol 47:1395–1404
Strzelewicz A, Grzywna ZJ (2007) Studies on the air
membrane separation in the presence of magnetic
field. J Membr Sci 294:60–67
P
Polymeric-Ceramic Catalytic
Membrane
Sophie Cerneaux
UMR 5635 ENSCM, CNRS, UM, Institut
Européen des Membranes, Montpellier, France
Polymer membranes and ceramic membranes are
two types of membranes prepared, respectively,
from organic or inorganic and metallic materials.
Polymer-ceramic membranes represent a differ-
ent class of membranes that combines properties
of both polymer and ceramic membranes. They
are often named as composite or hybrid mem-
branes and tailored regarding the targeted appli-
cation. They may consist mainly of ceramic
materials modified by various kinds of polymers
or polymer membranes including inorganic
nanoparticles, for instance.
Catalytic membranes are developed for reac-
tive separation processes that involve reaction
and separation steps either in gas or liquid
phase. Indeed, they are not only acting as
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_492-1
filtration media but also allow the reaction to
take place acting as heterogeneous catalysts.
Organic-inorganic catalytic membranes are
largely applied to biodiesel production (Shi
et al. 2010) for the conversion of methanol and
other esterification reactions requiring a high
permselectivity. A growing interest is focused
on applications such as photodegradation and
photocatalysis (Romanos et al. 2013) using mem-
brane processes and coupled technologies.
References
Romanos GE, Athanasekou CP, Likodimos V,
Aloupogiannis P, Falaras P (2013) Hybrid ultrafiltra-
tion/photocatalytic membranes for efficient water
treatment. Ind Eng Chem Res. 52(39):13938–13947.
doi:10.1021/ie303475b
Shi W, He B, Ding J, Li J, Yan F, Liang X (2010) Prep-
aration and characterization of the organic-inorganic
hybrid membrane for biodiesel production. Bioresour
Technol 101(5):1501–1505. doi:10.1016/j.
biortech.2009.07.014. Epub 2009 Aug 4
P
Premix Membrane Emulsification
Goran T. Vladisavljević and Richard G. Holdich
Chemical Engineering Department,
Loughborough University, Leicestershire, UK
Premix membrane emulsification (PME) is a
homogenization process based on passing
coarsely emulsified mixture of two immiscible
liquids (pre-emulsion) through a microporous
membrane (Suzuki et al. 1996) or porous bed of
particles (Yasuda et al. 2010). In conventional
PME (Fig. 1a), the dispersed phase does not wet
the membrane surface (y>90 ), and thus, hydro-
philic and hydrophobic membranes are needed to
manufacture oil-in-water (O/W) and water-in-oil
(W/O) emulsion, respectively. If the pressure dif-
ference is lower than the capillary pressure in a
pore (Fig. 1c), the droplets are retained by the
membrane, which leads to emulsion separation
rather than homogenization (Koltuniewicz
et al. 1995).
If the membrane surface is wetted by the dis-
persed phase of the original emulsion (y<90 )
and suitable surfactants are present in both liquid
phases, a phase inversion may occur during
homogenization (Fig. 1b), leading to the forma-
tion of W/O emulsion from an O/W premix or
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_500-4
vice versa (Suzuki et al. 1999). The main advan-
tage of PME with phase inversion is that a fine
emulsion with high disperse phase concentration
(over 80 vol.%) can be produced from a
low-concentration premix. Using a membrane
wetted by the middle phase of the multiple emul-
sion, W/O/W and O/W/O emulsion can be
inverted into a W/O or O/W emulsion, respec-
tively. In the case of inversion of W/O/W emul-
sion (Fig. 2), a lamellar structure is formed inside
the pores consisting of surfactant bilayers sepa-
rated by aqueous films. The aqueous films are
ruptured at the pore outlets forming reversed
micelles stabilized by mixed surfactants. This
W/O emulsion can be redispersed into an aqueous
surfactant solution to form a redispersed W/O/W
emulsion containing more uniform internal drop-
lets than the original W/O/W emulsion (Hino
et al. 2000).
In order to achieve additional droplet size
reduction and improve droplet size uniformity,
emulsion can repeatedly be passed through the
same membrane (Vladisavljević et al. 2004).
Repeated membrane homogenization was origi-
nally developed for homogenization of large lipid
vesicles using track-etch polycarbonate filters
(Olson et al. 1979). The advantages of premix
over direct membrane emulsification are in
smaller droplet sizes and higher droplet
2 Premix Membrane Emulsification

Premix Membrane Emulsification, Fig. 1 Pressure-
driven membrane processes with oil-in-water
pre-emulsion: (a) PME without phase inversion
(DP>Pcap, y>90 ) (Suzuki et al. 1996). (b) PME with
phase inversion (DP>Pcap, y<90 ) (Suzuki et al. 1999).
(c) Phase separation (DP<Pcap, y>90 ) (Koltuniewicz
et al. 1995). y is the contact angle at which a dispersed-
phase/continuous-phase interface meets the membrane
surface

Premix Membrane
Emulsification,
Fig. 2 Phase inversion of
W/O/W emulsion into W/O
emulsion using
hydrophobic polycarbonate
membrane. The original
W/O/W emulsion consisted
of liquid paraffin (middle
phase), Span
80 (a hydrophobic
surfactant), and Tween
20 (a hydrophilic
surfactant), and a pore size
was 3 or 8 mm (Hino
et al. 2000)

throughputs that can be achieved for the given
pore size but at the expense of lower degree of
monodispersity.
The droplet size in premix ME is determined
by the membrane pore size, transmembrane flux,
physical properties of the dispersed and continu-
ous phase and emulsion formulation. Small drop-
let size in the product emulsion is favored by
small membrane pore sizes, high transmembrane
fluxes, and low interfacial tensions between the
dispersed and continuous phase (Vladisavljević
et al. 2004, 2006). The membranes used in PME
are shirasu porous glass (SPG) membrane
(Fig. 3), polymeric microporous membranes
(Hino et al. 2000), and microsieves (Nazir
et al. 2011).
Premix Membrane Emulsification
Premix Membrane Emulsification, Fig. 3 PME using SPG membrane. The droplet size in the product emulsion was
9 mm and the membrane pore size was 10.7 mm (Vladisavljević et al. 2004)
References
Hino T, Kawashima Y, Shimabayashi S (2000) Basic
study for stabilization of w/o/w emulsion and its appli-
cation to transcatheter arterial embolization therapy.
Adv Drug Deliv Rev 45:27–45
Koltuniewicz AB, Field RW, Arnot TC (1995) Cross-flow
and dead-end microfiltration of oily-water emulsion.
Part I: experimental study and analysis of flux decline.
J Membr Sci 102:193–207
Nazir A, Schroën CGPH, Boom RM (2011) High-
throughput premix membrane emulsification using
nickel sieves having straight-through pores. J Membr
Sci 383:116–123
Olson F, Hunt CA, Szoka FC (1979) Preparation of lipo-
somes of defined size distribution by extrusion through
polycarbonate membranes. Biochim Biophys Acta
557:9–23
Suzuki K, Shuto I, Hagura Y (1996) Characteristics of the
membrane emulsification method combined with
3
preliminary emulsification for preparing corn oil-in-
water emulsions. Food Sci Technol Int Tokyo 2:43–47
Suzuki K, Fujiki I, Hagura Y (1999) Preparation of high
concentration of O/W and W/O emulsions by the
membrane phase inversion emulsification using
PTFE membranes. Food Sci Technol Int Tokyo
5:234–238
Vladisavljević GT, Shimizu M, Nakashima T (2004) Prep-
aration of monodisperse multiple emulsions at high
production rates by multi-stage premix membrane
emulsification. J Membr Sci 244:97–106
Vladisavljević GT, Shimizu M, Nakashima T (2006) Pro-
duction of multiple emulsions for drug delivery sys-
tems by repeated SPG membrane homogenization:
influence of mean pore size, interfacial tension and
continuous phase viscosity. J Membr Sci 284:373–383
Yasuda M, Goda T, Ogino H, Glomm WR, Takayanagi
H (2010) Preparation of uniform monomer droplets
using packed column and continuous polymerization
in tube reactor. J Colloid Interface Sci 349:392–410
P
Pressure-Retarded Osmosis
Chalida Klaysom and Ivo Vankelecom
Centre for Surface Chemistry and Catalysis, KU
Leuven, Leuven, Heverlee, Belgium
During the past decades, the world’s constantly
growing population and energy demand had
brought the great challenges to thoroughly search
for alternative energy resources. The mixing of
fresh and saline water releases a tremendous
energy that can potentially be used for power
generation (Pattle 1954). In fact, there are huge
resources where freshwater meets saline water
that have not been explored. It has been estimated
that this potential energy resource can generate
200 TWh/year of electric power, creating more
than 10 % for the world energy demand (Achilli
and Childress 2010). The energy released from
the mixing of fresh- and saltwater can be captured
by a membrane process, the so-called pressure-
retarded osmosis (PRO).
PRO utilizes osmotic pressure (p) as the driv-
ing force for water to transport across a semiper-
meable membrane from a water source with
lower salt concentration (low p) to a source with
higher salt concentration (high p). The flow of
water from the dilute source increases the volu-
metric flow at the concentrate side, and this flow
can be used for driving a turbine to generate
electricity (see Fig. 1).
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_501-3
There are three osmotic pressure-related
membrane processes: reverse osmosis (RO), for-
ward osmosis (FO), and PRO. Regarding applied
hydraulic pressure (P), the required pressure to
retain osmotic equilibrium, PRO can be viewed
as the transition process from FO to RO as shown
in Fig. 2.
RO membranes require a mechanical strength
that can withstand the high pressure applied,
while FO and PRO operate at much lower pres-
sures, thus no special strength is strictly required.
Typical RO membrane is thus designed to have a
thin selective layer on top of thick support layer.
The membrane performance and solute retention
are determined by the top-skin layer. The support
only provides the mechanical strength to the RO
membranes and the liquid flows through it under
the influence of a pressure gradient. On the other
hand, for FO and PRO, the physical and chemical
nature of support layers (e.g., porosity, tortuosity,
and hydrophilicity) play an equally important
role as the skin layer. The presence of unwetted
pores or gas trapped inside the pores of the sup-
port in FO or PRO can cause internal concentra-
tion polarization (ICP) and dramatic flux
reductions. Moreover, membranes suitable for
FO and PRO are required to possess high salt
rejection to prevent reverse salt passages and
ICP and to be thin, highly porous, and hydrophilic
in nature to favor high water fluxes and good
transport of leakage salts. Additional mechanical
strength (just enough to resist the installed oper-
ating pressure) is required for PRO.
2 Pressure-Retarded Osmosis

WATERWHEEL

PRESSURE
HEAD

PRESSURE CHAMBER
P GENERATOR

FRESH SEA
WATER WATER
MEMBRANE

PUMP

FLUSHING FLOW

b
Brackish water
PRESSURE
EXCHANGER
Power
WATER
FILTER

MEMBRANE MODULES
Sea water TURBINE

Brackish water

Fresh water
WATER
FILTER

bleed
Fresh water

Pressure-Retarded Osmosis, Fig. 1 Schematicdiagram the first prototype PRO, designed and operated by
of (a) the first osmotic salination energy converter, Statkraft (Oslo, Norway) (Skilhagen et al. 2008)
proposed by Norman in 1974 (Norman 1974), and (b)

The ideal water permeation rate across the J w ¼ AðDp  DPÞ

membrane is a linear function of both osmotic
pressure difference and the applied hydraulic where Jw is water flux and A is the water perme-
pressure: ability constant. The power generated by a PRO
system is expressed by
Pressure-Retarded Osmosis 3

a Operating pressure in
JW osmotic processes b RO c PRO d FO
Hydraulic Pressure Hydraulic Pressure
(ΔP> Δπ) (ΔP< Δπ) No Hydraulic
Pressure applied
Wmax RO

0
ΔP= Δπ/2 ΔP= Δπ ΔP Salt flux Salt flux Salt flux

PRO
Water flux(JW) Water flux(JW) Water flux(JW)

FO

Pressure-Retarded Osmosis, Fig. 2 (a) Illustration of the magnitude of the operating pressure and water flux of a
membrane in the ideal case and direction of water and salt flux for (b) RO, (c) PRO, and (d) FO process

W ¼ J w DP ¼ AðDp  DPÞDP References

I. t is clear that the power generated by PRO is a
parabolic function of in which the maximum
value is estimated to be at DP ¼ Dp=2 . Thus,
the maximum power generated from PRO
ðW max ¼ ADp2 =4Þ is proportional to the water
permeability constant and the square of the
osmotic pressure difference.
Achilli A, Childress AE (2010) Pressure retarded osmosis:
from the vision of Sidney Loeb to the first prototype
installation – review. Desalination 261:205–211
Norman RS (1974) Water salination: a source of energy.
Science 186:350–352
Pattle RE (1954) Production of electric power by mixing
fresh and salt water in the hydroelectric pile. Nature
174(4431):660
Skilhagen SE, Dugstad JE, Aaberg RJ (2008) Osmotic
power – power production based on the osmotic pres-
sure difference between waters with varying salt
gradients. Desalination 220(1–3):476–482
P
Propolis Extract Nanofiltration
Beatriz Mello
UFSCar, Federal University of Sao Carlos, Buri,
SP, Brazil
Propolis is a mixture of beeswax and resins col-
lected by the honeybee from plants, particularly
from flowers and leaf buds. Its composition
depends on the type of plants accessible to the
bees. There are changes in color, odor, and prob-
ably medicinal characteristics according to
source and the season of the year. The major
compounds are resins composed of flavonoids
and phenolic acids or their esters, which often
form up to 50 % of all ingredients. The variation
in beeswax content also influences the chemical
analysis. More than 500 different compounds
from propolis through several regions were iso-
lated, being impossible to determine their com-
position without first analysis.
Propolis composition is responsible for a lot of
studies relating antimicrobial, antioxidant,
anticarcinogenic and antifungal activities,
among other health benefits. Thanks to these
characteristics, a great interest exists to use prop-
olis for human consumption as being incorpo-
rated in drugs, cosmetics, and foods.
The most usual way to manipulate propolis is
by its extract. Ethanol is the most common sol-
vent used once it can extract the major
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_503-2
constituents from propolis at low cost. Other sol-
vents as water and propylene glycol are also
studied.
The excess of solvents in extracts can be
responsible for some limitation in industrial pro-
cess, causing some variation in the final product,
so it is necessary to concentrate it before use. The
most traditional methods are lyophilization
(freeze-drying), vacuum distillation, evaporation,
and distillation. These methods require a high
energy consumption and in some cases high tem-
peratures that can degrade some functional com-
pounds. To avoid these drawbacks, the method of
nanofiltration has been studied for propolis
concentration.
Nanofiltration membranes are the same as
reverse osmosis membranes; only the network
structure is more open, causing a lower retention
of monovalent salts (Mulder 1996). It has been
widely used in concentration process where the
objective is to retain functional compounds with
low molecular weight, especially phenolic
compounds.
Propolis nanofiltration has been studied for
some authors recently, and the process showed a
high efficiency in retaining flavonoids and phe-
nolic compounds, which are of major importance
to propolis quality, reaching more than 95 %
rejection in concentration factor of 3.0 and 4.0.
Moreover, the process had low fouling and con-
centration polarization, phenomena that can
make the whole process inviable through flux
decay (Tylkowski et al. 2010; Mello et al. 2010).
2 Propolis Extract Nanofiltration

Propolis Extract Nanofiltration, Fig. 1 Differences between conventional (a) and tangencial filtration (b)

Propolis Extract Nanofiltration, Fig. 2 Schematic diagram of propolis extracts nanofiltration process

Application of this technology could increase
the use of propolis in many industrial applica-
tions, in new research projects, and in the devel-
opment of new products with functional
properties. Furthermore, this process allows
removal of the solvent from the extract, reducing
the disadvantages associated with using alcoholic
extractions, and being feasible the use of another
solvent during extraction procedure. In the mem-
brane process, the product is not submitted to
high temperatures, and there is no change in the
physical state of the solvent, which means that the
functional properties of the compounds of inter-
est are preserved and the process as a whole is
energy saving.
Cross-flow nanofiltration experiments showed
that the nanofiltration process can be feasible
technology for medicine and nutritional additive
production based on propolis extracts (Fig. 1).
References
Mello BCBS, Petrus JCC, Hubinger MD (2010) Concen-
tration of flavonoids and phenolic compounds in aque-
ous and ethanolic propolis extracts through
nanofiltration. J Food Eng 96:533–539
Mulder M (1996) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht, Cap. VI
Tylkowski B, Trusheva B, Bankova V, Giamberini M,
Peev G, Nikolova A (2010) Extraction of biologically
active compounds from propolis and concentration of
extract by nanofiltration. J Membr Sci 348:124–130
P
Protein Separation by UF
Andrew L. Zydney
Department of Chemical Engineering,
The Pennsylvania State University, University
Park, PA, USA
Membrane processes have been used for
bioseparations since well before the start of the
modern membrane industry. For example, John
D. Ferry’s review article on ultrafiltration in 1936
(Ferry 1936) described the use of membrane tech-
nology for enzyme concentration, analysis of
bacteriophages and viruses, preparation of cell-
and protein-free ultrafiltrates from biological
solutions, and sterile filtration, although these
systems were limited to analytical-scale pro-
cesses due to limitations on the available
membranes and modules.
There has been considerable interest in using
ultrafiltration membranes for actual protein-
protein separations, taking advantage of the
relatively low cost, high throughput, and easy
scalability of membrane systems. Most early
efforts at protein separations using ultrafiltration
were unsuccessful (Nakatsuka and Michaels
1992), although there were some notable suc-
cesses in small-scale separations of model protein
systems. Considerable progress in this area has
been made over the past 15 years, with specific
applications in both the biotechnology industry
for the purification of therapeutic proteins and in
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_508-2
the fractionation of natural protein sources like
whey, egg white, and blood plasma. The key to all
of these processes is the development of ultrafil-
tration membranes/systems with high selectivity
between the product of interest and the impuri-
ties, where the selectivity is defined as the ratio of
the sieving coefficient for the more permeable
species to that of the more highly retained
species. Selectivities of 100 or greater have
been obtained for model systems involving
immunoglobulins and albumin, hemoglobin
from albumin, lysozyme and albumin, and many
others (van Reis and Zydney 2007; Zydney and
van Reis 2011).
In most cases, protein separation was accom-
plished by operating the membrane device at
relatively low transmembrane pressures, below
the “transition point” as defined by van Reis
et al. (1997). High selectivities are obtained by
proper choice of both membrane and buffer con-
ditions, with the latter chosen to maximize the
difference in electrostatic interactions for the two
proteins. For example, positively charged
ultrafiltration membranes have been successfully
employed for the purification of monoclonal
antibodies from mammalian host cell proteins,
with the positively charged antibody retained by
the charged membrane, while the smaller (and
weakly charged) impurities are washed into the
filtrate. High yields and purification factors
are obtained using a diafiltration mode to increase
the removal of impurities.
2 Protein Separation by UF
Protein ultrafiltration has been successfully
demonstrated for the purification of antigen-
binding fragments (Fab) and monoclonal anti-
bodies from host cell proteins (van Reis and
Zydney 2007). Data for monoclonal antibody
purification from a harvested cell culture fluid
show identical performance, as determined by
nonreduced SDS-PAGE and ELISA, for a
non-affinity monoclonal antibody purification
process using ultrafiltration, in combination
with cation and anion exchange chromatography,
compared to that of a process using protein
A affinity chromatography for the bulk of the
purification (Zydney and van Reis 2011).
References
Ferry JD (1936) Ultrafilter membranes and ultrafiltration.
Chem Rev 18:373
Nakatsuka S, Michaels AS (1992) Transport and separa-
tion of proteins by ultrafiltration through sorptive and
non-sorptive membranes. J Membr Sci 69:189–211
van Reis R, Zydney AL (2007) Bioprocess membrane
technology. J Membr Sci 297:16–50
van Reis R, van Reis R, Frautschy LN, Orlando S, Good-
rich EM, Saksena S, Kuriyel R, Simpson CM, Pearl S,
Zydney AL (1997) High performance tangential flow
filtration. Biotechnol Bioeng 56:71
Zydney AL, van Reis R (2011) Bioseparations: membrane
processes. In: Moo-Young M (ed) Comprehensive
biotechnology, 2nd edn. Academic, Burlington,
pp 499–520
P
Purification of Plasma from
Cholesterol by Immunoaffinity
Membranes
Nilay Bereli, Handan Yavuz and Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Coronary heart diseases are responsible for the
4.3 million deaths in all of Europe and also can
cause lifetime disability. The annual economic
cost is estimated to be 192 billion with a substan-
tial increase (Harland 2012). Together with the
high blood pressure, LDL cholesterol is widely
recognized as one of the major risk factors in the
development of coronary heart diseases because
of its ability to build up in the lining of arteries to
form atheromas and fatty acid deposits (Bruckert
1999; Thompson 2003). In the case where dietary
and drug therapy is insufficient to set safe blood
cholesterol level, extracorporeal cholesterol
removal techniques with different selectivity
and specificity have been used. Plasmapheresis,
cascade filtration, heparin induced LDL precipi-
tation (HELP), thermofiltration, dextran induced
LDL precipitation, and direct adsorption of lipo-
proteins are the examples (Blaha 2003). The most
selective removal of LDL has been achieved by
the use of monoclonal antibodies against the
apoB100, the main protein component of LDL,
as a ligand (Kane et al. 1975). This allows
removal of harmful LDL without decreasing
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_513-1
useful HDL and other plasma proteins. Conven-
tional gel-bead columns have certain limitations
especially when studying with viscous media
such as human blood. Alternative carriers such
as membranes, monoliths, and cryogels are
designed to solve drawbacks of gel-beads such
as high-pressure drop and flow rate limitations
that limit efficiency of applications (Bereli
et al. 2011). In random immobilization of anti-
bodies, they can bind to the polymer surface at
many different points (Denizli 2002; Yavuz and
Denizli 2003, 2005). This generally results in
decrease in the antigen-binding capacity because
the accessibility of the antigen-binding sites is
prevented in most cases. Anti-LDL immobiliza-
tion onto the polymeric carriers can be performed
in an oriented mode to leave its antigen-binding
fragments free. It can be done by either using Fc
receptor proteins such as Protein A and Protein G,
by using carbohydrate binding polymer in order
to bind through the carbohydrate moiety, or by
using artificial or digestion product Fab frag-
ments. Immunoaffinity adsorbent obtained by
oriented immobilization of anti-LDL onto the
biocompatible PHEMA cryogel membranes
show better LDL adsorption capacity (129 mg
LDL/g) from hypercholesterolemic human
plasma than random anti-LDL immobilized
adsorbent (111 mg LDL/g) while the amount of
anti-LDL bound in an oriented mode was the one
third of the random immobilized. Nonspecific
adsorption of other lipoproteins was very low in
both cases. It has been also shown that these
2 Purification of Plasma from Cholesterol by Immunoaffinity Membranes
adsorbents can be used many times without sig-
nificant decrease in the adsorption capacity
(Bereli et al. 2011).
References
Bereli N, Şener G, Yavuz H, Denizli A (2011) Oriented
immobilized anti-LDL antibody carrying poly
(hydroxyethyl methacrylate) cryogel for cholesterol
removal from human plasma. Mater Sci Eng
C 31:1078–1083
Blaha M (2003) Extracorporeal LDL-cholesterol elimina-
tion in the treatment of severe familial hypercholester-
olemia. Acta Med 46:3
Bruckert E (1999) LDL apheresis: questions for the future.
Transfus Sci 20:43
Denizli A (2002) Preparation of immunoaffinity mem-
branes for cholesterol removal from human plasma.
J Chromatogr B 772:357
Harland JI (2012) Food combinations for cholesterol low-
ering. Nutr Res Rev 25:249–266
Kane JP, Sata T, Hamilton RL, Havel RJ
(1975) Apoprotein composition of very low density
lipoproteins of human serum. J Clin Invest
56:1622–1634
Thompson GR (2003) LDL apheresis. Atherosclerosis
167:1
Yavuz H, Denizli A (2003) Immunoaffinity beads for
selective removal of cholesterol from human plasma.
J Biomater Sci Polym Ed 14:395
Yavuz H, Denizli A (2005) Immunoadsorption of choles-
terol on protein A oriented beads. Macromol Biosci
5:39–48
P
PVA-Based Anion-Exchange
Membranes
Mitsuru Higa
Graduate School of Science and Engineering,
Yamaguchi University, Ube, Yamaguchi, Japan
PVA-based anion-exchange membrane consists
of poly(vinyl alcohol)(PVA) matrix and anion-
exchange groups (positively charged groups);
hence, anions selectively permeate through the
membrane. PVA is one of the most popular poly-
mers that has been used as a membrane matrix,
because a film made from PVA shows good phys-
ical properties, high hydrophilicity, process abil-
ity, biocompatibility, and good chemical
resistance. PVA is a water-soluble polymer and
does not have any anion-exchange groups. Hence,
a PVA-based homogenious anion-exchange mem-
brane (AEM) can be prepared easily by casting an
aqueous solution of mixed PVA and polycations
and then cross-linked PVA polymer chains. PVA
is a semicrystalline polymer; thus, heat-treatment
above the glass-transition temperature increases
the crystallinity of the polymer, which acts as a
physical cross-linking. PVA chains can also be
chemically cross-linked using cross-linking agents
such as glutaraldehyde(GA) as shown in Fig. 1.
Hence, the degree of swelling of a PVA-based
AEM, which plays an important role in its
permselectivity for anions and membrane resis-
tance, can be easily controlled by varying the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_514-1
annealing and/or chemical cross-linking condi-
tions. The AEM thus obtained has a semi-
interpenetrating network (semi-IPN) structure in
which polycation chains are immobilized in the
polymer cross-linked network matrix. The
ion-exchange capacity of such membranes can
be easily controlled by changing the polymer
ratio of PVA to polycations. AEMs with a semi-
IPN structure have been prepared by blending
PVA and a polycation such as poly(acrylamide-
co-diallyldimethylammoniumchloride), poly(allyl
amine), etc. However, those electrodialytic trans-
port properties are not enough to compete with
commercially available homogeneous AEMs. An
additional disadvantage of AEMs with semi-IPN
structure is low long-term stability when
immersed in solution due to the dissolution of
uncross-linked water-soluble polyelectrolytes in
the network into the solution. To avoid the prob-
lem of dissolution of uncross-linked water-soluble
polycations, AEMs with IPN structure were pre-
pared by blending PVA and a PVA-based
copolymer-type polycation, such as poly(vinyl
alcohol-co-methacryloyl aminopropyl trimethyl
ammonium chloride) (Fig. 2). ED processes with
PVA-based AEMs have potential applications to
many industrial fields such as water treatment, food
industry, medical supplies, acid recovery from
pickling solution, wastewater treatment, etc. The
AEMs will also be potentially applicable to poly-
mer electrolytes for alkaline direct methanol fuel
cells because the AEMs have low methanol
crossover.
2 PVA-Based Anion-Exchange Membranes

PVA-Based Anion-
Exchange Membranes,
Fig. 1 Scheme of OH O O
chemical cross-linking of
OH OH OH CHO CH
poly(vinyl alcohol) (PVA) H+
using glutaraldehyde (GA) + CH2 CH2
(Higa et al. 2012) 3 −2H2O 3
OH OH OH CHO CH

OH O O

PVA chains GA
Cross-linked PVA

PVA crystal region

(physical cross-linking point)

Chemical cross-linking
point with GA

PVA-Based Anion-Exchange Membranes, Fig. 2 Schematic diagram of membrane structure of an AEM with IPN
structure

References prepared from poly(vinyl alcohol) and poly(vinyl

alcohol-b-styrene sulfonic acid). Int J Hydrog Energy
Higa M, Nishimura M, Kinoshita K, Jikihara A (2012) 37:6161–6168
Characterization of cation-exchange membranes
R
Radiation-Induced Grafting
Tauqir A. Sherazi
Department of Chemisty, COMSATS Institute of
Information Technology, Abbottabad, Pakistan
Grafting initiated by radiation technique is
known as radiation-induced grafting or
radiation-induced graft polymerization (see arti-
cle graft polymerization). Radiation acts as an
initiator in the grafting process which generates
controlled concentrations of active sites,
depending upon the irradiation type, rate, and
dose, which are distributed almost evenly
throughout the entire volume of the sample and
initiate polymerization. Owing to high energy,
radiation makes it possible to carry out the pro-
cess in the solid or viscous state at substantially
lower temperatures than in the case of traditional,
chemical initiators.
Types of Radiation
A variety of high-energy radiations can be used
for the grafting process (Heger 1990). This may
include electromagnetic radiation, such as x-rays
and gamma rays, or charged particles, such as
beta particles and electrons. The commonly
used gamma radiation source is CO60 which has
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_515-1
a long half-life of 5.3 years and emits radiation of
1.17 and 1.33 MeV (mean value of 1.25 MeV).
Methods of Radiation Grafting
Radiation-induced grafting could be proceeded
by simultaneous irradiation or pre-irradiation
technique.
In the case of the simultaneous irradiation
method, the polymer is irradiated in the presence
of a monomer under inert atmosphere. Since all
the components of the system exposed equally to
the radiation, it radiolyzed nonselectively. This
process has impact on the kinetics of polymeri-
zation, and as a result, the extent of homopoly-
merization is always high in simultaneous
radiation grafting. The pre-irradiation method,
on the other hand, involves the activation of the
base polymer prior to the grafting reaction. As a
result, considerable structural changes take place
during the irradiation of the polymer itself, which
have their impact on the physical properties of the
resultant membrane. During pre-irradiation, the
radicals generated on the polymer chains and the
radical at one chain may either combine with
another radical from the adjacent chain leading
to the cross-linking or undergo chain scission,
thereby producing terminal unsaturation. The
scission and cross-linking process also depends
upon the nature of polymer to be irradiated
(Sherazi et al. 2008; Gupta et al. 2004).
2 Radiation-Induced Grafting
Radiation-Induced Grafting Mechanism
The irradiation of polymers may cause homolytic
fission and thus generates free radicals on the
polymer. Since radiation is generating the radi-
cals for subsequent grafting, thus the presence of
any other initiator is not essential. The medium of
irradiation is important which affects the grafting
mechanism. If the irradiation is performed in an
inert atmosphere, then radicals are formed, but if
air or oxygen is present, then peroxides may be
formed on the polymer. The lifetime of the free
radical depends upon the nature of the backbone
polymer.
The mechanism for pre-irradiation grafting
and simultaneous grafting are as below:
Pre-irradiation Grafting (In an Inert
Atmosphere)
As already described in the pre-irradiation tech-
nique, the polymer backbone is first irradiated in
vacuum or in the presence of an inert gas to form
free radicals. The irradiated polymer substrate is
then treated with the monomer, in liquid or vapor
state or as a solution in a suitable solvent.
radiation
P ƒƒƒƒ! P •
P • þ M ! PM •
Pre-irradiation Grafting (In the Presence
of Air/Oxygen)
If irradiation performed in the presence of air or
oxygen, hydroperoxides or diperoxides will be
formed, depending on the nature of the polymeric
backbone and the irradiation conditions. When
the grafting has to be performed, these stable
peroxy products are treated with the monomer
at higher temperature. The peroxides undergo
decomposition to radicals, which then initiate
grafting.
radiation
P ! POOH or POOP
O2
POOH or POOP ! PO • þ OH • or 2PO •
PO • þ OH • or 2PO • þ M ! POM
Peroxy products have the advantage that these
can be stored for long periods before performing
the grafting step.
Simultaneous Irradiation Grafting
In the case of simultaneous irradiation technique,
the polymer and the monomers are irradiated
simultaneously, to form free radicals and subse-
quent addition.
Since the monomers are also exposed to radi-
ation in this technique, thus homopolymer forma-
tion also takes place. The simple representation
of the process is as below.
radiation
P þ M ƒƒƒƒ!P • þ M •
P• þ M• ! P  M•
References
Gupta B, Anjum N, Jain R, Revagade N, Singh H (2004)
Development of membranes by radiation induced graft
polymerization of monomers onto polyethylene films.
J Macromol Sci Polym Rev 44(3):275–309
Heger A (1990) Technologie der Strahlenchemie von
Polymeren. Carl Hanser Verlag, Mu¨nchen
Sherazi TA, Ahmad S, Kashmiri MA, Guiver MD
(2008) Radiation induced grafting of styrene onto
ultra-high molecular weight polyethylene powder and
subsequent film fabrication for application as polymer
electrolyte membranes. I: influence of grafting condi-
tions. J Membr Sci 325:964–972
R
Retentate
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
The retentate is the whole mass leaving the mem-
brane on the same side as the feed. It is collected
in a volume or as a stream, leaving the membrane
module in a batch or continuous operations,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_518-1
respectively. Together with the permeate, the
retentate is one of the two outlets of a membrane
unit. The other two streams are the feed and,
optionally, the sweep.
Since no species can quantitatively/totally
pass through the membrane except in the case of
infinitive permeation driving force, generally, it
contains all the species feed to the membrane
module.
R
Reverse Electrodialysis
Piotr Dydo and Marian Turek
Silesian University of Technology, Gliwice,
Poland
Synonyms
Electrodialysis reversal
Electrodialysis reversal (EDR) is a modification
of the simple ED commercially introduced by
Ionics in 1967 to overcome major electrodialysis
shortcomings such as membrane fouling and
scaling. In the EDR system, the polarity of the
direct current applied to the ED stack electrodes
is reversed at specific time intervals ranging from
a few minutes to several hours (typically two to
four times per hour) (Meller 1984). If the polarity
is reversed, the negatively charged colloids will
now be removed from the anion-exchange mem-
brane back into the bulk and the membrane prop-
erties are restored. Not only colloidal materials
but also freshly precipitated sparingly soluble
salts are effectively removed from the membrane
with this procedure before they can solidify.
In the reverse polarity operating mode, the
hydraulic flow streams are reversed simulta-
neously with the reversed polarity, i.e., the
diluate cell will become the concentrate cell and
vice versa. During the reversal of polarity and
flow streams, there is a brief period when the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_519-4
concentration of the desalted water exceeds the
required product salinity. Therefore, the ED
diluate outlet has a concentration sensor which
controls an additional three-way valve. This
valve diverts diluate with a too high concentra-
tion, the so-called off-spec product, into the ED
concentrate or feed. Then, when the concentra-
tion drops to the specified value, the product flow
is directed back to the product outlet. Thus, the
necessity to clean the ED channels between
changing the polarity causes some loss of overall
efficiency as a certain amount of product is lost to
the waste stream or has to be treated again.
Employing the use of four-way valves instead of
three-way ones enables one to decrease the
amount of off-spec product during the reversal
to some extent (Strathmann 2010).
In the classical EDR, the diluate and concen-
trate chamber dimensions as well as flow, and
velocity of dilute and concentrate are equal.
Thus, the concentrate is recycled to gain a high
diluate recovery ratio. The resulting residence
time is thus very high, which limits the maximum
permissible level of CaSO4 and/or CaCO3 super-
saturation. The mean ion residence time (MIRTc)
in a typical EDR design was estimated at
130 min (Myint et al. 2011). The resulting
Langelier Saturation Index (LSI, determining
the CaCO3 precipitation risk) and CaSO4 relative
saturation level that are commonly used indices
to control the scaling process are limited to
2.16 % and 200 %, respectively. The addition of
mineral acid into the concentrate stream
2 Reverse Electrodialysis
decreases the risk of CaCO3 precipitation, while
the addition of antiscalant, usually SHMP, shifts
the scaling-free EDR operation to the region of
gypsum saturation up to 300 % (Meller 1984).
However, if comprehensive utilization of waste-
water and controlled crystallization of CaSO4

2H2O in the concentrate stream is considered,
then any chemical addition is not allowed. Thus,
a further increase in saturation level may be
achieved only by decreasing the concentrate res-
idence time value (Turek et al. 2007).
In terms of unit costs of desalination, EDR is
comparable to RO for waters with TDS
<3000 mg/L, but it is especially suitable for the
treatment of waters and wastewaters with high
scaling and fouling potential.
Cross-References
▶ Application of Electrodialysis
▶ Electrodialysis
▶ Reverse Electrodialysis in High Supersatura-
tion Mode
References
Meller FH (1984) Electrodialysis (ED) and electrodialysis
reversal (EDR) technology. Ionics Incorporated,
Watertown
Myint MT, Ghassem A, Nirmalakhandan N (2011) Low
energy/cost desalination: low dose and low mean ion
resident time in concentrate stream of electro-dialysis
reversal. Water Sci Technol 63(9):1855–1863
Strathmann H (2010) Electrodialysis, a mature technology
with a multitude of new applications. Desalination
264:268–288
Turek M, Dydo P, Waś J (2007) High efficiency electro-
dialysis reversal of concentrated calcium sulfate and
calcium carbonate solutions. Desalination 205:62–66
R
Reverse Electrodialysis in High
Supersaturation Mode
Piotr Dydo and Marian Turek
Faculty of Chemistry, Silesian University of
Technology, Gliwice, Poland
Synonyms
Electrodialysis reversal in high supersaturation
mode
The supersaturation level with sparingly soluble
salts, mainly calcium carbonate and calcium
sulfate, and resulting product water recovery in
the classical electrodialysis reversal with
recycling of ED concentrate are limited by a
relatively long mean residence time in the con-
centrate loop (Myint et al. 2011). A substantial
increase in scale-free operation at a high super-
saturation level may be gained in a single-pass
mode of operation only. In this case, the mean
residence time (favorably accompanied by low
variance of residence time distribution (RTD))
should be small when compared to nucleation
time of crystallization of the sparingly soluble
salt in question (Turek et al. 2006).
Electrodialysis was carried out in a single-pass
mode with symmetric reversed polarity every
6–10 h. The problem of CaSO4 precipitation
was prevented by continuous removal of gypsum
from the brine in a separate precipitator, in which
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_520-4
gypsum seeds were used to increase the rate of
gypsum nucleation and significantly reduce the
level of CaSO4 supersaturation in the EDR con-
centrate (Korngold et al. 2005). It was found that
antiscalant diminished the seeding effect on gyp-
sum crystallization and increased the onset of
crystallization time. Thus, it was demonstrated
that the ED process combined with continuous
CaSO4 precipitation (in a separate precipitator)
may be successfully carried out under a reverse
polarity operation regime.
In a novel EDR design (Turek et al. 2006),
different diluate and concentrate linear velocity
values are applied instead of recirculation of con-
centrate. Thus, the concentrate’s linear flow veloc-
ity is several times lower than the diluate’s, so a
certain diluate concentration decrement results in
a several times higher increment in the concentrate
salt concentration. At the same time, low resi-
dence time is gained due to a single-pass mode.
The ED process with different diluate and concen-
trate flow velocities may be carried only when
applying a thin, e.g., 0.19 mm, net spacer with
high strand density that protects the membrane
against bulging. The intermembrane distance
also influences the rate of both diluate and con-
centrate salt content changes along the ED mem-
brane. The amount of salt passing a certain
membrane surface in a certain period of time
results from the current density value. When
added to a small volume of the solution, being
inversely proportional to the intermembrane dis-
tance, it would increase its concentration to a large
2 Reverse Electrodialysis in High Supersaturation Mode
extent. The avoidance of concentrate recirculation
and low mean residence time are the essential
advantages of single-pass EDR. It was demon-
strated that EDR in this mode can operate with
no chemical addition at CaSO4 saturation levels of
Ca 500 % and +2.3 LSI (Turek et al. 2009, 2012).
EDR carried out at small intermembrane distance
and low residence time enables one to increase
working time without changing the polarity and
to decrease the ED channel cleaning period
between changing it. Both of these features result
in an increase in product recovery and a reduction
of the unit costs of desalination.
It was demonstrated that EDR in a single-pass
mode can operate at a high supersaturation level
which up till now has only been achieved with a
chemical addition to the concentrate stream. The
lack of antiscalants allows for the controlled crys-
tallization of CaSO4
2H2O and CaCO3 in the
concentrate stream. In the case of waters
containing calcium sulfate and calcium bicarbon-
ate as dominant solutes (over NaCl), crystalliza-
tion of the aforementioned species might
decrease the total concentrate salinity to a large
extent. This will allow zero-discharge technology
to develop (Turek et al. 2007, 2009).
Cross-References
▶ Application of Electrodialysis
▶ Electrodialysis
▶ Reverse Electrodialysis
References
Korngold E, Aronov L, Belayev N, Kock K (2005) Elec-
trodialysis with brine solutions oversaturated with cal-
cium sulfate. Desalination 172:63–75
Myint MT, Ghassem A, Nirmalakhandan N (2011) Low
energy/cost desalination: low dose and low mean ion
resident time in concentrate stream of electro-dialysis
reversal. Water Sci Technol 63(9):1855–1863
Turek M, Dydo P, Waś J (2006) Electrodialysis reversal in
high CaSO4 supersaturation mode. Desalination
198:288–294
Turek M, Dydo P, Waś J (2007) High efficiency electro-
dialysis reversal of concentrated calcium sulfate and
calcium carbonate solutions. Desalination 205:62–66
Turek M, Was J, Dydo P (2009) Brackish water desalina-
tion in RO – single pass EDR system. Desalin Water
Treat 7:263–266
Turek M, Waś J, Mitko K (2012) Scaling prediction in
electrodialytic desalination. Desalin Water Treat
44:255–260
R
Richardson Law
Fausto Gallucci
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
The Richardson equation relates the permeation
flux of hydrogen through dense membranes to the
temperature, pressure difference, and membrane
characteristics (Gallucci et al. 2007). In general,
the hydrogen mass transfer mechanism through
(Pd-based) membranes can be described by: (a) a
traditional solution–diffusion mechanism for
dense membranes and (b) a Knudsen diffusion
mechanism or combined mechanism of Knudsen
diffusion and surface diffusion for porous
membranes.
More in detail, the hydrogen permeation
through a dense palladium layer is a complex
process which consists of the following seven-
step activated mechanism:
1. Mass transfer of hydrogen upstream toward
the membrane surface and adsorption of
hydrogen molecules on the membrane surface
2. Dissociation of hydrogen molecules on the
same surface
3. Dissociation of the chemisorbed molecule into
atomic form H* consisting of a proton and an
electron
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_523-1
4. Solution of the dissociated hydrogen atoms H*
into the lattice of the metal
5. Diffusion of the dissociated hydrogen atoms
H* through the lattice toward the downstream
surface of the membrane
6. Recombination of H* into hydrogen mole-
cules H2
7. Desorption of the H2 molecules and mass
transfer into the downstream bulk
For thick membranes, step 5 (diffusion of
hydrogen atoms through the lattice) results in
controlling the whole process. The diffusion of
hydrogen atoms through the lattice can be
described by the well-known Fick law:
dc
J¼D
dx
where J is the hydrogen flux through the lattice,
D is the hydrogen diffusion coefficient, and c is
the hydrogen concentration.
Under these conditions, the thermodynamic
equilibrium between the hydrogen molecules in
the gas phase and hydrogen atoms dissolved at
the interface would be established and it can be
described by
c ¼ S  pn
where S is the hydrogen solubility and p the
hydrogen partial pressure.
2 Richardson Law
The hydrogen permeation at constant temper-
ature through a dense palladium membrane is
described by the following general expression:
 
pnH2 , upstream  pnH2 , downstream
J H 2 ¼ PH 2
t
where J H2 is the hydrogen flux through the mem-
brane, PH2 the hydrogen permeability, t the mem-
brane thickness, p the hydrogen partial pressure,
and n the dependence factor of the hydrogen flux
on the hydrogen partial pressure, experimentally
determined in the range 0.5–1 (Dittmeyer
et al. 2001). When n is 0.5, the hydrogen flux
follows the so-called Sieverts’ law.
The hydrogen permeation through membranes
is an activated process ruled by an Arrhenius law:
 
Ea
PH 2 ¼ P0H2 exp
RT
where P0H2, Ea, R, and T are the pre-exponential
factor, the apparent activation energy, the univer-
sal gas constant, and the absolute temperature,
respectively. Consequently, when n is 0.5, the
hydrogen flux can be written in terms of the
so-called Richardson equation:
 
  pn
H 2 , upstream  pH 2 , downstream
n
Ea
J H2 ¼ P0H2 exp :
RT t
References
Dittmeyer R, Höllein V, Daub K (2001) Membrane reac-
tors for hydrogenation and dehydrogenation processes
based on supported palladium. J Mol Catal A Chem
173:135–184
Gallucci F, De Falco M, Tosti S, Marrelli L, Basile
A (2007) The effect of the hydrogen flux pressure
and temperature dependence factors on the membrane
reactor performances. Int J Hydrog Energy
32(16):4052–4058
S

 
G p~ 1
Sanchez and Lacombe Theory r þ þ T~

¼ e  1 lnð1  e
rÞ
rNRT e
r e
r
#
Giulio C. Sarti 1 Xf
Department of Chemical Engineering, Mining þ lnðe
rÞ þ i
lnðfi Þ : (1)
r i
r i
and Environmental Technology, University of
Bologna, Bologna, Italy
and by the expression of the volumetric equation
of state:
This is a molecular theory for classical fluids,    
~ 1
based on a compressible lattice fluid (LF) model e þ p~ þ T lnð1  e
r2
rÞ þ 1  e r ¼ 0 (2)
for the representation of the microstates of pure r
components and mixtures. Each molecular spe-
cies is considered decomposed in a sequence of Equation 1 has been written for the common case
contiguous segments (r-mers). The lattice cells in which the number of configurations available
are either empty or occupied by a molecular for each ri-mer in the close-packed pure state is
segment of the components in the mixture. The unity. The quantities used by the model are
volume of the cells is allowed to vary with com- defined in Table 1. The model expressions con-
position. Statistical arguments are used to calcu- tain pure component parameters and one binary
late the number of configurations available for a interaction parameter for each couple of compo-
system of N molecules with given configurational nents in the mixture.
energy and volume; the partition function is cal- The pure component parameters for a series of
culated from statistical mechanics results as a classical fluids are available (Sanchez and
function of temperature and pressure, in a mean Lacombe 1976, 1978; Sanchez and Panayiotou
field approximation, and finally, a simple expres- 1994). The model can describe the liquid-vapor
sion for the total Gibbs free energy is obtained for equilibrium conditions for pure components rea-
pure species (Sanchez and Lacombe 1976) and sonably below the critical point (Sanchez and
for mixtures (Lacombe and Sanchez 1976). In the Lacombe 1976), as well as the phase equilibrium
derivation, the flexibility parameter of the r-mers properties of different binary mixtures of simple
and the close-packed volume of a molecule are classical fluids (Lacombe and Sanchez 1976),
assumed independent of temperature and based on a single value of the binary interaction
pressure. parameter; the latter value can be obtained from
Relevant results of the theory are represented different experimental data for the mixture, i.e.,
by the expression of Gibbs free energy: from azeotropic temperature, change in volume

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_524-2
2 Sanchez and Lacombe Theory

Sanchez and Lacombe Theory, Table 1 List of symbols and properties used in the lattice fluid theory by Sanchez
and Lacombe
Symbol Name Definition/property
Pure ri* Characteristic
component density of pure
i component i
pi* Characteristic
pressure of pure
component i
Ti* Characteristic
temperature of
pure component i
ri0 Number of lattice r 0i ¼ rM
vi

i i
sites occupied by a
mole of pure
component i
vi * RT
i
Volume occupied v
i ¼ p
i
by a mole of lattice
sites of pure
substance
ei* T
i
Characteristic e
i ¼ k
energy of pure
component i
Mixtures N Total number of
moles
T Temperature
p Pressure
r Density
ri Density of species i ri ¼ oi r
oi Mass fraction, oi ¼ rri
i=1,2,. . .,Nt
fi Volume fraction fi ¼ X i i

o =r

oi =ri
i
X oi
r* Characteristic 1
¼
r
r
i
density of the i
mixture
X X X
p* Characteristic p
¼ fi p
i  12 fi fj  Dp
ij
pressure of the i i j6¼i
mixture
 pffiffiffiffiffiffiffiffiffiffiffiffi
ffi
Dp
ij Binary parameter Dp
ij ¼ p
i þ p
j  2 1  kij p
i  p
j
kij, Cij Dimensionless Cij ¼ 1  kij
binary parameter
X
r Molar average r¼ xi r i
number of lattice i
sites occupied by a
molecule in the
mixture
T* Characteristic
X T
i


T
¼ pr xi r 0i ¼ p Rv
temperature of the
i
p
i
mixture


e* Characteristic e
¼ Tk
energy
(continued)
Sanchez and Lacombe Theory 3

Sanchez and Lacombe Theory, Table 1 (continued)

Symbol Name Definition/property


v* Average close- v
¼ RT
p

packed mer molar
volume in the
mixture
e
r Dimensionless r ¼ rr

e
density
T~ Dimensionless T~ ¼ TT

temperature
p~ Dimensionless p~ ¼ pp

pressure
 

Volumetric r 2 þ p~ þ T~ lnð1  e
e r Þ þ 1  1r e
r ¼0
equation of state
" #
A Total Helmholtz   XNt
fi
free energy
A
r þ T~
¼ e 1
 1 lnð1  e
rÞ þ e
r lnðr Þ
1
þ lnðfi Þ
rNRT
er r
i¼1 i
" #
G Total Gibbs free   XNt
fi
energy
G
¼ e
r þ p~ þ T~ 1
 1 lnð1  e
rÞ þ e
r lnðr Þ
1
þ lnðfi Þ
rNRT
er er r
i¼1 i

or change in enthalpy upon mixing, mixture boil- References

ing point, UCST, and LCST (Lacombe and
Sanchez 1976).
The model has been extended also to poly-
meric solutions (Sanchez and Lacombe 1978),
considering that for the polymer species, the
number of r-mers per molecule becomes infi-
nitely large. The enthalpy of mixing of low
molecular weight solutes in polymeric liquids
may be well described by the model (Sanchez
and Lacombe 1978). For polymeric mixtures the
binary interaction parameters can be also reason-
ably predicted on the basis of the solubility
parameters of the mixture constituents (Rodgers
and Sanchez 1993). For its nature the model can
describe well the equilibrium behavior of mix-
tures in the absence of strong polar interactions
among the different components of the mixture.
Lacombe RH, Sanchez IC (1976) Statistical thermody-
namics of fluid mixtures. J Phys Chem 80:2568–2580
Rodgers PA, Sanchez IC (1993) Improvement to the
lattice-fluid prediction of gas solubilities in polymer
liquids. J Polym Sci Polym Phys Ed 31:273
Sanchez IC, Lacombe RH (1976) An elementary molecu-
lar theory of classical fluids. Pur Fluids J Phys Chem
80:2352–2362
Sanchez IC, Lacombe RH (1978) Statistical thermody-
namics of polymer solutions. Macromolecules
11:1145
Sanchez IC, Panayiotou C (1994) In: Sandler SI
(ed) Models for thermodynamic and phase equilibria
calculations. Dekker, New York, pp 187–285
S

Sand Filter This is the scientific term for electrokinetic

potential in a colloidal system. Its value is related
C. V. Vedavyasan to the stability of colloidal dispersions. It also
Department of Technology, Annamalai indicates the degree of repulsion between adja-
University, Chidambaram, Tamil Nadu, India cent similarly charged particles in a dispersion.

Introduction
Filter Comparison
Sand filters are employed as primary treatment in Sand Depth
a water/wastewater industry. Raw water with Media Single Three
various particle sizes of colloidals need to be Bed usage 1–3 % 90 %
coagulated/flocculated with coagulants and floc- Service rate 2–4 gpm/ft2 7–10 gpm/ft2
culants. The filter is filled with media such as Backwash 15 gpm/ft2 15 gpm/ft2
garnet, sand of varying sizes, and anthracite. Removal 40 m 10 m
These filters could be dual-media or multimedia
based on the raw water characteristics. A very
high degree of clarity is achieved in the filtered
water on account of finer particles of garnet at the
bottom which trap finer turbidity particles. Tur-
Types of Sand filter
bidity is trapped and held throughout the entire
bed depth, rather than the top 1 or 2 in.
Filtration is used in addition to regular coagula-
Mechanical filtration will remove almost all
tion and sedimentation for removal of solids from
forms of turbidity. In many cases, filters
surface water or wastewater. This prepares the
containing specially graded and sized gravel and
water for use as a portable boiler or cooling
sand are effective in screening out turbid parti-
makeup. Filtration is a simple mechanical pro-
cles. With such units, a periodic backwashing to
cess involving mechanisms of adsorption
remove the filtered material is all the mainte-
(physical and chemical), straining, sedimenta-
nance necessary.
tion, interception, diffusion, and inertial
Zeta Potential: This is a commonly used term
compaction.
in filtration. An increase or decrease of zeta
potential along with pH is an important criterion • Dual-media filter
in particle adhesion during the filtration process. • Multimedia filter
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_525-2
2 Sand Filter
The sand in a pool sand filter (# 20 silica sand;
45–55 mm) is specially graded to trap particles in
the 20–100 m range. The size and shape of the filter
media affect the efficiency of the solids removal.
Sharp, angular media form large voids and remove
less-than-rounded media of equivalent size. Though
most suspended solids are trapped at the surface or
in the first 1–2 in. of bed depth, some penetration is
essential to prevent a sharp increase in pressure
drop. As a sand filter collects dirt, its efficiency
increases, trapping more dirt. The media need to
be sufficiently coarse to allow solids to penetrate
the bed for 2–4 in.. It is time to backwash the
captured dirt out of the filter. They need the lowest
maintenance of the three types of pool filters. You
may need to open up the tank every 5 years or
so. Sand filters are the easiest to operate and main-
tain. If your sand filter requires frequent
backwashing every week or two, the sand bed may
be “mothballed,” or it may be “channeled.” It may
calcify with calcium deposits. A properly sized sand
filter could go over 10 years between sand changes.
The major advantages of dual media filtration
are higher rates and the longer runs.
Soft swim require annual cleaning of the filter
sand to prevent it from “gumming up.” High
amounts of bather oils can gum up a sand bed.
Types of Media
Quartz sand, silica sand, anthracite coal, garnet,
magnetite, and other materials may be used as
filtration media. Silica sand and anthracite are the
most commonly used types (e.g., in filters follow-
ing a hot process softener where the treated water is
intended for boiler feed, anthracite is usually used).
The terms “multilayer,” “in-depth,” and
“mixed media” apply to a type of filter bed
which is graded by size and density. Coarse
media, often 0.6–1.0 mm (0.024–0.04 in.) are
used for closely controlled coagulation and sedi-
mentation. Coarse, less dense particles are at the
top of the filter bed, and fine, denser particles are
at the bottom. Downflow filtration allows deep,
uniform penetration by particulate matter and
permits high filtration rates and long service
runs. Because small particles at the bottom are
also more dense (less space between particles),
they remain at the bottom. Even after high-rate
backwashings, the layers remain in their proper
location in the mixed media filter bed.
The table below lists four media used in mul-
timedia filtration. The use of too many different
media combinations causes severe backwashing
difficulties. High wash rates expand the magne-
tite layer which might wash away the anthracite
from the filter necessitating high wash water.
Media in multimedia filters:
Effective size, mm Specific
Media (in.) gravity
Anthracite 0.7–1.7 (0.03–0.07) 1.4
Sand 0.3–0.7 (0.01–0.03) 2.6
Garnet 0.4–0.6 (0.016–0.024) 3.8
Magnetite 0.3–0.5 (0.01–0.02) 4.9
Slow Sand Filtration (SSF)
Slow sand filtration technology is especially ideal
for small communities required to use filtration to
comply with new regulations.
How SSF Works
Slow sand filtration relies on both physical and
biological activity in controlling plant pathogens.
The filter bed in SSF is constructed of a medium
with high surface area colonized by suppressive
microorganisms. The media also presents a phys-
ical barrier to the passage of spores of plant
pathogens (Figs. 1 and 2).
Advantages of SSF:
• It is low-energy consuming process.
• Has great adaptability in components and
applications. Maintenance is minimal.
• Systems can be built and installed by laymen.
• Costs of building and running significantly
lower than other disinfection methods.
In Australia, chlorination/bromination pro-
cesses are most widely used for water disinfesta-
tion in nurseries. Chemical treatments have
Sand Filter
proven effective when used carefully; however,
they are relatively expensive and present safety
issues to the handlers and the environment.
A disadvantage of the SSF is the large amount
of land required, a consequence of the slow rates
of water filtration that are possible, typically only
Sand Filter, Fig. 1 A typical sand filter configuration
Sand Filter, Fig. 2 A typical slow sand filter for water purification
3
10 % or less of the rates that are possible in rapid
filtration.
Sand Specifications
Sand is characterized by the diameter of the indi-
vidual sand grain (0.15–0.35 mm) and the effec-
tive size of the composite sand, ES or d10. d10 is
defined as the sieve size in mm that permits
passage of 10 % by weight of the sand. The
uniformity coefficient (UC) of sand is defined as
d60/d10. Effective size (ES) is such that approx-
imately 10 % of the total grains by weight are
smaller and 90 % are larger. ES is the minimum
size of most of the particles. Uniformity is mea-
sured by comparison of effective size to the size
at which 60 % of the grains by weight are smaller
and 40 % are larger. This latter size, divided by
the ES, is called the uniformity coefficient – the
smaller the UC, the more uniform the media
particle size.
It is recommended to use fine-grade sand
(0.15–0.35 mm), uniformity coefficient
(UC) always <3, preferably <2 and be washed
free of clay, loam, and organic matter. Fine
4 Sand Filter
particles will quickly clog the filters and frequent
cleaning will be required. Sand that is not uni-
form will also settle in volume, reducing the
porosity and slowing the passage of water.
Biological Activity
Microbial activity builds up very quickly in
greenhouse nutrient solutions, and slow sand fil-
ters become active in biological suppression
without any special inoculation. Safe drinking
water is a high priority for people without main
facilities.
Slow gravity sand filters remove bacteria and
other small particles from drinking water, making
it safe to drink. Sand filters cannot cope with
heavy metals or other excessive pollutants.
Their prime purpose is to remove bacteria and
particles. If the source of raw water has a high
level of contamination, locate a new one. Even
spring water or very clean water is to be checked
for undesirable contaminants. If the water con-
tains sediment, it should be passed through an
initial settling tank before it gets into the sand
filter.
How the Filter Works
The water passes through the sand from top to
bottom. Any larger suspended particles are left
behind in the top layers of sand. Smaller particles
of organic sediment left in the sand filter are eaten
by bacteria and protozoans which “stick” in the
layers of slime that form around the sand parti-
cles, and the clean water which passes through
the filter is safe to drink. Provided that the grain
size is around 0.1 mm in diameter, a sand filter
can remove all fecal coliforms (bacteria that orig-
inate from feces) and virtually all viruses.
Conclusion
Sand filters serve as the major equipment of fil-
tration in every area of daily use – from swim-
ming pools to household and water treatment
plants. This primary treatment shall reduce the
load on subsequent pressure filtration. Best engi-
neering practices are advocated in the design of
sand filters and operation thereafter for clear
water suitable for downstream hygienic use.
Clarifier effluents of 2–10 NTU may be improved
to 0.1–1.0 NTU by conventional sand filtration.
References
Colorado State University, CH2M Hill Engineers, Denver
(CO) Water Department
http://www.gewater.com/handbook/ext_treatment/ch_6_
filteration.jsp
http://www.poolcenter.com/sand-pool-filter-information.
html
Manual of design for slow sand filtration
The Davnor BioSand Water Filter
S
Saturated and Supersaturated
Solutions
Bart Van der Bruggen
Department of Chemical Engineering, Process
Engineering for Sustainable Systems (ProcESS),
KU Leuven, Leuven, Belgium
A solution is saturated with respect to a given
substance when the maximum solubility of the
substance is reached. This is reflected by the sol-
ubility constant of the solution (Linke and Seidell
1965). For example, for the precipitation reaction:
Anþ þ Bn $ AB ðsÞ
The solubility is determined by the equilibrium
constant of the reaction, KAB:
KAB ¼ ½Anþ ½Bn 
½Anþ ½Bn 
or ¼1
KAB
with ½Anþ  and ½Bn  the activities of A and B,
respectively. The logarithmic form of this equa-
tion is the stability index, SI:
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_526-1
½Anþ ½Bn 
SI ¼ log
KAB
When SI = 0, the solution is saturated. When
SI > 0, there is an excess of AB (l) in the solution,
and the solution is oversaturated. When
SI < 0, the solution is undersaturated.
AB can be any species, and the stoichiometry
can be more complex than in this simple example.
The saturation point (or the equilibrium constant)
depends on the temperature and pressure of solu-
tion and is different for each species.
When a solution is oversaturated, precipitation
may occur. Nevertheless, kinetics also play a
role: for homogeneous precipitation (in the
absence of an external surface), an SI of 3–4 is
to be applied in general, whereas for heteroge-
neous precipitation, an SI of 1–2 is needed.
Precipitation of a supersaturated solution is
important for membrane applications in two
ways. First, the increase of the concentration of
rejected species in the retentate may lead to
oversaturation, depending on the initial concentra-
tion and the ratio of permeate to feed. These spe-
cies, typically salts, can subsequently precipitate
on the membrane surface and block permeation;
this phenomenon is referred to as scaling. Scaling
leads to an increase in energy consumption and
chemical cleaning frequency. The most well-
known sparingly soluble salts are CaSO4 and
CaCO3 (Pervov 1991), but other salts may also
precipitate, such as BaSO4 and phosphate and
silica salts (Semiat et al. 2003, Chesters 2009).
2 Saturated and Supersaturated Solutions

Saturated and Supersaturated Solutions, Table 1 Pretreatment methods and their effect on scaling in reverse
osmosis (Baker 2001) (XX highly effective, X moderately effective)
Pretreatment method CaCO3 CaSO4 SiO2
Acid dosage XX
Antiscalant dosage X XX
Softening/ion exchange XX XX
Preventive cleansing X X
Adjustment of process parameters X XX
Quick filtration X
Flocculation X
Micro- and ultrafiltration XX
Candle filters X

Solutions to prevent scaling include the use of
antiscalants or acids such as hydrochloric acid
(HCl) and sulfuric acid (H2SO4). The use of
acids is an effective solution, since the solubility
of salts increases significantly at lower
pH. Sulfuric acid is the most commonly used
acid for this purpose. However, the trend is to
use more hydrochloric acid, because sulfuric acid
can negatively influence the fouling speed of a
membrane by the addition of sulfate ions, which
can stimulate precipitation of e.g., gypsum
(CaSO4).
A separate unit for removal of the scalant prior
to the membrane separation might be necessary
(Bremere et al. 1998), especially when going
from high to very high feed recoveries (very
high permeate to feed ratio). Some pretreatment
methods and their effect on scaling are summa-
rized in Table 1 (Baker 2001). However, a higher
recovery shifts the problem to scaling of other
salts with lower initial concentrations, which are
not removed in advance. In any case, diagnosis,
prediction, prevention, and control of scaling are
important in any membrane application with
scaling potential (Vrouwenvelder et al. 2003).
The membrane process in which the highest
risk for scaling is encountered is reverse osmosis,
because ions present in sparingly soluble salts are
rejected by reverse osmosis membranes. Other
processes related to salt removal or transport,
such as electrodialysis and nanofiltration (and to
a lesser extent, forward osmosis), are also at risk.
Supersaturation of salts is also crucial – and in
this case a desired phenomenon – in the mem-
brane crystallizers. It has been shown that in a
membrane contactor producing supersaturated
solutions, crystals with extremely high purity
can be obtained, as shown in Fig. 1 for NaCl
(Drioli et al. 2004). Similar results can be
obtained for CaCO3 and MgSO4  7H2O as solid
products. Crystal growth generally starts at solute
concentrations at which the nucleation occurs;
the growth rate, depending on the supersaturation
degree, is determined by a combination of the
nature of the growing crystal surface and the
diffusional rate (Curcio et al. 2001). Direct con-
tact membrane distillation can be employed to
reach the supersaturation required for
crystallization.
Saturated and Supersaturated Solutions 3

Saturated
and Supersaturated
Solutions, Fig. 1 High-
purity NaCl salts obtained
in a membrane crystallizer
(Drioli et al. 2004, used
with permission of
Elsevier)

Cross-References Curcio E, Criscuoli A, Drioli E (2001) Membrane crystal-

lizers. Ind Eng Chem Res 40(12):2679–2684
Drioli E, Curcio E, Criscuoli A, Di Profio G (2004) Inte-
▶ Direct Contact Membrane Distillation grated system for recovery of CaCO3, NaCl and
▶ Electrodialysis MgSO4  7H2O from nanofiltration retentate.
▶ Forward Osmosis J Membr Sci 239:27–38
▶ Membrane Contactor Linke WF, Seidell A (1965) Solubilities of inorganic and
metal organic compounds, 4th edn. Van Nostrand,
▶ Membrane Crystallizer Princeton
▶ Nanofiltration Pervov AG (1991) Scale formation prognosis and cleaning
▶ Reverse Osmosis procedure schedules in reverse osmosis systems oper-
▶ Scaling ation. Desalination 83:77–118
Semiat R, Sutzkover I, Hasson D (2003) Scaling of RO
membranes from silica supersaturated solutions. Desa-
lination 157:169–191
References Vrouwenvelder JS, Kappelhof JWNM, Heijman SGJ,
Schippers JC, Van der Kooij D (2003) Tools for foul-
Baker RW (2001) Membrane technology. In: Encyclope- ing diagnosis of NF and RO membranes and assess-
dia of polymer science and technology. Wiley, ment of the fouling potential of feed water.
New York Desalination 157:361–365
Bremere I, Kennedy M, Johnson A, Van Emmerik R,
Witkamp GJ, Schippers JC (1998) Increasing conver-
sion in membrane filtration systems using a desupersa- Further Reading
turation unit to prevent scaling. Desalination Drioli E, Criscuoli A, Curcio E (2006) Membrane
119:199–204 contactors: fundamentals, applications and potentiali-
Chesters SP (2009) Innovations in the inhibition and ties, vol 11, Membrane science and technology series.
cleaning of reverse osmosis membrane scaling and Elsevier, Amsterdam
fouling. Desalination 238:22–29
S
Scale Inhibitor
C. V. Vedavyasan
Department of Technology, Desalination Process
Specialist, Annamalai University, Chidambaram,
Tamil Nadu, India
Synonyms
Antiscalant
Introduction
Antiscalants (scale inhibitors) are used in drink-
ing water and process industry to prevent scaling
or scale deposits on the membrane surface in a
membrane-operated water treatment plant. Scal-
ing occurs when the solubility limit of sparingly
soluble salts/minerals is reached leading to the
salt precipitation on the membrane surface as the
temperatures and pressures change. Scale inhibi-
tors delay this process and allow higher concen-
trations of salts resulting in enhanced water
recovery. Antiscalants are stable in process
equipment and are slowly biodegradable in the
receiving surface water.
What Is Scale?
Scale is a white chalky buildup of calcium min-
erals that occur as a result of the precipitation of
normally soluble solids that become insoluble as
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_527-4
temperature increases. Common examples of
scale are calcium carbonate (CaCO3), calcium
sulfate (CaSO4), barium sulfate (BaSO4), and
strontium sulfate (SrSO4). Equally problematic
are silica (SiO2) and calcium fluoride (CaF)
scales. Over time, without proper treatment,
scale and other contaminants build up and reduce
the flow. RO scale inhibitors eliminate scale and
reduce fouling on the membranes, while specific
scale inhibitors reduce corrosion on the boilers.
The scale inhibitors prevent undesirable scale
buildup on the equipments and affect the effi-
ciency. Appropriate treatment by scale inhibitor,
conforming to the source water chemistry, will
extend the life of industrial equipment and pro-
vide optimal process condition.
Process Description
The chemical treatment of water associated with
oil and gas includes the application of scale
inhibitors – phosphonates – to help maintain the
integrity of equipment used during the drilling
and production phases. Treatment is used to
reduce the concentration of scale-forming com-
pounds. The accumulation of scale can reduce
flow rates or lower the efficiencies in heat
exchanger. The inhibitors can be applied
downhole of the wellhead and classified as:
• Oil miscible
• Totally water-free
• Emulsified and solid
2 Scale Inhibitor
Technical Capabilities
Available scale-inhibiting chemicals are effec-
tive at preventing mineral deposits caused by
compounds such as CaCO3, SrSO4, CaSO4,
BaSO4, FeS, and FeO. Appropriate scale inhibitor
and dose will identify types and concentrations of
scale-forming compounds in the water.
Phosphonate-based scale inhibitors are effective
in preventing carbonate and sulfate scales,
whereas polymer base inhibitors are effective
for sulfate/carbonate scales of barium, strontium,
and calcium.
Reverse Osmosis (RO)
RO is a pressure-driven process, while its
pretreatment being site specific is dictated by
the raw water chemistry. Antiscalants reduce the
extent of contaminants that attach to the mem-
brane surface during operation. Primarily, they
delay or retard the process of membrane fouling.
Many antiscalants combat scaling and fouling by
bonding with the contaminants in the water,
thereby preventing it from attaching or sticking
to the membrane surface. These contaminants are
finally directed to the RO reject or drain.
A variety of antiscalants are available with
varying chemistries based on phosphonates,
phosphates, acrylates, maleic and carboxylic
acids, and dendrimers. Selection of antiscalant
is site and application specific; they have differ-
ent capabilities for inhibiting scales that are
encountered in RO system. Different antiscalant
chemistries have unique mechanisms for slowing
crystal growth. However, the antiscalants delay
crystal formation by slowing induction time – the
time between nucleation (birth of a new crystal)
and crystal growth.
Three methods of scale control employed are:
• Αcidification
• Ion exchange (zeolite) softening
• Αntiscalant addition
Acidification
Acid addition destroys carbonate ions, removing
one of the reactants necessary for calcium car-
bonate precipitation. This is very effective in
preventing the precipitation of calcium carbonate
while ineffective in preventing other types of
scale. Disadvantages include corrosivity of the
acid, the cost of tanks, monitoring equipment,
and the fact that acid lowers the pH of the RO
permeate.
Ion Exchange Softening
Sodium is utilized here which is exchanged for
magnesium and calcium ions that are concen-
trated in the RO feed water:
Ca2þ þ 2 Na Z ¼> 2 Naþ þ CaZ2
Mg2þ þ 2 Na Z ¼> 2 Naþ þ MgZ2
(NaZ represents the sodium exchange resin)
When all the sodium ions have been replaced
by calcium and magnesium, the resin is
regenerated with brine. Ion exchange softening
eliminates the need for continuous feed of either
acid or antiscalant.
Threshold Inhibition
It is the ability of an antiscalant to keep supersat-
urated solutions of sparingly soluble salts. It pre-
vents the precipitation of salts once the salt has
exceeded its solubility product. The chemical
inhibitors retard or delay the clustering process
of charged ions and protonuclei. The most effec-
tive threshold inhibitors are based on phosphonic
acids (or their salts) which have the added advan-
tage of sequestering iron in a stoichiometric reac-
tion. This is critical in membrane application as
any soluble iron will cause rapid fouling while it
oxidizes and becomes insoluble.
Performance
Antiscalant offers a variety of performance and
application benefits. They are a powerful inhibi-
tor tool against a variety of scales listed below.
Scale Inhibitor 3

CaCO3 CCPP >900 (LSI >2.8) The following categories of information must
CaSO4 3.0  Ksp be present on the MSDS:
BaSO4 105  Ksp
SrSO4 20  Ksp • Product information – product identifier
CaF 1,000  Ksp (name), manufacturer and suppliers names,
SiO2 120 ppm addresses, and emergency phone numbers
• Hazardous ingredients
The available antiscalants are highly effective • Physical data
at low dose rates in a wide range of feed water • Fire or explosion hazard data
types and pH ranges. They provide both scale • Reactivity data: information on the chemical
and inorganic fouling control while compatible instability of a product and the substances it
with all membrane configuration and types. may react with
CCPP: calcium carbonate precipitation • Toxicological properties: health effects
potential. http://www.awwa.org/Resources/ • Preventive measures
RTWCorrosivityCalc • First aid measures
Saturation-level formulas for common scale- • Preparation information: who is responsible
forming species for preparation and date of preparing the
MSDS
Calcium carbonate (Ca)(CO3)/KSP CaCO3
Barium carbonate (Ba)(CO3)/Ksp BaCO3
Calcium sulfate (Ca)(SO4)/Ksp CaSO4 Scale Prediction and Saturation
Barium sulfate (Ba) (SO4)/Ksp BaSO4 Water is said to be saturated with a compound
Amorphous silica H4 SiO4/(H20)2 x Ksp SiO2 such as calcium carbonate if it will not precipitate
Calcium fluoride (Ca) (F)2/KspCaF2 the said compound or dissolve any of the solid
Strontium carbonate (Sr)(CO3)/Ksp SrCO3 phase of the compound when left undisturbed,
Strontium sulfate (Sr) (SO4)/Ksp SrSO4 under the same conditions, for an infinite period
Magnesium hydroxide (Mg) (OH)2/KSP Mg(OH)2 of time. Water that will not precipitate or dissolve
Tricalcium phosphate (Mg) (OH)2/Ksp Mg(OH)2 a compound is at equilibrium for that compound.
The amount of a chemical compound that can
Material Safety Data Sheet (MSDS) be dissolved in water and remain in solution for
A Material Safety Data Sheet is a document that this infinite period of time is described by the
contains information on the potential hazards solubility product (Ksp). In the case of calcium
(health, fire, reactivity, and environmental) and carbonate, solubility product is defined by
how to work safely with the chemical product and relationship:
an essential starting point for the development of
a complete health and safety program. It also ðCaÞðCO3 Þ ¼ KSP ;
contains information on the use, storage, han-
dling, and emergency procedures related to the where (Ca) is the activity of sodium.
hazards of the material. The MSDS contains (CO3) is the carbonate activity.
much more information about the material than KSP is the solubility product for calcium carbon-
the label. MSDSs are prepared by the supplier or ate at the temperature.
manufacturer of the material. It is intended to tell
what the hazards of the product are, how to use In a more generalized sense, the term (Ca)
the product safely, what to expect if the recom- (CO3) can be called the ion activity product
mendations are not followed, what to do if acci- (IAP) and the equilibrium condition described
dents occur, how to recognize symptoms of by the relationship IAP = Ksp.
overexposure, and what to do if such incidents Scale indices developed are derived from the
occur. basic concept of saturation:
4 Scale Inhibitor

Scale Inhibitor, Table 1 Antiscalant consumption inevitable by extending induction time (Ferguson
Consumption (kg/h) without second-pass brine 1984, Ferguson et al. 2011; Gill et al. 1983;
recirculation Tomson et al. 2002; Amjad and Masler 1985).
First-pass RO 13.3 Time selected is the residence time the
Second-pass front/rear 3.2/3.8 inhibited water will be in the system. The inhib-
Total 20.3 itor must prevent scale formation or growth until
Consumption with recirculation the water has passed through the system and been
First pass 9.5 discharged.
Second-pass front/rear 3.2/0.6
Temperature affects the rate constant for the
Total 13.3
induction time relationship. As in any kinetic
Consumption in conventional RO design
formula, the temperature has a great effect on
First pass 7.0
reactants collision frequency. This effect is inde-
Second pass 7.0
pendent of the effect of temperature on
Total 14.0
saturation-level calculations. A basic chemistry
concept is that reaction rates increase with tem-
perature. The rates approximately double for
• If a water is undersaturated with a compound, every 10  C increase in temperature.
IAP<Ksp. It will tend to dissolve the pH affects saturation level, but it also affects
compound. the dissociation state and stereochemistry of the
• If a water is supersaturated with a compound, inhibitors (Tomson et al. 2002). By virtue of its
IAP>Ksp. It tends to precipitate the impact on the charge and shape of an inhibitor
compound. molecule, inhibitor effectiveness can be a func-
• If a water is at equilibrium with a compound, tion of pH, but may not always be significant in
IAP =Ksp. It tends not to dissolve or precipi- the pH range of interest (6.5–9.5). Acid
tate the compound. dosage and consequently the pH of the medium
IAP = ion activity product; have a significant bearing on the antiscalant
Ksp = solubility product. dosage in a membrane-based treatment plant.
Few BWRO (Brackish Water Reverse Osmosis)
units can run without scale inhibitor.
Table 1 summarizes the overall results of
antiscalant consumption at 300-ML/day of Ade-
Concentration Polarization
laide (Southern Australia) Desalination Plant
Concentration polarization is a phenomenon in
(ADP). It has been estimated that the antiscalant
which ion concentrations in a membrane’s
dose at this facility shall be 5 % lower than for a
boundary layer are projected to be higher than
conventional RO design due to brine
those of the bulk water. The amount of boundary
recirculation of the second pass ahead of the RO
layer concentration can vary from 1.12 to 1.4 
process.
that of the bulk water for clean membranes
(Byrne 2002). Higher concentrations have been
Dosage Optimization reported for fouled systems due to “cake-
Induction time. Reactions do not occur instanta- enhanced” concentration polarization.
neously. A time delay occurs when all reactants Concentration polarization can affect all
are combined. They must come together in the concentration-dependent calculations, including:
reaction media to allow the reaction to occur.
Thermodynamic evaluations of a water scale • pH
potential predict what will happen if water is • Brine ion concentrations
allowed to sit undisturbed under the same condi- • Recovery limits
tions for an infinite period of time. Scale inhibi- • Maximum recovery based on antiscalant
tors do not prevent precipitation; they delay the saturation-level maximum
Scale Inhibitor
• Dosage
Conclusion
Dosage models are available or can be developed
for new inhibitors that allow accurate prediction
of dosage requirements and treatment failure
points. Specific scale inhibitors have been devel-
oped for specific applications like for cooling
systems, steam boiler systems, sulfamic acid-
based descaler, corrosion nitrite inhibitor for
chilled system, corrosion inhibitor (hard water)
for open cooling systems, and air conditioning
plant. Appropriate inhibitor is chosen after
predicting the scaling tendency of the medium.
Corrections in the modeling in high TDS brine
are required as RO predictions lack accuracy due
to use of simple indices. Such corrections are
required for noncarbonate alkalinity and free ion
concentrations. Scale inhibitor is an indispens-
able chemical in water and non-water segment.
They aid in keeping the membranes from fouling
so that the water will flow smoothly through. It is
highlighted that appropriate selection or rather
optimization of RO configuration can result in
savings of up to 5 % as compared to conventional
design.
5
References
Amjad Z, Masler WF (1985) The inhibition of calcium
sulfate dihydrate crystal growth by polyacrylates and
the influence of molecular weight. NACE Interna-
tional, Houston, Corrosion, 85 Paper No 357
Antiscalant technical data sheet http://www.avistatech.
com/antiscalants
Byrne W (2002) Reverse osmosis: a practical guide for
industrial users, vol 158. Tall Oaks Publishing, Little-
ton, pp 457–458
Ferguson RJ (1984) A kinetic model for calcium carbon-
ate scale. NACE International Corrosion, Houston,
84, Paper No 46
Ferguson RJ, Ferguson BR, Stancavage RF (2011) Model-
ing scale formation and optimizing scale inhibitor
dosages. IDA J Desalin Water Reuse 3(2):30–39
Gill JS, Anderson CD, Varsanik RG. 1983. Mechanism of
scale inhibition by phosphonates. In: International
water conference, 44th annual meeting, IWC -83-4,
Pittsburgh
Hijos G, Artal J, Ajuriagogeascoa I, Bidaurrazasa JA
(2012) Adelaide desalination plant process design:
energy use optimization. IDA J 4(2):52–56
Tomson MB, Fu G, Watson MA, Kan AT (2002) Mecha-
nism of mineral scale inhibition, society of petroleum
engineers. Oilfield Scale Symposium, Aberdeen
Water Treatment Technology Fact sheet http://www.
aquaclear.com/scale-inhibitor-control.pdf. Accessed
Dec 2010
S
Segmented Block Copolymer
Anja Car
Department of Chemistry, University of Basel,
Basel, Switzerland
Segmented block copolymers or multi-block
copolymers with general formula (AB)n are lin-
ear macromolecules containing different rigid
and flexible polymeric segment or block
(Richard 2000). Usually, the flexible block has a
glass transition temperature (Tg) below room
temperature, whereas the rigid block has a glass
transition temperature or melting temperature
(Tm) distinctly higher (Holden et al. 2004).
Microphase separation in the solid state derived
from incompatible blocks is one of the most typ-
ical characteristic properties of segmented block
copolymers (van der Schuur and Gaymans 2007).
The morphology depends on chemical composi-
tions, chain structure, molecular weight of con-
stituent blocks, thermodynamic interaction
parameters, and used solvent during its process
(Timothy 2003). They allow to extent signifi-
cantly the property profiles of defined polymer
materials by combining useful properties of two
or more different prepolymers or polymers in one
final product (Khastgir and Bhowmick 1998).
The influence of the chemical structure and the
chain length of segments upon the formation of
“micro-domains” of the certain phase is very
important and determines the final properties of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_529-2
polymer. Hence, at room temperature, these
materials behave like elastomers, but at a temper-
ature above Tg or Tm of the rigid block, the
materials can be processed like thermoplastics
(Richard 2000). Thus, these copolymers are con-
sidered as thermoplastic elastomeric materials,
with several aspects of rubberlike behavior.
Multi-block copolymers can be synthesized
from different polymer segments having active
functional groups at the chain end (Ebeling and
Vana 2011). Basically, segmented block copoly-
mers are formed in such a way that the chemical
reaction employs both monomer and preformed
functional terminated oligomers. Earlier, the seg-
mented systems were synthesized through basic
linkages involving isocyanate chemistry (Riegel
and Kent 2003). In contrast to the segmented
urethanes, amides, or urea copolymers, seg-
mented polyester ether copolymers are generally
prepared by the melt transesterification (Thomas
et al. 2011).
References
Ebeling B, Vana P (2011) Multiblock copolymers of sty-
rene and butyl acrylate via polytrithiocarbonate-
mediated RAFT polymerization. Polymers 3:719–739
Holden G, Kricheldorf HR, Quirk RP (2004) Thermoplas-
tic elastomer. Carl Hanser Verlag, Munich
Lodge TP (2003) Block copolymers: past successes and
future challenges. Macromol Chem Phys 204:265–273
Riegel ER, Kent JA (2003) Riegel’s handbook of indus-
trial chemistry. Kluwer, New York
2 Segmented Block Copolymer

Spontak RJ, Patel NP (2000) Thermoplastic elastomers:
fundamentals and applications. Curr Opin Colloid
Interface Sci 5:333–340
Subiman G, Khastgir, Bhowmick AK (1998) Effect of
block molecular weight on the mechanical and
dynamic mechanical properties of segmented polyam-
ide. Polymer 39:3967–3975
Thomas S, Visakh P. M (2011) Handbook of engineering
and specialty thermoplastics, Scrivener Publishing
van der Schuur MJ, Gaymans RJ (2007) Influence of
morphology on the properties of segmented block
copolymers. Polymer 48:1998–2006
S
Serum Proteins
Karin Schroen
Laboratory of Food Process Engineering,
Wageningen University and Research Centre,
Wageningen, The Netherlands
Roughly 10 kg of milk consisting of 4 % fat,
2.6 % casein, and 0.7 % serum protein, but mostly
of water (Walstra et al. 1999), is needed to pro-
duce 1 kg of cheese. The fat and casein are mainly
incorporated in the cheese, while the serum pro-
teins together with k-casein and most of the water
become the whey. As indicated in Table 1, the
whey proteins are considerably smaller (3–6 nm)
than the casein micelles which are typically
20–300 nm.
Serum protein was previously considered a
by-product, but nowadays, serum proteins have
considerable economic value due to their out-
standing emulsification, gelling, and foaming
properties, either as a serum protein isolate or
concentrate or as a specific protein. To preserve
these special properties, in some cases the cheese
process is started from a concentrated casein
stream, while most of the serum proteins are
separated and don’t receive a heat treatment that
can be detrimental to their functional properties.
We discuss here separation of serum proteins
from regular serum, separation of serum protein
from casein during a case in concentration step,
and isolation of specific proteins.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_531-3
The salt concentration in serum is high, and
therefore demineralization is needed.
Nanofiltration has a great benefit over ion
exchange and electrodialysis that it reduces
energy consumption and the partly demineralized
can be processed further into powders (van der
Horst et al. 1995). When comparing various
membranes (PSF/PVP, ZrO2, ZrO2/PSF), Doyen
and coworkers (1996) concluded that the flux of
the membranes is determined by the fouling layer
and not the permeability of the membranes. Pre-
vention of gel layer formation is a critical step
and limits the concentration factors that can be
reached.
Various authors have investigated concentra-
tion of casein either with ultrafiltration (all pro-
tein is in that case concentrated to reduce the
liquid flow in the cheese production lines) or
microfiltration, which allows for concentration
of casein over serum protein. When focusing on
this latter option, four studies are illustrative for
what is possible, as shown in Table 2. The
obtained process conditions were very compara-
ble with the exception of the work of Krstic
et al. (2002) who used turbulence promoters, but
also did not reach high concentration factors. In
general it can be said that for concentration of
casein micelles, control over the membrane flux
and related fouling are the most important factors
to keep into account and that high concentration
factors of up to 10 are feasible.
The individual serum proteins have many dif-
ferent applications, as have their hydrolysates
2 Serum Proteins

Serum Proteins, Table 1 Concentrations and sizes of proteins present in milk (Walstra et al. 1999)
Concentration in whole milk (g/l) Average molecular size or weight
Total serum proteins 0.7 3–6 nm
a-Lactalbumin 0.12 14 kD
B-Lactoglobulin 0.32 18 kD
BSA 0.04 66 kD
Proteose-peptone 0.08 4–40 kD
Immunoglobulins 0.08 150–900 kD
Lactoferrin 0.01 86 kD
Transferrin 0.01 76 kD
Others 0.04

Serum Proteins, Table 2 Comparison of casein concentration processes

Process conditions cross flow/ Concentration
Membrane type and flux pressure factor Source
Ceraflo 0.22 mm; 2.5•10 5 m/s 6.9 m/s; 190 kPa 3 Pouliot et al. 1996
Membralox 0.2 mm 1.9•10 5 m/s 7.2 m/s; 193 kPa 2 Vadi and Rizvi 2001
1.3•10 5 m/s 10
CeraMem asymmetric 0.05 mm; 5.4 m/s; 138 kPa 2 Punidadas and Rizvi
3.1•10 5 m/s 1998
Membralox 0.1 mm; 9.7•10 5 m/s 0.45 m/s; 34 kPa turbulence 1 Krstic et al. 2002
promoters
4
2.5•10 m/s 12.5 m/s; 65 kPa

that are known to contain bioactive components.
Since hydrolysates are much smaller as the pro-
teins, they can be easily removed through with
ultrafiltration. Separating the whole protein from
a mixture is still a challenge; a-lactalbumin may,
for example, first be thermally aggregated, prior
to membrane ultrafiltration; alternatively also
adjustment of pH and salt concentration can be
used to influence electrostatic and steric interac-
tion and in this way enhance the selectivity of
ultrafiltration as described in, e.g., Cheang and
Zydney (2003).
References
Cheang B, Zydney AL (2003) Separation of a-lactalbumin
and b-lactoglobulin using membrane ultrafiltration.
Biotechnol Bioeng 83:201
Doyen W, Adriansens W, Molenberghs B, Leysen
R (1996) A comparison between polysulfone, zirconia
and organo-mineral membranes for use in ultrafiltra-
tion. J Membr Sci 113:247
Krstic DM, Tekic MN, Caric MD, Milanovic DS
(2002) The effect of turbulence promoter on cross-
flow microfiltration of skim milk. J Membr Sci
208:303
Pouliot M, Pouliot Y, Britten M (1996) On the conven-
tional cross-flow microfiltration of skim milk for the
production of native phosphocaseinate. Int Dairy
J 6:105
Punidadas P, Rizvi SSH (1998) Separation of milk pro-
teins into fractions rich in casein or whey proteins by
cross flow filtration. Food Res Int 31:265
Vadi PK, Rizvi SSH (2001) Experimental evaluation of a
uniform transmembrane pressure crossflow
microfiltration unit for the concentration of micellar
casein from skim milk. J Membr Sci 189:69
Van der Horst HC, Timmer JMK, Robbertsen T, Leenders
J (1995) Use of nanofiltration for concentration and
demineralization in the dairy industry: model for mass
transport. J Membr Sci 104:205
Walstra P, Geurts TJ, Noomen A, Jellema A, van Boekel
MAJS (1999) Dairy technology: principles of milk
properties and processes. Marcel Dekker, New York
S
Silica DDR Membrane
A. F. Ismail1,2 and M. H. D. Othman1,2
1
Advanced Membrane Technology Research
Centre (AMTEC), Universiti Teknologi
Malaysia, Skudai, Johor, Malaysia
2
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia
Synonyms
All-silica DDR membrane
Zeolite is an aluminosilicate mineral and pos-
sesses different crystal structures that determine
the pore diameters, which vary between 0.3 and
1 nm (Hedlund 1998). Cavities and pores are
uniform in size within a specific zeolite material
and permit only molecules of certain size and
shape to penetrate inside the channels and reject
those of larger dimensions. This type of separa-
tion is termed as molecular sieving. Therefore,
small-pore 8-ring window zeolites were devel-
oped for the separation of light gases. An exam-
ple of such zeolite is all-silica decadodecasil
3 rhombohedral (DDR) with a window opening
of 0.36  0.44 nm (Gies 1986). The topology of
all-silica DDR consists of window-connected
cages in the absence of aluminum, in contrast to
zeolite frameworks, which makes this material a
member of the group of clathrasils. Clathrasils
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_533-2
are all-silica clathrate compounds with three-
dimensional frameworks built of [SiO4]4 tetra-
hedral linked in the corners with cage-like voids
in between (Zhu et al. 2000). All-silica DDR can
be considered as a link between zeolites and
clathrasils because it possesses zeolitic properties
through a clathrasil structure. The chemical com-
position of all-silica DDR can be represented as
[(C10H17N)6(N2)9][Si120O240], where C10H17N is
1-aminoadamantane used as a template molecule
in the synthesis.
The preparation of all-silica DDR membranes
have been widely reported (Tomita et al. 2004;
Bergh et al. 2008; Kuhn et al. 2008). As a general
procedure of synthesis, all-silica DDR seed crys-
tals are initially deposited on the surface of
porous alumina substrate prior to the immersion
in mixture solution of 1-aminoadamantane agent
to grow a continuous DDR membrane and
followed by the calcination process at high tem-
perature (~700  C). The general microstructures
of the resulted all-silica membrane are shown in
Fig. 1. This figure indicated that dense all-silica
DDR membrane was formed uniformly and the
thickness of the membrane was 5–10 mm. The
porous alumina substrate was commonly used as
a support to provide high mechanical strength and
low flow resistance to the membrane.
According to Bergh et al. (2008), the perme-
ation and separation characteristics of light gases
through all-silica membranes can be explained by
taking into account three factors, which are
(1) steric effects introduced by the window
2 Silica DDR Membrane
Silica DDR Membrane, Fig. 1 SEM images of the
microstructure of a DDR type zeolite membrane formed
on a porous alumina substrate, (a) surface and (b) cross-
opening of all-silica DDR leading to molecular
sieving and activated transport, (2) competitive
adsorption effects, and (3) interaction between
diffusing molecules in the cages of the zeolite.
Pore dimension of 0.36  0.44 nm allowed
the all-silica DDR membrane to be very suitable
for the separation of CO2 and CH4, which have
kinetic diameters of 0.33 and 0.38 nm, respec-
tively. As reported by Tomita et al. (2004), the
separation factor (SF) of CO2 to CH4 in 50 % CO2
and 50 % CH4 mixed gas feed for the synthesized
all-silica membrane was in the range of
100–220 at 0.5 MPa total gas feed pressure,
which is much higher than that of other types of
zeolite membranes such as FAU-type zeolite
membrane (SF 20) (Kusakabe et al. 1997),
MFI-type zeolite membrane (SF 16) (Lovallo
et al. 1998), SAPO-34-type zeolite membrane
(SF 30) (Poshusta et al. 2001), and LTA-type
zeolite membrane (SF 0.5) (Aoki et al. 1998).
Apart from its high potential in CO2/CH4 separa-
tion application, all-silica DDR membranes are
also a good candidate for the separation of nitro-
gen/methane (SF 20-45), carbon dioxide and
nitrous oxide/air (SF 20-400), and air/krypton
(SF 5-10) (Bergh et al. 2008).
section (Tomita et al. 2004). Reprinted with permission
from ref. Tomita et al. 2004. Copyright 2016, Elsevier
References
Aoki K, Kusakabe K, Morooka S (1998) Gas permeation
properties of A-type zeolite membrane formed on
porous substrate by hydrothermal synthesis, Journal
of Membrane Science 141:197–205
Bergh JVD, Zhu W, Gascon J, Moulijn JA, Kapteijn F
(2008) Separation and permeation characteristics of
a DD3R zeolite membrane. J Membr Sci
2008(316):35–45
Gies H (1986) Studies on clathrasils.9. Crystal-structure of
deca-dodecasil 3R, the missing link between zeolites
and clathrasils. Z Kristallogr 175:93–104
Hedlund J (1998) Thin films of molecular sieves. PhD
Thesis. Lulea University of Technology, Sweden
Kuhn J, Yajima K, Tomita T, Gross J, Kapteijn F (2008)
Dehydration performance of a hydrophobic DD3R
zeolite membrane. J Membr Sci 321:344–349
Kusakabe K, Kuroda T, Murata A, Morooka S (1997)
Formation of A Y-Type Zeolite Membrane on a
Porous alpha-Alumina Tube for Gas Separation,
Industrial & Engineering Chemistry Research,
36:649–655
Lovallo MC, Gouzinis A, Tsapatsis M (1998) Synthesis
and characterization of oriented MFI membranes pre-
pared by secondary growth. AIChE Journal
44:1903–1913.
Poshusta JC, Noble RD, Falconer JL (2001) Characteriza-
tion of SAPO-34 membranes by water adsoprtion,
Journal of Membrane Science 186:25–40
Tomita T, Nakayama K, Sakai H (2004) Gas separation
characteristics of DDR type zeolite membrane. Micro-
porous Mesoporous Mater 68:71–75
Zhu W, Kapteijn F, Moulijn JA, Exter MCD, Jansen JC
(2000) Shape selectivity in adsorption on the all-silica
DD3R. Langmuir 16:3322–3329
S
Silver Recovery by Bulk Liquid
Membrane (BLM)
Argurio Pietro
Department of Environmental and Chemical
Engineering, University of Calabria, Arcavacata
di Rende (CS), Italy
The occurrence of silver in the natural water
environment is of great relevance owing to its
toxicity to aquatic plants and animals even at
very low concentration, particularly when it is
in the free ion form (Ag+). Silver content into
the aquatic environment has increased in the last
years owing to its increasing use in the medical
and photographic-imaging industry and in the
manufacturing of electronics, silverware, and
jewelry. An estimated amount of 150 tons of
silver is released into the aquatic environment
every year. As a result, separation and recovery
of silver from industrial wastewaters is of great
importance (Altin et al. 2010).
Conventional separation process includes pro-
cesses like solvent extraction, chemical precipi-
tation, adsorption, and membrane filtration.
These techniques efficiently remove metal ions
producing water within international health stan-
dards, but present some limitations: (i) large
amount of solvent required when dilute solutions
were processed, making solvent extraction not
very cheap and safe, since the used solvents are
often chlorinated and sometimes carcinogenic;
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_538-6
(ii) production of a large amount of toxic chem-
ical sludge in which disposal/treatment is a very
costly affair and it is not eco-friendly; (iii) poor
process selectivity, thus metal recovery is not
achieved; (iv) adsorption-based processes are
not continuous, requiring regeneration steps that
negatively affect process economy.
Carrier-mediated transport through liquid
membrane (LM) has been recently considered
as one of the most powerful technology to con-
centrate, separate, and recover metal ions from
diluted solutions. LM-based separation tech-
niques combine extraction and stripping into a
one-step process, thus having great potential for
reducing the solvent inventory requirement and
also allowing the use of expensive and highly
selective extractant (Molinari and Argurio
2009). The lower capital and operating costs,
the low energy consumed, and the high selectiv-
ity are the main advantages of LM systems.
Thanks to these characteristics, LM-based tech-
niques permit to obtain the recovery of heavy
metal ions and the production of water with
good quality, resulting into both environmental
and economic benefits.
LM-based process includes bulk liquid mem-
brane (BLM), emulsion liquid membrane (ELM),
and supported liquid membrane (SLM). BLM
usually consists of two aqueous phase (feed and
strip) separated by a water-immiscible liquid
membrane phase (Molinari and Argurio 2011).
Usually the organic solvents, employed as LM
phase, are pre-saturated with water by shaking a
2 Silver Recovery by Bulk Liquid Membrane (BLM)
Feed Liquid membrane
L
Ag+
CI−
(AgL)CI
Ag+ Ag+
CI− CI−
Silver Recovery by Bulk Liquid Membrane (BLM),
Fig. 1 Facilitated coupled cotransport for Ag(I) transfer
across a liquid membrane
two-phase mixture and then removing the aque-
ous phase.
N,N-diethyl-N0 -camphanyl thiourea is a very
efficient carrier that showed very selective Ag
(I) extraction and transport in the presence of
Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb
(II) using the pH gradient method (Berhe
et al. 2006). The aqueous feed phase pH, higher
than that one of the strip phase, is usually lower
than 5 to avoid metal hydroxides precipitation.
The strip phase usually consists of an acid (e.g.,
HNO3) dissolved in deionized water. The main
operating parameters affecting transport selectiv-
ity are the operating pH and the carrier/metal
ratio. It was found that process selectivity
decreases by increasing the carrier concentration
in the LM phase.
Macrocyclic ligands (e.g., crown) represent a
promising class of complexing agents tested in
the previous years in silver recovery by BLM
(Rounaghi et al. 2008, 2011). In this case the Ag
(I) is transported from the feed aqueous phase to
the strip phase by the so-called facilitated
coupled cotransport (Fig. 1). At feed-LM inter-
face (Fig. 1), the carrier L extracts both Ag+ ion
and the counterion CI- by the reversible reaction
(1):
Strip Agþ ðaqÞ þ CI ðaqÞ þ LðorgÞ
, ðAgLÞ CIðorgÞ (1)
Ag+
The so formed complex diffuses through the
membrane towards the stripping solution where
the de-complexation reaction takes place, and CI-
and Ag+ ions are released. The so regenerated
CI− carrier molecule diffuses back to the feed, and
the transport cycle begins again (Fig. 1).
Thiosulfate (Rounaghi et al. 2008), cyanide, or
sulfite ions or other ligands can be used as strip-
ping agent to improve the permeating flux. Ag+
ions released in the strip phase react with the
ligand to form a complex:
Agþ þ S2 O3 2 , ½AgS2 O3  (2)
This reaction facilitates the release of Ag+ ions
from the LM phase into the strip phase that usu-
ally is the rate determining step of the membrane
transport. The permeating flux largely depends
on the nature and concentration of the stripping
ligand: for Ag+, recovery by BLM with
dibenzopyridino-18-crown-6 and the presence
of thiosulfate as stripping reagent in the strip
phase caused an evident enhancement in trans-
port efficiency.
References
Altin S, Yildirim Y, Altin A (2010) Transport of silver
ions through a flat-sheet supported liquid membrane.
Hydrometallurgy 103:44–149
Berhe HG, Bourne SA, Bredenkamp MW, Esterhuysen C,
Habtu MM, Koch KR, Luckay RC (2006) High and
selective Ag(I) bulk liquid membrane transport with N,
N-diethyl-N’-camphanyl thiourea and structure of the
complex. Inorg Chem Commun 9:99–102
Molinari R, Argurio P (2009) Membrane processes based
on complexation reactions of pollutants as sustainable
wastewater treatments. Sustainability 1:978–993
Molinari R, Argurio P (2011) Recent progress in
supported liquid membrane technology: stabilization
and feasible applications. Membr Water Treat
2:207–223
Silver Recovery by Bulk Liquid Membrane (BLM)
Rounaghi GH, Kazemi MS, Sadeghian H (2008) Trans-
port of silver ion through bulk liquid membrane using
macrocyclic and acyclic ligands as carriers in organic
solvents. J Incl Phenom Macro 60:79–83
3
Rounaghi GH, Hosseiny MS, Chamsaz M (2011) Study of
competitive transport of metal cations through bulk
liquid membrane using 40-nitrobenzo-18-crown-6
and diaza-18-crown-6. J Incl Phenom Macro
69:221–229
S
Solid Electrolyte
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Solid electrolytes (SE) also termed “superionic
solids” or “fast ion conductors” are solid state
ionic materials exhibiting an exceptionally high
ionic conductivity, in the range of ionic conduc-
tivities of liquid/aqueous electrolytes (Agrawal
and Pandey 2008). They found applications in
different electrochemical systems, like batteries
and fuel cells, since their use eliminates leakage
problems associated with liquid electrolytes and
improves system safety and durability. In electro-
chemical systems, (see “▶ Electrochemical
Processing”) in addition to charge transport,
solid electrolytes serve as separators, i.e., mem-
branes as well.
In general, there are two classes of these mate-
rials: inorganic ceramics and organic polymers.
In the case of ceramic solid electrolytes, the ionic
conduction relies on movement of ionic point
defects, which usually implies high ionic conduc-
tivity only at elevated temperatures. Examples of
these materials utilizing O2 ion as a charge
carrier are yttria stabilized zirconia (YSZ),
scandia stabilized zirconia (ScSZ), as well as
perovskite materials such as Sr/Mg-doped
lanthan gallat (LSGM) (Sunmdacher
et al. 2005). These materials have found an
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_542-2
application in high temperature fuel cells and
electrolyzers. In addition to oxygen ion conduc-
tors, proton conductors and Li-ion conductors are
interesting for technical applications. The Li+ ion
conductors have importance for development of
Li-ion batteries. Among these materials,
Li1+xAlxGe2-x(PO4)3 (LAGP) showed so far the
best conductivity (Fergus).
Solid polymer electrolytes are an ion
conducting membranes with ionic conductivity
above 10 7 S cm 1 at room temperature
(Agrawal and Pandey 2008). For technical appli-
cations conductivities higher than 10 4 S cm 1 at
room temperature, in addition to chemical and
thermal stability, the capacity to be manufactured
in thin-sheets and low permeability for reactants/
products are favored. Solid polymer electrolytes
can be roughly classified into three groups: dry
solid polymer electrolytes, polymer gel electro-
lytes, and polyelectrolytes. In the first group,
polymer itself serves as a solvent, solvating
ionic salts into a polymer host. An example is
poly(ethylene)oxide which is effective in solvat-
ing lithium salts for application in Li-ion batte-
ries. In the second group, organic or inorganic
liquid electrolyte is incorporated into the polymer
matrix forming a polymer gel electrolyte. Exam-
ple is poly(benzimidazole) doped with phospho-
ric acid, which found an application in high
temperature fuel cells and poly(methyl methac-
rylate) (PMMA) and poly-acrylonitrile (PAN)
cross-linked with lithium or sodium salts with
applications in batteries. Third group makes
2 Solid Electrolyte
so-called polyelectrolytes. They are macromole-
cules which upon placing into water or other
ionizing solvent dissociate into highly charged
polymeric molecules. An example is sulfonated
tetrafluoroethylene based fluoropolymer-
copolymer commercially (Nafion ®) by DuPont
which found an application in low temperature
fuel cells and electrolysers.
References
Agrawal RC, Pandey GP (2008) Solid polymer electro-
lytes: materials designing and all solid-state battery
applications: an overview. J Phys D Appl Phys
41:223001
Fergus JW (2010) Ceramic and polymeric solid electro-
lytes for lithium-ion batteries. Journal of Power
Sources 195:4554–4569
Sunmdacher K, Rihko-Struckmann L, Galvita V (2005)
Solid electrolyte membrane reactors: status and trends.
Catal Today 104:185–199
S
Solid Electrolyte Membrane Reactor
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Solid electrolyte membrane reactor is a type of
an electrochemical reactor which utilizes a solid
electrolyte (an ion-conducting membrane) as an
ion-conducting medium and a separator
(Sundmacher et al. 2005). These reactors found
an application in electrochemical processing.
Examples are fuel cells, batteries, and
electrolyzers. Electrochemical oxidation and
reduction reactions in solid electrolyte mem-
brane reactor take place in porous electrodes
which are usually directly applied on different
sides of the solid electrolyte. These electrodes
are complex composite structures which have to
fulfill different requirements. They should pos-
sess catalytic activity such that electrochemical
reactions can take place; they should be able to
conduct electrons and ions which are released or
consumed in electrochemical reactions, and they
should transport non-charged reactants or prod-
ucts of reactions to or away from the reaction site.
In practice it is difficult to satisfy all these
requirements. Currently so-called gas diffusion
electrodes which found major application in fuel
cells and electrolyzers show practically the best
balance of mentioned requirements. Gas diffu-
sion electrodes are usually prepared by mixing
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_543-2
of a solid electrolyte, with an inert electron-
conducting phase (e.g., carbon nanomaterials
for low-temperature applications) and catalyst
particles (e.g., platinum).
In fuel cells the main goal of operation is
conversion of chemical energy of a fuel, typically
hydrogen or hydrocarbons into electrical energy
with high efficiency. Fuel cells work in a wide
temperature range (25–1000  C), for which dif-
ferent solid electrolytes (ceramics or polymers,
see solid electrolytes) are used. Typical examples
are solid oxide fuel cells which utilize ceramic
oxygen ion-conducting membrane (e.g., yttria-
stabilized zirconia) and polymer electrolyte fuel
cell where polymer proton-conducting mem-
brane (e.g., sulfonated tetrafluoroethylene-based
fluoropolymer-copolymer, commercially
Nafion® by DuPont) is used.
Similar to fuel cells, in batteries the main goal
of operation is efficient conversion of stored
chemical energy into electrical energy. One
example is lithium-ion polymer battery. This
type of battery exhibits up to date the highest
energy density of all batteries (380 Wh kg 1)
and allows a great variety of geometries as well
as thicknesses of about 1 mm, which has found
wide commercial application in cell phones and
laptop computers.
Unlike electrochemical energy-conversion
devices (fuel cells and batteries), the main pur-
pose of electrolyzers is high production rate of a
specific product at high selectivity and low
energy consumption. In some cases the desired
2 Solid Electrolyte Membrane Reactor

product and electrical power can be cogenerated. References

A detailed survey of applications of high-
temperature solid electrolyte membrane reactors Garagounis I, Kyriakou V, Anagnostou C, Bourganis V,
Papachristou I, Stoukides M (2011) Solid electrolytes:
for production of different industrially relevant
applications in heterogeneous catalysis and chemical
products is presented in Garagounis et al. 2011. cogeneration. Ind Eng Chem Res 50:431–472
Although in some cases notable advantages of Sundmacher K, Rihko-Struckmann L, Galvita V (2005)
solid electrolyte membrane reactors in compari- Solid electrolyte membrane reactors: Status and
trends. Catal Today 104:185–199
son to conventional catalytic reactor have been
identified, this technology still did not reach com-
mercial stage.
S
Solvent-Resistant Nanofiltration
Sanne Hermans and Ivo Vankelecom
Centre for Surface Chemistry and Catalysis,
Department of M2S, Faculty Bioscience
Engineering, KU Leuven, Leuven, Belgium
Synonyms
Organic solvent nanofiltration (OSN)
Solvent-resistant nanofiltration (SRNF) is a
pressure-driven technique to realize separations
up to the molecular level in solvent streams
(Vandezande et al. 2008). Small solvent mole-
cules will permeate through the membrane, while
solutes (with a molecular weight between
200 and 1000 Da) will be retained. Applications
are widespread and mainly found in the (petro)
chemical, pharmaceutical, and food industry.
A good SRNF membrane is characterized by an
excellent performance (high flux as well as high
selectivity); long-term mechanical, chemical, and
thermal stability; low fouling tendency; and a
cost-effective and defect-free production.
Both ceramic and polymeric membranes can
be applied in SRNF. Ceramic membranes are
often synthesized from alumina, zirconia, or tita-
nia. Considering chemical, thermal, and physical
stability, these membranes are most robust. They
are able to combine a good selectivity with a long
lifetime. However, ceramic membranes are
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_548-3
expensive due to a complicated large-scale
production process, rather brittle and intrinsically
hydrophilic (low flux in apolar solvents unless
surface treated). Therefore, polymeric mem-
branes are considered to be the most interesting
material for SRNF applications. Advantages are
the large variety of available polymers, their rel-
atively low price, and the ease of processing and
upscaling. An important issue with polymeric
membranes is their limited thermal and chemical
stability. Interactions between organic solvent and
membrane can cause these membranes to swell
extensively (or even dissolve) resulting in loss of
selectivity. Cross-linking of the membrane matrix
is often performed to increase the polymer stabil-
ity in strong solvents (e.g., dimethylformamide).
Cross-linking can be achieved chemically, ther-
mally, or by irradiation (UV, plasma). Typical
cross-linked polymers for SRNF are polyimide,
polydimethylsiloxane, and polyacrylonitrile.
Polymeric membranes mostly have an asym-
metric structure consisting of a thin, dense top
layer on a porous support. They can be divided
into two categories: integrally skinned and com-
posite materials (Peeva et al. 2010). The first are
synthesized via phase inversion, in which a poly-
mer film is transformed from a liquid to a solid
state in a controlled manner. The latter consist of
two different materials, where the porous support
is often prepared via phase inversion, while the
dense layer is put on top via a different technique
(e.g., dip or spin coating, interfacial polymeriza-
tion, grafting).
2 Solvent-Resistant Nanofiltration

Solvent-Resistant Nanofiltration, Table 1 Suppliers of commercial SRNF membranes and their products (as in
October 2012)
Company Membrane Material Stability range MWCO
Evonik DuraMem ® Lenzing P84® Acetone, ethanol, methanol, 150–900 Da
(Germany)a polyimide tetrahydrofuran, dimethylformamide*,
(*cross- dimethyl sulfoxide*,
linked) dimethylacetamide*, isopropanol,
acetonitrile, methyl ethyl ketone, ethyl
acetate, and more
PuraMem ® Lenzing P84® Toluene, heptane, hexane, methyl ethyl 280–600 Da
polyimide ketone, methyl isobutyl ketone, ethyl
acetate, and more
SolSep BV (the SolSep UF Diverse Alcohols, aromatics, esters, ketones, 10,000–20,000 Da
Netherlands)b (unspecified) chlorinated solvents
SolSep NF Diverse Methanol, ethanol, propanol, acetone, 300–750 Da
(unspecified) ethyl acetate, hexane, toluene,
chlorobenzene
Borsig GMT-oNF PDMS-based Alkanes, alcohols, aromatics, ethers, Unspecified
Membrane composites esters, ketones
Technology
(Germany)c
Inopor ® Inopor ® TiO2, SiO2 Unspecified 450–750 Da
(Germany)d nano
a
http://duramem.evonik.com/product/duramem-puramem/en/Pages/default.aspx
b
http://www.solsep.com/
c
http://mt.borsig.de/
d
http://www.inopor.com/en/index.html

Transport through SRNF membranes is com-
plex due to the interactions between solvent, sol-
ute, and membrane (e.g., swelling). Two models
are often applied to describe the transport mech-
anism but also the combination of both appears.
For loose SRNF membranes, the pore-flow model
is used while the solution-diffusion model is
applied for dense SRNF membranes. Both take
into account membrane properties, which can vary
depending on the feed characteristics. This implies
that the same membrane can behave as loose in
one solvent and as dense in another solvent.
Currently, only a limited number of compa-
nies supply commercial SRNF membranes (listed
in Table 1). In the past, Koch Membrane Systems
(USA) was another producer of SRNF mem-
branes (MPF series), but they ceased their
SRNF production. Together with StarMem
(MET-Evonik, previously Membrane Extraction
Technology), the MPF membranes were the first
commercially available SRNF membranes, mak-
ing them the subject of many studies. Evonik,
SolSep, and Borsig offer polymeric membranes
in flat sheet form or spiral-wound modules. Inopor
supplies ceramic mono- and multichannel tubes.
Cross-References
▶ Organic Solvent Nanofiltration
▶ Organic Solvent Nanofiltration Technique
▶ Organic Solvent-Resistant (OSR) Membrane
▶ Solvent Filtration
References
Peeva LG, Sairam M, Livingston AG
(2010) Nanofiltration operations in nonaqueous sys-
tems. In: Drioli E, Giorna L (eds) Comprehensive
membrane science and engineering, vol 2, 1st edn.
Elsevier, Oxford, pp 91–113
Vandezande P, Gevers LEM, Vankelecom IFJ (2008) Sol-
vent resistant nanofiltration: separating on a molecular
level. Chem Soc Rev 37(2):365–405
S
Spray Coating
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Pakistan
Coating
A coating is applied to the surface of an object to
protect it from environmental effects or to
enhance its surface properties such as appear-
ance, corrosion resistance, wear resistance,
scratch resistance, adhesion, wettability, dielec-
tric property, electrical conductivity, etc. The
object to be coated may also be referred as sub-
strate. In some cases, the coatings act as an essen-
tial part of the finished product such as in the case
of semiconductor devices fabrication where the
substrate material is silicon wafer.
Coatings may be applied as liquids, gases, or
solids. “The coating which is applied on an object
with a liquid spray is known as spray coating.”
Suspension and solution thermal spraying are
the emerging methods of coating (Pawlowski
2009). Thermal spraying is a process that utilizes
thermal energy to melt material in powder, wire, or
rod form followed by providing kinetic energy to
the molten or semi-molten material to propel it
toward a prepared surface by expanding process
gases. The impact of these molten or semi-molten
particles on the surface of substrate creates a
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_552-1
coating buildup called spray coating. Thermal
spraying could be achieved by various techniques
including:
Plasma Coating
In plasma spray method, plasma gas such as argon/
hydrogen or argon/hydrogen is heated by an arc
between the two electrodes. This heating process
causes expansion of plasma gas which accelerated
through a shaped nozzle, creating very high veloc-
ity. Temperature of the plasma gas in the arc zone
approaches about 20,000 K which remains up to
10,000 K even after exiting from the nozzle for
several centimeters. This stream carries the coat-
ing material in molten form and applies to the
substrate. Plasma spray coatings are commonly
used in jet engines where it provides high-
temperature protection to the parts which are
exposed to combustion gases. This increases the
life and efficiency of the system.
Electric-Arc Spray
An electric arc is created when two conductive
wires carrying charges of opposite polarity meet
in front of spray device. This electric arc melts the
wires which are acting as feedstock for coating.
Electric-arc spraying technique has the fastest
coating rates among coating technologies. Flame
or plasma is not involved in this coating technique
2 Spray Coating
which significantly reduces the heat transfer to the
substrate material, making the process thermally
efficient. The electric-arc spray is commonly used
in the automotive industry and to coat large
objects such as bridges with aluminum and zinc
which provide corrosion resistance properties.
High-Velocity, Oxy-Fuel (HVOF) Coating
HVOF utilizes an extended nozzle to heat and
accelerate the coating material. Typical HVOF
devices operate at hypersonic gas velocities
which provide kinetic energy helping to produce
dense and well-adhered coatings. HVOF coatings
can be used for coating the high-tech medical
devices and coating of carbide material to bolts
used in agricultural machine which greatly
extends the life of the bolt.
Flame Spray
Flame spray uses combustion of gases to melt
powder, wire, or rod material and propels the
molten droplets onto a surface to create a coating.
Flame coatings are commonly used for materials
requiring good wear resistance and excellent
impact resistance such as agricultural harvesting
components, oil-drilling parts, etc.
Cold Spray
Cold spray is technically not a thermal spray
process since it does not use thermal energy as
the primary energy source. In cold spraying,
particles are accelerated to very high speeds
by the carrier gas forced through a
converging–diverging de Laval type nozzle.
High-energy impact of feedstock solid particle
causes plastically deformation of particles at
substrate surface which subsequently bond
metallurgically to the substrate to form a coating.
The velocity is an important parameter to
obtain such coating, and critical velocity value
for bonding depends on the material properties
such as nature of feedstock, powder size, and
temperature. Some hard materials are also
reported, but soft metals such as Cu and Al are
best suited for cold spraying process (Seiji
et al. 2008).
References
Pawlowski L (2009) Suspension and solution thermal
spray coatings. Surf Coat Technol 203:2807–2829
Seiji K, Jin K, Makoto W, Hiroshi K (2008) Warm
spraying–a novel coating process based on high-
velocity impact of solid particles. Sci Technol Adv
Mater 9(3):033002 (17pp)
S
Static Membrane Emulsification
Emma Piacentini1, Alessandra Imbrogno1 and
Richard G. Holdich2
1
Institute on Membrane Technology
(ITM-CNR), University of Calabria, Rende (CS),
Italy
2
Department of Chemical Engineering,
Loughborough University, Loughborough,
Leicestershire, UK
Static membrane emulsification (ME) refers to
the formation of emulsion droplets by extruding
the dispersed phase through the membrane pores
into the continuous phase in the absence of sur-
face shear (Fig. 1).
In the absence of shear flow at the membrane
surface, the main forces acting on the droplets
forming at the membrane pore level are (see
Fig. 2):
• The interfacial tension (or capillary) force (Fg)
(retaining force) that represents the effect of
the dispersed phase adhesion on the pore
opening. It is a function of the dynamic inter-
facial tension g(t). This force is typically
assumed to be determined by the Young-
Laplace equation with the continuous phase
assumed to fully “wet” the membrane surface.
Surfactant type and concentration greatly
influence the adsorption kinetics of the surfac-
tant and thus the dynamic interfacial tension
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_553-1
between the two liquid phases. During the
droplet formation process, the surfactant mol-
ecules adsorb to the newly formed oil-water
interface reducing the interfacial tension and
facilitating droplet formation. The transfer
rate of the surfactant molecules from bulk
solution to the newly formed oil-water inter-
face is mainly determined by their diffusional
transfer because of the absence of continuous-
phase flow.
• The buoyancy force (FBG) due to the density
difference between continuous phase (rc) and
dispersed phase (rd) and influenced by the
volume of droplet (Vd). It is a detaching
force which counteracts the interfacial tension
force or capillary force.
• “Push-off” or “push-to-detach” force (G), that
is, an additional detaching force applicable
when there are a large number of drops at the
membrane surface causing drops to deform
from their thermodynamically more stable
spherical shape. The contribution of this addi-
tional force is likely to be more noticeable
with a regular array membrane, such as
micro-sieve metallic membrane with highly
uniform pore spacing and pore size compared
to conventional membranes such as the
Shirasu porous glass (SPG) type.
The dispersed phase flux has a great influence
on the spontaneous droplet formation behavior
and depends on the viscosities of disperse and
2 Static Membrane Emulsification
Static Membrane
Emulsification,
Fig. 1 Static membrane
emulsification
continuous phases and flow velocity of the dis-
perse phase through the membrane pore. The
push-off force occurs when a critical injection
rate is exceeded and all, or nearly all, of the
membrane pores become active. In this condition,
a large number of drops grow simultaneously at
the membrane surface, and the drop diameter is
bigger than the distance between the pores, so
that the drops push each other off at the mem-
brane surface. In the limiting case, when only
relatively few pores are active and the distance
between those pores is bigger than the size of the
Static Membrane Emulsification, Fig. 2 Forces acting
on the droplets forming at the membrane pore level in
static membrane emulsification
drops, the push-off force is zero and final drop
size is defined only by an equilibrium of buoy-
ancy and capillary forces (interfacial tension). At
increasing injection rate, more and more pores
will be activated and the push-off force becomes
significant (Kosvintsev et al. 2008).
Another parameter affecting the droplet
detachment from the pore openings is the shape
of the pore openings: noncircular pore openings
encouraging the spontaneous detachment of
droplets. During droplet formation from tortuous
pores with a noncircular cross section, the
distorted dispersed phase is spontaneously
transformed into spherical droplets by interfacial
tension at the membrane surface because of the
minimization of the interfacial free energy of the
system. This phenomenon has been observed
with SPG membranes (Sugiura et al. 2001;
Christov et al. 2002).
The static ME has several advantages over
dynamic ME:
1. Simple experimental setup
2. Low energy input
3. Suitable for the production of less viscous
and/or larger droplets with uniform size
because droplet breakup due to the shear
force caused by a cross-flow pump is avoided
References
Christov NC, Ganchev DN, Vassileva ND, Denkov ND,
Danov KD, Kralchevsky PA (2002) Capillary
Static Membrane Emulsification
mechanisms in membrane emulsification: oil-in-water
emulsions stabilized by tween 20 and milk proteins.
Colloids Surf A 209:83–104
Kosvintsev SR, Gasparin G, Holdich RG (2008) Mem-
brane emulsification: droplet size and uniformity in the
absence of surface shear. J Membr Sci 313:182–189
3
Sugiura S, Nakajima M, Iwamoto S, Seki M (2001) Inter-
facial tension driven monodispersed droplet formation
from microfabricated channel array. Langmuir
17:5562–5566
S
Strip Dispersion Supported Liquid
Membrane
Argurio Pietro
Department of Chemical and Environmental
Enginnering, University of Calabria, Arcavacata
di Rende (CS), Italy
A liquid membrane (LM) is a thin liquid film that
separates two other liquid phases with which it is
immiscible. There are three basic forms of LM
processes: bulk liquid membrane (BLM), emul-
sion liquid membrane (ELM), and supported liq-
uid membrane (SLM) (Molinari and Argurio
2009). The small membrane surface area per
unit volume represents the most important draw-
back of BLMs, making them not attractive by a
technological point of view. ELMs are character-
ized by a large surface area per unit source phase
volume, which enhances the transport rate. One
disadvantage of ELMs is the low emulsion sta-
bility, so that if for any reason the membrane does
not remain intact during operation, the separation
achieved to that point is destroyed. SLMs usually
consist of an organic solvent impregnated in the
pores of a hydrophobic microfiltration membrane
(Molinari and Argurio 2011). SLM combines
extraction and stripping processes into one single
step, which provides the maximum driving force
for the separation of a target species. SLM has
many advantages over traditional separation
technologies such as solvent extraction including
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_556-5
high selectivity, low carrier and solvent con-
sumption, high degree of concentration enrich-
ment, and so on. Despite the abovementioned
advantages, SLMs are not currently used on a
large scale in the industry, since membrane sta-
bility or lifetime is, in general, far too low to
assure good commercial applications. Instability
of SLMs is due to the loss of carrier and/or mem-
brane solvent from the membrane phase which
has an influence on both flux and selectivity of the
membrane (Kemperman et al. 1996). In addition,
the flux of solute through SLM is lower because
of the higher resistance of mass transfer from the
presence of static membrane solution filled in
microporous supports.
For solving the above difficulties and
obtaining LM system with high efficiency, new
configurations have been proposed. Ho (2002)
and Teramoto et al. (2000) proposed a combined
SLM/strip dispersion process (i.e., the strip solu-
tion was dispersed in the membrane organic
phase) for the removal and recovery of target
species from a feed solution. This new LM con-
figuration has several advantages: (i) increased
stability, (ii) reduced costs, (iii) increased sim-
plicity of operation, (iv) extremely efficient strip-
ping of the target species from the organic phase,
and (v) high flux and a high concentration of the
recovered target species in the aqueous strip solu-
tion. An important limitation of SLM with strip
dispersion system is represented by impossibility
to avoid the pollution of the aqueous solutions
with membrane solution due to its dissolution in
2 Strip Dispersion Supported Liquid Membrane

Hydrophobic membrane support

with organic solution in the pores

Feed phase

Strip phase

Phase Mixer
(organic + strip)

Organic phase

Continuous organic phase

Dispersed droplets of
strip phase Strip pump
Feed pump

Strip Dispersion Supported Liquid Membrane, Fig. 1 Schematization of the combined supported liquid mem-
brane/strip dispersion system (elaborated from He et al. (2006))

both aqueous feed and strip solutions. In this
context, the choice of membrane solution with
water-insoluble components is a key step.
The combined SLM/strip dispersion system
can be schematized as reported in Fig. 1: a micro-
porous hydrophobic support (e.g., polypropyl-
ene) acts as the liquid membrane support. The
strip dispersion is a mixture of an aqueous strip
phase, containing a stripping agent, and an
organic phase containing an extractant. During
the extraction process, the dispersion flows
through one side of the SLM. A feed solution
containing the target species is passed on the
other side of the SLM.
In 2006, He et al. studied the recovery of Zn
(II) ions by using the SLM/strip dispersion sys-
tem. The influence of various experimental
parameters on the separation of binary Zn
(II) and Cu(II) ions, that is, system of great
importance to hydrometallurgy and environmen-
tal protection, was investigated. Obtained results
evidenced that this new configuration of LM is
applicable in the separation and recovery of sol-
utes from aqueous solutions.
The same LM configuration, called strip dis-
persion hybrid liquid membrane (SDHLM), was
studied by Gu et al. (2006) for the transport and
separation of Cd(II) from Zn(II) ions from aque-
ous media. The results evidenced that cadmium
(II) can be effectively transported into the strip-
ping solution from the feed phase by the
SDHLM using tri-n-octylamine-secondary
octanol in kerosene as carrier. The proposed
system has superiority over SLMs and ELMs in
terms of: (i) transport rate, since the efficient
contact area between organic and stripping solu-
tion results in an extra mass transfer surface;
(ii) permeability coefficient and extraction or
recovery percentage of Cd(II); (iii) efficiency
of uphill transport; (iv) membrane stability;
and (v) no usage of high active surfactant and
demulsification device.
Strip Dispersion Supported Liquid Membrane
A hollow fiber supported liquid membrane
(HFSLM) with strip dispersion was tested by Li
et al. (2009) in the recovery of fumaric acid from
aqueous effluents. Under the optimum operating
conditions, the extraction of fumaric acid was
89.5 %, and the total TOC removal reached
96.5 %. Compared with the results obtained
with SLM, the extraction was enhanced by
26.6 % and the TOC removal by 9.5 %. Besides,
no significant loss of the membrane phase was
observed, and the stability of the HFSLM with
strip dispersion system was remarkably good.
A not negligible pollution of the aqueous solu-
tions with membrane solutions was observed, so
that the author concluded that further research
needs to be carried out to solve this important
issue.
More recently (Vilt and Ho 2009, 2011), SLM
with strip dispersion has been applied to the
recovery of cephalexin, an important and widely
used semisynthetic antibiotic traditionally pro-
duced by a ten-step chemical synthesis. An enzy-
matic synthesis for cephalexin, offering several
advantages over the classical route, has been
developed, but it requires an in situ extraction
which ensures enzyme stability. Obtained results
evidenced that yield of cephalexin was increased
from 32 % to 42 % when in situ removal was
conducted using two hollow fiber modules and an
organic membrane solution containing 10 wt.%
Aliquat 336. Enzyme stability experiments
showed that the organic membrane solution did
not significantly deactivate the enzyme. The final
recovery of cephalexin from aqueous stripping
solutions was achieved using complexing agents.
3
References
Gu S, Yu Y, He D, Ma M (2006) Comparison of transport
and separation of Cd(II) between strip dispersion
hybrid liquid membrane (SDHLM) and supported liq-
uid membrane (SLM) using tri-n-octylamine as car-
rier. Sep Purif Technol 51:277–284
He D, Luo X, Yang C, Ma M, Wan Y (2006) Study of
transport and separation of Zn(II) by a combined
supported liquid membrane/strip dispersion process
containing D2EHPA in kerosene as the carrier. Desa-
lination 194:40–51
Ho WSW (2002) Combined supported liquid membrane/
strip dispersion process for the removal and recovery
of metals. US Patent 6,350,419
Kemperman AJB, Bargeman D, van Den Boomgaard T,
Strathmann H (1996) Stability of supported liquid
membranes: state of the art. Sep Sci Technol
31:2733–2762
Li S-J, Chena H-L, Zhang L (2009) Recovery of fumaric
acid by hollow-fiber supported liquid membrane with
strip dispersion using trialkylamine carrier. Sep Purif
Technol 66:25–34
Molinari R, Argurio P (2009) Membrane processes based
on complexation reactions of pollutants as sustainable
wastewater treatments. Sustainability 1:978–993
Molinari R, Argurio P (2011) Recent progress in
supported liquid membrane technology: stabilization
and feasible applications. Membr Water Treat
2:207–223
Teramoto M, Sakaida Y, Fu SS, Ohnishi N, Matsuyama H,
Maki T, Fukui T, Arai K (2000) An attempt for the
stabilization of supported liquid membrane. Sep Purif
Technol 21:137–144
Vilt ME, Ho WSW (2009) Supported liquid membranes
with strip dispersion for the recovery of Cephalexin.
J Membr Sci 342:80–87
Vilt ME, Ho WSW (2011) In situ removal of Cephalexin
by supported liquid membrane with strip dispersion.
J Membr Sci 367:71–77
S

Styrene-Grafted Film the nature of base polymer and the degree of

grafting (Sherazi et al. 2008; Hwang et al.
Tauqir A. Sherazi 2015). Another advantage to graft styrene mono-
Department of Chemistry, COMSATS Institute mers is that it contains benzene ring which is
of Information Technology, Abbottabad, readily amenable to some application based
Pakistan functionalization such as sulfonation,
halomethylation, (Gubler et al. 2005; Varcoe
and Slade 2005) etc.
Styrene is an organic compound with the chemi- Many of the polymers have been investigated
cal formula C6H5CH=CH2. Styrene is also for the grafting of styrene and followed by sulfo-
known as vinyl benzene and phenylethene. Due nation to develop membranes for fuel cells appli-
to the presence of vinyl group, styrene can easily cations. Almost all commercially available
be polymerized to polystyrene. Styrene can also fluorinated polymers, such as polytetrafluor-
be used as precursor for several copolymers and oethylene (PTFE) (Ismail et al. 2005), Teflon-
also can be used for graft polymerization or FEP (Saneto et al. 2005), fluorinated ethylene
grafting (see graft polymerization) (Fig. 1). propylene copolymer (FEP) (Nasef et al. 2000),
Styrene is of commercial importance and used tetrafluoroethylene perfluoro(propyl vinyl ether)
in the production of commercially significant
products including polystyrene, styrene-
butadiene rubber (SBR), acrylonitrile butadiene
styrene (ABS), styrene-butadiene latex, styrene-
isoprene-styrene (SIS), styrene-ethylene/
butylene-styrene (S-EB-S), styrene-
divinylbenzene (S-DVB), styrene-acrylonitrile
resin (SAN), and unsaturated polyesters. These
materials are used in rubber, plastic, insulation,
fiberglass, pipes, automobile and boat parts, food
containers, and carpet backing.
The presence of the vinyl group allows styrene
to graft onto base polymer matrix. Styrene-
grafted films could be produced by grafting onto
ready-made polymer films, or films can also be Styrene-Grafted Film, Fig. 1 Chemical structure of
prepared after grafting process depending upon styrene

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_557-1
2 Styrene-Grafted Film
Styrene-Grafted Film,
Scheme 1 Styrene
grafting onto polymer
copolymer (PFA) (Cardona et al. 2002),
polyvinylidene fluoride (PVDF) (Elomaa
et al. 2000), ethylene-tetrafluoroethylene copoly-
mer (ETFE) (Scott et al. 2000), polychlorotri-
fluoroethylene (PCTFE) (Zhao and Jin 1988),
etc., were reported to be used for grafting with
styrene. Styrene-grafted films have also been
developed using polyethylene (Sherazi
et al. 2008, 2009, 2013) as base polymer.
Styrene-grafted and sulfonated poly(ethylene
terephthalate) films were also studied as bioactive
polymers to produce a “biointegrable” artificial
anterior cruciate ligament (ACL) (Ciobanu
et al. 2006). The scheme of styrene grafting
onto polymer to produce styrene-grafted film
can be represented by Scheme 1.
Grafting can be initiated by various methods
including chemical initiator, radiation technique,
etc. (see graft polymerization).
References
Cardona F, George GA, Hill DJT, Aasoul FR, Maeji
J (2002) Copolymers obtained by the radiation-
induced grafting of styrene onto poly
(tetrafluoroethylene-co-perfluoropropylvinyl ether)
substrates. 1. Preparation and structural investigation.
Macromolecules 35:355–364
Ciobanu M, Siove A, Gueguen V, Gamble LJ, Castner
DG, Migonney V (2006) Radical graft polymerization
of styrene sulfonate on poly(ethylene terephthalate)
films for ACL applications: “grafting from” and chem-
ical characterization. Biomacromolecules
7(3):755–760
Elomaa M, Hietala S, Paronen M, Walsby N, Jokela K,
Serimaa R, Torkkeli M, Lehtinen T, Sundholm G,
Sundholm F (2000) The state of water and the nature
of ion clusters in crosslinked proton conducting mem-
branes of styrene grafted and sulfonated poly(vinyli-
dene fluoride). J Mater Chem 10:2678–2684
Gubler L, Gursel SA, Scherer GG (2005) Radiation
grafted membranes for polymer electrolyte fuel cells.
Fuel Cells 5:317–335
Hwang DS, Sherazi TA, Sohn JY, Chang NY, Park CH,
Guiver MD, Lee YM (2015) Anisotropic radio-chem-
ically pore-filled anion exchange membranes for Solid
alkaline fuel cell (SAFC), J Membr Sci, 495:206–215
Ismail AF, Zubir N, Nasef MM, Dahlan KM, Hassan AR
(2005) Physico-chemical study of sulfonated polysty-
rene pore-filled electrolyte membranes by electrons
induced grafting. J Membr Sci 254:189–196
Nasef MM, Saidi H, Nor HM (2000) Proton exchange
membranes prepare d by simultaneous radiation
grafting of styrene onto poly(tetrafluoroethylene-co-
hexafluoropropylene) films. I. Effect of grafting con-
ditions. J Appl Polym Sci 76:220–227
Saneto A, Fumihiro M, Shogo I, Li J, Takaharu M,
Akihiro O, Yosuke K, Masakazu W (2005) Fabrication
of PEFC membrane based on PTFE/FEP polymer-
alloy using radiation-grafting. Nucl Instrum Methods
B 236(437):442
Scott K, Taama WM, Argyropoulos P (2000) Performance
of the direct methanol fuel cell with radiation-grafted
polymer membranes. J Membr Sci 171:119–130
Sherazi TA, Ahmad S, Kashmiri MA, Guiver MD
(2008) Radiation induced grafting of styrene onto
ultra-high molecular weight polyethylene powder and
subsequent film fabrication for application as polymer
electrolyte membranes. I: influence of grafting condi-
tions. J Membr Sci 325:964–972
Sherazi TA, Ahmad S, Kashmiri MA, Kim DS, Guiver
MD (2009) Radiation induced grafting of styrene onto
ultra-high molecular weight polyethylene powder and
subsequent film fabrication for application as polymer
electrolyte membrane. II: sulfonation and characteri-
zation. J Membr Sci 333:59–67
Sherazi TA, Sohn JY, Guiver MD, Lee YM (2013) Poly-
ethylene based anionic exchange membranes for solid
alkaline fuel cells (SAFC). J Membr Sci 441:148–157
Varcoe JR, Slade RCT (2005) Prospects for alkaline
anion-exchange membranes in low temperature fuel
cells. Fuel Cells 5:187–200
Zhao XZ, Jin JL (1988) Study of radiation graft styrene
onto pre-irradiated poly-chlorotrifluoroethylene films.
Radiat Phys Chem 31:805–808
S
Submerged Membrane
A. B. Koltuniewicz
Warsaw University of Technology, Faculty of
Chemical and Process Engineering,
Biotechnology and Bioprocess Engineering
Division, Warsaw, Poland
Synonyms
Submerged flat-sheet module; Zeolite membrane
-characterization
Submerged (immersed) membrane (SM) is an
original idea, representing cheaper alternative to
conventional membrane modules employed in
cross-flow system. SM design involves placing
flat or capillary membranes directly in the tank,
usually vertically (capillary can also be laid hor-
izontally). The air (or other gas) is supplied from
the bottom of the tank. Very small transmem-
brane pressure (below 1 bar) is generated hydro-
statically but often enhanced by a small vacuum.
Although the permeate flux is smaller (up to
35 LMH) compared with the cross-flow, which
requires a larger membrane surface area, but then
power consumption is significantly lower. In con-
ventional cross-flow systems, the feed flows tan-
gentially to membrane surface to reduce the
concentration polarization or to remove cake.
Therefore, conventional (cross-flow) membrane
system solutions consume large amounts of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_558-3
energy to maintain the flux, which often exceeds
10 kWh/m3 for circulation. Moreover, in a typical
membrane modules (especially capillary, spiral,
and flat plates), the requirements as to the mate-
rials combined with a complicated structure
cause additional serious costs. Another important
parameter is the right choice of membrane mate-
rial (chemical compatibility) as well as appropri-
ate pore size distribution. Membranes should
have the narrowest pore size distribution as pos-
sible. There is also a rule that the smaller the pore
size, the smaller is the tendency for the inner pore
blocking, which may be irreversible.
In immersed membrane systems (Fig. 1), the
innovative approach is to take use of the newer
concepts such as critical flux theory or turbu-
lences generated by gas sparging. The role of
gas sparging in submerged membrane is similar
to cross-flow (to facilitate turbulences) but much
more cheaper. The gas flowing between the cap-
illaries or sheets causes reciprocal and gentle
movement that keep the flow of permeate flux
with lower amount of energy (below 3 kWh/m3).
In some cases the costs for periodic
backflushing and/or cleaning of membranes
(CIP cleaning in place) have to be added. This
requires the use of additional expenditure on
chemicals and to dispose and further complicates
the process (automation) and causes the system
downtime. However, during ultrafiltration, only
stopping of the plant, is sufficient for polarizing
layer that spontaneously be dissolved in the core
(bulk) due to back-diffusion. In the
2 Submerged Membrane

Submerged Membrane,
Fig. 1 Submerged
membranes

microfiltration process, the gas sparging gently (expansion and modification) of existing systems.
moves the membranes which cause crushing of Thanks to its numerous advantages, submerged
the filter cake layer. In individual cases, where membranes found itself since its inauguration
possible, it is used in addition to other methods of popularity in the following areas:
cleaning the membranes, such as flushing of the
liquid phase (penetration) or gas phase and chem- • Food industry (beverages, alcohols, dairy)
ical cleaning of various intensities. Thus, the best • Chemical industry
adapted strategies for cleaning the submerged • Electronic
membranes should be adapted for the specific • Mechanics
case. The chemically supported backflushing is • Laundries
used daily, chemical cleaning of high concentra- • Bathing
tion once per week, or intensive chemical • Photo
cleaning annually. • Medicine
The main advantages of SM system should • Agriculture (livestock and aquaculture)
therefore be low investment costs, which result • Wastewater treatment
from a simple and reliable design, easy installa-
tion, and compact size (small footprints). Low
operating costs result from the low power con-
References
sumption, low maintenance costs, and ease of use
and repairs, through continuous monitoring. In Koltuniewicz AB (2010) Integrated Membrane Opera-
addition to these economic advantages, sub- tions in various Industrial Sectors. In: Drioli E and
merged membrane also features high perfor- Giorno L (eds) Membrane Science and Engineering.
mance and high efficiency. Submerged Elsevier 4(1):109–154
membranes can be easily used for retrofitting
S
Submerged Membrane Bioreactor
A. B. Koltuniewicz
Faculty of Chemical and Process Engineering,
Biotechnology and Bioprocess Engineering
Division, Warsaw University of Technology,
Warsaw, Poland
Synonyms
Immersed Membrane Bioreactor (IMBR)
Submerged membrane bioreactors (SMBs) are
a type of membrane bioreactor MBR, where two
processes, i.e., the chemical reaction and separa-
tion, took place simultaneously to produce a syn-
ergistic effect. The first idea of membrane reactor
connection was founded at Rensselaer Polytech-
nic Institute, Troy, New York (Smith et al. 1969).
The first use of MBR to the activated sludge in
wastewater treatment plants has been done by
Dörr-Oliver, Inc., Milford, Connecticut, USA
(Hardt et al. 1970). After several years this idea
was popularized in Japan and developed by
Yamamoto et al. (1989) and the company
KUBOTA, which introduced further integration
in the form of flat sheet membranes immersed
directly in the reactor tank. The first application
of submerged membrane reactor is the sewage
system, which is considerably simplified compar-
ing to conventional (see Fig. 1). The rapid devel-
opment of SMB applications has been caused by
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_559-4
the following: (1) legislation, (2) local water
scarcity, (3) return on investments, (4) environ-
mental impact, and (5) public and politician
acceptance (Judd 2011).
Flat plate or capillary membranes are usually
immersed vertically in a tank where feed is deliv-
ered. The capillary membranes can also be
arranged horizontally (see Table 1). The perme-
ate is discharged by means of collectors on the
outside of the tank under hydrostatic pressure or
light vacuum using a pump. The integration of
membrane and reactor introduces well-known
benefits, such as accelerating the kinetics of the
process and increasing its efficiency. Continuous
removal of the products from the reaction space
and the retention of the substrates shifts the equi-
librium to the right (toward product), thus
increasing the efficiency of the process. In this
case, the membrane also helps to avoid adverse
reactions, which can lead to transient products.
Submerged membrane bioreactors are much
more cost-effective when compared to conven-
tional cross-flow membrane modules (see
Table 1).
The role of the costly cross-flow has been
replaced in SMB by mild hydrodynamic condi-
tions, where gas sparging is often used (see
Fig. 2). For this purpose, the gas is supplied
from the bottom so as to flow over the surface
of the membrane. The role of gas sparging in
submerged membrane bioreactors is twofold,
i.e., hydrodynamics and mass transfer enhance-
ment. The gas flow increases the turbulence and
2 Submerged Membrane Bioreactor

a
sand pretreat- sand
grids aeration settler disinfection
wastewater filtration ment filtration
effluent

sludge to disposal

b Membrane
Aeration
Bioconversion
Sedimentation

SMB

sand
wastewater grids
filter
pretreatment effluent

gas sparging

sludge to disposal

Submerged Membrane Bioreactor, Fig. 1 Comparison between (a) conventional wastewater plant and (b) SMB
wastewater plant

Submerged Membrane Bioreactor, Table 1 Comparison of two types of membrane bioreactors manufactured by
ZENON ®, i.e., sidestream tubular MBR and submerged SMB (Cote and Thompson 2000)
Membrane bioreactor MBR Submerged membrane bioreactor SMB
Model Permaflow Z-8 ZeeWeed ZW-500
Surface area [m2] 2 46
Permeate flux [l/m2h = LMH] 50–100 20–50
Pressure [bar] 4 0,2–0,5
Airflow rate [m3/h] – 40
Energy [kWh/m3] 4–12 0,3–0,6

produces smooth movements which help to
remove the filter cake from the membrane surface
during microfiltration and reduces the concentra-
tion polarization layer during the ultrafiltration.
In the case of aerobic bioreactor, the gas may
simply be air. In the case of anaerobic bioreac-
tors, inert gas is used to assist desorption of gas-
eous products from the liquid.
The SMB is most often used to remove xeno-
biotic and various biological nutrients, i.e., sub-
stances such as carbon, nitrogen, and phosphorus,
for the treatment of municipal, industrial waste-
water, water treatment, and recycling of different
process waters. SMB is also used for the purifi-
cation of groundwater and surface waters
(Yimaza et al. 2006), as well as waters for irriga-
tion. Industrial sectors that use the SMB are food
and beverages, where high loads of chemical
oxygen demand must be reduced. Other sectors
of the industrial wastewater treatment plants are
in the textile, electronics, pharmaceutical, chem-
ical, metal finishing, automotive, petrochemical,
and pulp and paper. SMB reactors are also used
on offshore oil and gas platforms and on barges,
ships, boats, and yachts (Table 2).
SMB has a lot of advantages compared with
conventional systems, in particular activated
sludge (ASB Yilmaz et al. 2006). The use of
microorganisms floating freely allows for easier
access to the substrate (a few microns) and thus a
Submerged Membrane Bioreactor 3

faster bioconversion compared with ASB
(several hundred microns of flocks in activated
sludge). SMB can operate effectively in all dilute
solutions even below threshold values for ASB
that is 0.01 kg COD/(m3 day). This is because the
kinetics of bioconversion in the SMB is faster
since it is limited only by chemical reaction,
Submerged Membrane Bioreactor, Fig. 2 Gas sparg-
ing around the capillary membranes in the laboratory
stand
which is much faster compared to mass transport
in the activated sludge. Thus, using SMB is cheap
and easy, because it helps minimize capital and
operating expenses. Low energy costs are associ-
ated with the use of energy-efficient method of
removing a filter cake (in MF) or a polarizing film
(in UF) from the surface of the membrane, such
as gas sparging in moderate hydrodynamic con-
ditions. Low capital cost based on a simple and
very compact design, which consists of closely
arranged membranes directly immersed in the
tank bioreactor design with compact stacked
membranes that are placed directly in the reactor.
In addition, the SMB does not require settlers,
thus occupying less space (footprint) in sewage
treatment plants, which, in case of conventional
solutions, can be very burdensome to the envi-
ronment, particularly in the open air. Using SMB
ensures greater bioconversion kinetics and shows
better flexibility and versatility of bioconversion.
SMB bioreactor has many other important fea-
tures such as high-performance density and ease
of membrane replacement and disposal of waste,
ease of automation, and ease of design and scale-
up. SMB systems are easy to operate and main-
tain, allow for remote monitoring and control,
and are much easier to control by the operator.
These characteristics predestine the SMB to
development and retrofitting existing facilities.
The global market is growing rapidly at a 20 %
annual rate value that is estimated to exceed 1bln
$ in 2012 (Judd 2011).
The main suppliers of bioreactors with sub-
merged membranes are:

Submerged Membrane Bioreactor, Table 2 Comparison of main different SMBs (Yang et al. 2006)
Manufacturer KUBOTA ® MITSUBISHI RAYON ® ZENON ®
Membrane type Flat sheet Hollow fiber Hollow fiber
Membrane pore size [mm] 0,4 0,1–0,4 0,04
Membrane material PE (chlorinated) PE PVDF
Membrane configuration Vertical Horizontal Vertical
Surface area in module [m2] 0,8 105 31,6
Industrial plants 400 204 127
Municipal plants 1138 170 204
4 Submerged Membrane Bioreactor

1. KUBOTA ®, MICRODYN-NADIR ®, concentrated activated sludge. J Water Pollut Control

WEISE , TORRAY , KUBER® (flat sheet
® ® Fed 42:2135–2148
Judd S (2011) The MBR book. Principles and applications
membranes) of membrane bioreactors for water and wastewater,
2. ZENON ®, MITSUBISHI RAYON ®, 2nd edn. Elsevier, Oxford, UK
SIEMENS-MEMCOR , KOCH-PURON ®,
®
Smith JCV, Gregorio DD, Talcott RM (1969) The use of
ASAHI KASEI ®, KMS KOREA ultrafiltration membranes for activated sludge separa-
tion. In: Proceedings of the 24th Annual Purdue Indus-
LENNTECH BV ®, TRIQUA ®, TORRAY ®, trial Waste Conference. Purdue University, Lafayette,
COLLOIDE ®, MEMSTAR®, ASIA pp 1300–1310
GIANT ®, MOTIMO ® (hollow fiber) Yamamoto K, Hiasa M, Mahmood T, Matsuo T (1989)
3. NORIT ® (tubular) Direct solid-liquid separation using hollow fiber mem-
brane in an activated sludge aeration tank. Water Sci
Technol 21:43–54
Yang W, Cicek N, Ilg J (2006) State-of-the art of mem-
brane bioreactors: world wide research and commer-
References cial applications in North America. J Membr Sci
270:201–211
Cote P, Thompson D (2000) Wastewater treatment using Yilmaz I, Kabay N, Bryjak M, Y€ uksela M, Wolska J,
membranes: the North American experience. Water Koltuniewicz AB, (2006) Submerged
Sci Technol 41:209–215 membrane–ionexchange hybrid process for boron
Hardt FW, Clesceri LS, Nemerow NL, Washington DR removal. Desalination, 198: 310–315. DOI:10.1016/j.
(1970) Solids separation by ultrafiltration for desal.2006.01.031.
 S
Sulfonated Aromatic Polymer
S. M. Javaid Zaidi1,2 and Kripal S. Lakhi1
1
Australian Institute for Bioengineering and
Nanotechnology, The University of Queensland,
Brisbane, QLD, Australia
2
King Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia
Sulfonated aromatic polymers (SAP hereafter), as
the name suggests, are polymers obtained by
sulfonation of the aromatic polymers. Mem-
branes fabricated from the sulfonated aromatic
polymers are SAP membranes. Sulfonation pro-
cess imparts a number of desirable and useful
properties such as high ionic conductivity, better
hydrophilicity, and relatively higher solubility of
the parent aromatic polymer (Vona and Knauth
2013). Sulfonation introduces sulfonic acid func-
tionality by simple electrophilic aromatic substi-
tution thereby enabling enhanced proton
transport necessary for high proton conduction
in fuel cells applications (Vona and Knauth
2013). Additionally, presence of sulfonic acid
groups converts the parent polymer into ionomers
without polymer chain degradation and increases
its glass transition temperature (Zaidi 2003; Xing
and Kerres 2006). The number of sulfonic acid
groups, also called degree of sulfonation (DS in
short), can be controlled by controlling the sulfo-
nation reaction parameters, such as temperature
and time (Meyer and Schrickel 2013; Zaidi
# Her Majesty the Queen in Right of Australia 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_560-1
2003). A high degree of sulfonation results in
swelling of the membrane which is manifested
in the form of lower or reduced mechanical sta-
bility (Meyer and Schrickel 2013). Sulfonation is
the best technique to make the polymer soluble in
appropriate solvents especially good for thermo-
plastics which are not soluble in any solvents,
such as polyether ether ketone. Exposing the
sulfonated polymers to temperatures higher than
300  C results in degradation of the polymer after
which sulfonic acid groups are released from the
polymer backbone (Meyer and Schrickel 2013;
Zaidi 2003). Incorporation of sulfonic acid
groups into the polymer backbone widens the
scope and application of parent aromatic poly-
mer. The applications of SAP includes such
diverse and important areas as fuel cells, electro-
dialysis, ion-exchange resins and catalysts, surgi-
cal instruments, implant, and wound healing and
dressing to name a few (Vona and Knauth 2013).
SAP membranes are widely viewed by the scien-
tific community as a possible replacement of the
existing state of the art Nafion ® membrane devel-
oped by Du Pont. Some of the key and important
properties of SAP that are of interest to the sci-
entific community and industry include ionic
conductivity, water uptake, permeability,
increased solubility, and mechanical stability
(Vona and Knauth 2013; Zaidi 2003; Othman
et al. 2007). Besides, SAP membranes are eco-
nomical and easy to introduce sulfonic acid
groups by a simple method.
2 Sulfonated Aromatic Polymer
Sulfonated Aromatic Polymer, Fig. 1 Structures of common sulfonated aromatic polymers
Several variations of SAP based membranes
such as sulfonated poly (ether ether) ketones
(SPEEK), sulfonated polyphenylsulfones
(SPPSU), sulfonated polyethersulfone (SPES),
etc., to name a few, have been investigated as
polymer electrolyte membrane in polymer fuel
cells. Of these, the most studied and highly prom-
ising SAP is the polymer based on poly (ether
ether ketones) or PEEK. Sulfonated PEEK
(or SPEEK) is known to have high proton con-
ductivity and high thermal and mechanical sta-
bility. High level of sulfonation makes polymer
membranes amorphous and reduces its mechani-
cal strength, making membranes brittle (Zaidi
2003; Tohidian et al. 2013). Structures of some
common sulfonated aromatic polymers are
shown in Fig. 1.
Sulfonation of aromatic polymer membranes
can be achieved by two different approaches
namely postsulfonation approach and direct sul-
fonation of the aromatic polymers. In this
method, the aromatic polymer is first sulfonated
to the desired degree and then membranes are
fabricated from it. In the other approach, the
membranes are first fabricated and then sulfona-
tion is carried out on the membrane. In this case
the surface of the membrane is modified, while in
the other case the whole of the polymer is mod-
ified by sulfonation (See also ▶ postsulfonation
membrane). However, the latter approach is most
commonly used than the former for a variety of
reasons. Each of the two approaches has its own
advantages and disadvantages. In post-
sulfonation, it is difficult to control and is limited
by the solubility of the polymer as it is carried out
in homogeneous medium, whereas direct sulfo-
nation consumes large quantity of solvent and
often separation of sulfonated polymer from the
reaction mixtures poses a challenge. The choice
of the approach is dictated by the properties and
functionality desired in the SAP membranes
(Vona and Knauth 2013; Meyer and Schrickel
2013; Zaidi 2003; Tohidian et al. 2013).
Sulfonation can be accomplished using a vari-
ety of sulfonating agents such as fuming sulfuric
acid, concentrated sulfuric acid, chlorosulfonic
acids, and sulfur trioxide (both in liquid and gas-
eous forms) (Vona and Knauth 2013; Meyer and
Schrickel 2013; Zaidi 2003). These agents are
classified as strong and mild agents and conse-
quently affect the final yield and extent of sulfo-
nation. As with any organic reaction, sulfonation
process is also marred with unwanted side reac-
tions, cleavage of chain to mention a few if not
properly carried out especially with fuming sul-
furic acid (Meyer and Schrickel 2013; Zaidi
2003). Each of these sulfonating agents has
some adverse effect on the sulfonation process.
Use of fuming sulfuric acid generates lots of
water as a by-product thereby promoting the
reverse reaction, i.e., desulfonation. The genera-
tion of HCl as a by-product limits the use of
cholorosulfonic acid as a sulfonation agent as
the generated acid must be neutralized. Some
milder forms of sulfonating agents are
trimethylsilyl chlorosulfonate, acetylsulfate, or a
complex of SO3 with amine or trialkyl phos-
phates also commonly used (Meyer and Schrickel
2013; Zaidi 2003). Choice of the sulfonating
agent depends on the kind and type of the aro-
matic polymer and its molecular weight. Utmost
care should be taken when sulfonation reaction is
carried out to avoid these side reactions.
Sulfonated Aromatic Polymer
References
Meyer,M, Schrickel J (2013) Sulfonated polymers: simple
chemistry for high-tech materials and applications.
Speciality chemicals magazine
Othman MHD, Ismail AF, Mustafa A (2007) Physico-
chemical study of sulfonated poly (ether ether ketone)
membranes for direct methanol fuel cell application.
Malays Polym J 2(1):10–28
Tohidian M, Ghaffarian SR, Shakeri SE, Bahlakeh
G (2013) Sulfonated aromatic polymers and organi-
cally modified montmorillonite nanocomposite
3
membranes for fuel cells applications. J Macromol
Sci B Phys 52:1578–1590
Vona M,D, Knauth P (2013) Sulfonated aromatic poly-
mers as proton-conducting solid electrolytes for fuel
cells: a short review. J Phys Chem 227:595–614
Xing D, Kerres J (2006) Improvement of synthesis proce-
dure and characterization of sulfonated poly(arylene
ether sulfone) for proton exchange membranes. J New
Mater Electrochem Syst 9:51–60
Zaidi SM (2003) Polymer sulfonation-A versatile route to
prepare proton-conducting membrane material for
advanced technologies. Arab J Sci Eng 28(2B):183
S
Sulfonated Block Copolymer
Membrane
S. M. Javaid Zaidi1,2 and Kripal S. Lakhi1
1
Australian Institute for Bioengineering and
Nanotechnology, The University of Queensland,
Brisbane, Australia
2
King Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia
When two different monomers couple in all pos-
sible ways, it gives rise to what is known as a
copolymer. Depending on the coupling pattern,
copolymers are of following three types: random
copolymer, block copolymer, and graft copoly-
mer. In block copolymer, two separate chains
(or blocks) of two monomers A and B are linked
together as shown in Fig. 1. A typical structure of
a multiblock copolymer is shown in Fig. 2.
It is well established in literature that
sulfonated polymer membranes have superior
properties such as high proton conductivity,
higher glass transition temperature, and higher
mechanical, thermal, and chemical stability as
compared to non-sulfonated or parent polymeric
membranes. It is also well known that a sulfona-
tion process introduces sulfonic group function-
ality which is the main reason for high
performance of these sulfonated membranes.
Chemical modification of polymeric materials
by treatment with a variety of sulfonating agents
has given birth to a host of sulfonated polymeric
# Her Majesty the Queen in Right of Australia 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_561-1
membranes such as sulfonated polyimides, poly
(ether ether ketone)s (PEEK), poly(ether sulfone)s
(PES), poly(phenylene sulfide) (PPS), etc. with
improved properties. Sulfonated polymer mem-
branes however have their own disadvantages.
Sulfonation of polymers is prone to side reactions
resulting in cross-linking. Additionally, due to
the inherent insolubility of sulfonated polymers,
the nature of the solution changes from homoge-
nous to non-homogenous as a result of sulfona-
tion process (Meier-Haack et al. 2005). High
degree of sulfonation is essential for higher pro-
ton conductivity but it causes swelling and a
consequent loss of mechanical strength (Meier-
Haack et al. 2005; Yeo et al. 2012; Lee
et al. 2013a). The aforementioned problems can
be overcome partially if not completely by using
a sulfonated block copolymer. The unique feature
of sulfonated block copolymer is the existence of
micro-phase separation since the two blocks are
chemically different and incompatible while
covalently bonded to each other. The micro-
phase separation is a function of the chemical
nature of the different blocks and/or length of
the blocks. The presence of high density of sul-
fonic groups on the hydrophilic side results in a
well-connected phase-separated ion transport
path which enhances proton conductivity without
affecting physical properties (Lee et al. 2013a).
Polystyrene is an example of a block copolymer
which exhibits phase-separated morphology
(Meier-Haack et al. 2005). This morphological
feature of block copolymers is most desirable
2 Sulfonated Block Copolymer Membrane
Sulfonated Block Copolymer Membrane, Fig. 1 Typical coupling pattern in a block copolymer
O O
C C N O
H H
Sulfonated Block Copolymer Membrane, Fig. 2 General structure of a typical multiblock copolymer: sulfonated
polyaramide multiblock copolymer
especially in electrochemical applications such
as in direct methanol fuel cells (DMFC) and in
water treatment. Many studies dealing with
sulfonated multiblock copolymers with ion
exchange capacities (IEC) ranging from 4.1 to
5.6 meq/g for fuel cells applications have been
reported, for example, sulfonated polymer
obtained from 4,40 -dichlorodiphenyl sulfone
(SDCDPS), and hydroquinone shows IEC
value of 4.1 meq/g. Another interesting
sulfonated block copolymer obtained from
4,40 -dichlorodiphenyl sulfone and bis
(hydroxyphenyl)fluorene shows IEC value of
4.5 meq/g (Takamuku and Jannasch 2012). It is
also reported that sulfonated multiblock copoly-
mer membranes have higher proton conductivity
at high temperatures and low relative humidities
(RHs) as compared to sulfonated polymer mem-
branes (Meier-Haack et al. 2005; Yeo et al. 2012;
Takamuku and Jannasch 2012). Sulfonated block
copolymer membranes also find application in
water treatment for removal of ionic pollutants
from wastewater where block copolymer com-
prising of polystyrene sulfonate (PSS) and hydro-
genated polyisoprene (hPI) has been used for
membrane fabrication (Yeo et al. 2012). Reverse
osmosis (RO) and nanofiltration are currently the
most widely used technique for water treatment,
where the use of sulfonated block copolymers has
been investigated to improve the mechanical
integrity and enhance water permeability. In a
recent report, sulfonated block copolymer
SO3H
O O
N C C N N
H H
Y
X
Z
comprising of polystyrene sulfonate (PSS) and
hydrogenated polyisoprene (hPI) blocks has
been employed as a nanofiltration
(NF) membrane with excellent results for the
removal of metal ions such as copper, cadmium,
and nickel ions (Yeo et al. 2012). It is believed
that (hPI) chains perform a dual role of providing
flexible support matrix and induce thermody-
namic incompatibility with the PSS chains. This
helps in controlling the self-assembly of struc-
tures in the nanometer scale (Yeo et al. 2012).
Additionally, these nanostructured membranes
allow higher water flux as compared to conven-
tional RO membranes due to sulfonated block
copolymers (Lee et al. 2013b).
References
Geise GM, Freeman BD, Paul DR (2010) Characterization
of a sulfonated pentablock copolymer for desalination
applications. Polymer 51:5815–5822
Lee KH, Chu JY, Kim AR, Nahm KS, Kim C-J, Yoo DJ
(2013a) Densely sulfonated block copolymer compos-
ite membranes containing phosphotungstic acid for
fuel cell membranes. J Membr Sci 434:35–43
Lee KH, Chu JY, Kim AR, Nahm KS, Yoo DJ (2013b)
Highly sulfonated poly(arylene biphenylsulfone
ketone) block copolymers prepared via post sulfona-
tion for proton conducting electrolyte membranes.
Bull Korean Chem Soc 24(6):1763
Meier-Haack J, Taeger A, Vogel C, Schlenstedt K,
Lenk W, Lehmann D (2005) Membranes from
sulfonated block copolymers for use in fuel cells. Sep
Purif Technol 41:207–220
Sulfonated Block Copolymer Membrane
Takamuku S, Jannasch P (2012) Multiblock copolymers
with highly sulfonated blocks containing di- and
tetrasulfonated arylene sulfone segments for proton
exchange membrane fuel cell applications. Adv
Energy Mater 2:129–140
3
Yeo J, Kim SY, Kim S, Ryu DY, Kim T-H, Park MJ
(2012) Mechanically and structurally robust
sulfonated block copolymer membranes for water
purification applications. Nanotechnology 12:11
S
Supported Liquid Membrane
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Supported or immobilized liquid membrane
(SLM or ILM) is one of the three-phase liquid
membrane systems in which the membrane phase
(liquid) is held by capillary forces in the pores of
microporous polymeric or inorganic film. Sup-
port separates two aqueous solutions: the feed
(donor) and the strip (receiving, acceptor) phase
(see Fig. 1). The compounds of interest are sepa-
rated from the aqueous sample feed phase into an
organic liquid membrane phase, and then they are
continuously back extracted to the other side of
the membrane into the strip phase. The driving
force is the difference in concentration of the
compounds between the phases.
A SLM usually consists of an organic solvent
immobilized in the pores of a hydrophobic
microfiltration membrane. In many cases, the
organic solvent contains a carrier which is able
to selectively bind one of the components from
the separated mixture (feed solution) which
improves selectivity. The general term for mass
transport through liquid membranes under the
chemical potential gradient as a driving force is
permeation. The permeants from liquid feed
(donor solution) are transported through a
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_566-2
nonporous, polymeric, or liquid membrane
phase and desorbed into another liquid phase.
Some authors called this process pertraction.
While solvent extraction is an equilibrium pro-
cess, SLM separation is a dynamic,
nonequilibrium diffusion process governed by
the kinetics of the membrane transport. There-
fore, the amount of transported compounds is not
proportional to the amount of the organic, mem-
brane phase as it is in extraction.
Usually SLMs are based on hydrophobic
organic solvent immobilized in a polymeric
membrane separating two aqueous solutions. In
some cases, the arrangements are opposite, and
the pores in the support separating two
nonaqueous phases are impregnated by water.
The SLM may be fabricated in different geome-
tries. Flat sheet SLM is useful for research, but
the surface area to volume ratio is too low for
industrial applications. Spiral-wound and
hollow-fiber SLMs have much higher surface
areas of the LM modules (103 and 104 m2/m3,
respectively).
The main problem of SLM technology is the
stability: the chemical stability of the carrier, the
mechanical stability of porous support,
etc. Relatively new LM technologies, developed
with the aim to improve stability parameters, are
gel LM formed by liquid-phase gelation in the
pores, ion-exchange membranes as supports,
ionic liquids (ILs) used as a membrane phase,
swollen polymeric membranes, and polymeric
inclusion membranes (PIM), formed by casting
2 Supported Liquid Membrane
Supported Liquid
Membrane,
Fig. 1 Scheme of a
supported liquid membrane
the solution of polymer and plasticizer (solvent
characterized by high viscosity) to form a thin,
flexible, and stable film. All these technologies
are considered as modifications of the SLMs.
SLM can also be formed by immobilizing the
membrane phase between two nonporous films
which are permeable to transported substances
and usually nonselective. The latter is much
more stable but is less suitable due to a higher
mass transfer resistance.
Successful applications of SLMs are possible
due to their advantages compared to other sepa-
ration methods. The main advantages of SLMs
are the small amounts of organic phase and
extractant (carrier) used, one-step mass transfer,
the possibility of achieving high separation fac-
tors, concentration of extracted compound
(s) during separation, and low separation costs.
SLMs have been used to solve an increasing
number of separation problems, including metal
and organic compound separation and the resolu-
tion of stereoisomers. The unique flexibility and
ease of preparation of SLMs in various configu-
rations, despite some stability and lifetime
problems, have resulted in their application in
many sometimes very different fields where
selective and efficient separation methods are
necessary: in hydrometallurgy, biotechnology,
wastewater treatment, the capture of greenhouse
gases, analytical and environmental chemistry,
and in the pharmaceutical industry.
SLM separation systems can be classified into
several different groups, according to their
preparation methods, types of membrane support
and membrane liquids, module types used, and
their application (for details, see Dzygiel and
Wieczorek 2010).
References
Dzygiel P, Wieczorek P (2010) Supported liquid mem-
brane and their modifications:definition, classifica-
tions, theory, stability, applications and perspectives.
In: Kislik V (ed) Liquid membranes principles and
applications in chemical separations and Wastewater
treatment, 1st edn. Elsevier, Amsterdam, The Nether-
lands, Ch. 3 pp 73–140
T
Temperature Polarization
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Szczecin, Poland
In the membrane distillation (MD) process, mass
and heat transfer through a hydrophobic micro-
porous membrane occurs simultaneously. The
mass transfer proceeds through the membrane
pores, whereas the heat is transferred both
through the pores (with permeate flux) and across
the membrane material.
According to the mechanism of MD, water
and volatile solutes present in the feeding solu-
tion evaporate from the liquid–vapor interface on
the feed side of a hydrophobic membrane. The
vapor is transferred through the membrane pores
and subsequently is either condensed in the
stream of cold distillate flowing along the mem-
brane or removed from a membrane module on
the distillate side.
Since the mass transfer in MD occurs in a
vapor form, the energy for water evaporation
has to be supplied from the hot feed to the
liquid-membrane interface. When the vapor is
condensed at the vapor–liquid interface on the
cold side of the membrane, the energy (heat) is
released. Moreover, a part of energy accumulated
in the hot feed is transferred across the membrane
material and the gas trapped in the pores. Around
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_573-4
50–80 % of energy is consumed as the latent heat
for the water vapor production, whereas 20–40 %
is lost by conduction through the membrane
(Alkhudhiri et al. 2012). Thus, the temperatures
in the bulk feed and permeate solutions (Tf and
Tp, respectively) differ from the corresponding
temperatures at the membrane/solution interface
where vapor–liquid transition occurs (Tmf and
Tmp), which is presented in Fig. 1. This phenom-
enon is termed as temperature polarization
(TP). A decrease of temperature on the feed
side reduces the partial vapor pressure being in
equilibrium with the liquid phase, whereas higher
temperature on the permeate side increases the
partial pressure which results in a reduction of
both the driving force (i.e., vapor pressure differ-
ence (pf pp)) and the permeate flux through MD
membranes. The boundary layers are formed at
the membrane surfaces both on the feed and per-
meate sides. This causes an additional resistance,
besides a membrane resistance, and is considered
as the limiting factor of the mass transport effi-
ciency (Khayet 2011).
Regardless of MD configuration, the mass and
heat transport through the membrane as well as
the effects of temperature boundary layers at the
membrane surfaces which affected the magnitude
(extent) of TP should be taken into account. The
most severe, negative influence of TP can be
expected in DCMD, where a substantial resis-
tance of the boundary layers present in a liquid
form on the both sides of the membrane can be
observed.
2 Temperature Polarization

Temperature Heat and mass

Polarization, Fig. 1 Heat
and mass transfer through
the membrane in DCMD
configuration Tmf
Tf Vapor
cmf Tmp
cf Tp
Heat, conduction

Hot feed
Heat with

permeate
Vapor

Cold
Pf
Pp

Boundary Membrane
layer

In the vacuum membrane distillation (VMD) – Optimized thickness, because it is inversely

process, the vacuum provides insulation against
conductive heat loss through the membrane, and
the boundary layer resistance on the permeate
side is negligible. In the air gap membrane distil-
lation (AGMD), a stagnant air is introduced
between the membrane and the condensation sur-
face which reduces a heat loss by conduction.
However, an additional resistance to mass trans-
fer is generated. In sweep gas membrane distilla-
tion (SGMD), an inert gas is used to sweep the
vapor at the permeate side of a membrane. The
gas barrier reduces the heat loss, but the condi-
tions are not stationary, and the mass transfer
coefficient increases (Alkhudhiri et al. 2012).
TP in MD can be reduced by using appropriate
membranes, which are characterized by:
– As low as possible, thermal conductivity of the
membrane material to reduce heat loss
through conduction
proportional to the rate of mass and heat trans-
port through the membrane
– High porosity, since the conductive heat trans-
fer coefficients of the gases entrapped in the
pores are an order of magnitude smaller than
those of the used membrane materials
TP can be also diminished when the flow rate
of streams along the membrane surface reduces
the boundary layer thickness.
References
Alkhudhiri A, Darwish N, Hilal H (2012) Membrane
distillation: a comprehensive review. Desalination
287:2–18
Khayet M (2011) Membranes and theoretical modeling of
membrane distillation: a review. Adv Colloid Interf
Sci 287:2–18
T
Temperature Polarization
Coefficient (TPC)
Maria Tomaszewska
West Pomeranian University of Technology,
Szczecin, Szczecin, Poland
In all membrane distillation (MD) configurations,
the mass and heat transfer takes place simulta-
neously. In the process the water vapor is trans-
ferred through a porous hydrophobic membrane.
In order to achieve evaporation of water at the
membrane-liquid interface, the heat has to be
supplied from the warm feed. In direct contact
membrane distillation (DCMD), the vapor con-
denses at the cold membrane-liquid interface, and
the heat is released to a cold distillate. This cre-
ates temperature gradients in the boundary layers
adjacent to both sides of the membrane. The
temperatures in the bulk solution (Tf and Tp) are
different from the corresponding values on the
membrane surfaces (Tfm and Tpm). The heat trans-
fer across the boundary layers is often considered
as the limiting factor for mass transfer in DCM-
D. The temperature polarization coefficient
(TPC) (Y) is generally used as a measure of the
magnitude of the boundary layer resistance in
relation to the total heat transfer resistance. TPC
can be also written as a function of the heat
transfer coefficients in the thermal boundary
layers:
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_574-3



Y ¼ T fm  T pm = T f  T p
¼ 1  H=h where 1=h ¼ 1=hf  1=hp
The hf and hp are the heat transfer coefficients in
the feed and permeate boundary layers, respec-
tively, and H is the global heat transfer coefficient
of the MD process.
TPC indicates a reduction in the effective
driving force (vapor pressure difference through
the hydrophobic membrane) and has a negative
influence on DCMD productivity.
When the thermal boundary layer resistances
are reduced, the temperature differences between
the liquid-vapor interfaces and the bulk tempera-
tures become close to each other, and TPC
approaches to 1. This value can be achieved in a
properly designed module, in which the only
limitation is mass transfer. For a poorly designed
module with high heat resistance of boundary
layers, the value of Y approaches to zero and
the process is limited by heat transfer. Usually,
for the appropriate designed systems, the value of
Y is in the range of 0.4–0.7.
The performance of DCMD module can be
improved by the application of turbulent flow
promoters or net spacers to minimize the heat
resistance and to increase the heat transfer coef-
ficients of the boundary layers (Khayet and
Matsuura 2011). Generally, TPC increases with
increasing feed and permeate flow rates and is
reduced with increasing temperature of a feed.
Moreover, this coefficient strongly depends on
the membrane characteristics. The driving force
2 Temperature Polarization Coefficient (TPC)

of MD is decreased by both temperature polari-
zation and concentration polarization. Therefore,
they can be combined in one coefficient called the
vapor pressure polarization coefficient (Khayet
2011).
TPC defined and calculated for DCMD can be
also applied to other MD configurations. In sweep
gas membrane distillation (SGMD) and air gap
membrane distillation, the heat transfer coeffi-
cient on the permeate side is much smaller than
that on the liquid side. Therefore, in SGMD the
flow rate of sweeping gas controls the process. In
vacuum membrane distillation, the boundary
layer resistance on the permeate side is
negligible. In this case TPC depends on the heat
transfer coefficient in feed boundary layer and
increases with a membrane permeability (pore
size and porosity).
References
Khayet M (2011) Membranes and theoretical modeling of
membrane distillation: a review. Adv Colloid Interf
Sci 164:56–88
Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
T
Tetrazole Group
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Pakistan
Tetrazoles are a class of heterocyclic compounds
consisting of a five-member ring of four nitrogen
and one carbon atom. The chemical formula for
simplest tetrazole is CN4H2 and the chemical
structure is represented in Fig. 1.
Tetrazoles have wide range of applications
which are currently receiving considerable atten-
tion (Butler 1996); therefore, the literature on
tetrazole is expanding rapidly. This functional
group has a role in coordination chemistry as a
ligand (Du et al. 2011), as well as in various
materials sciences applications including photog-
raphy, energetic materials, and membranes
(Gomes 2012; Herr 2002; Miyata et al. 2004,
2005). Tetrazole and its derivatives such as
5-aminotetrazole are sometimes used as a com-
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_575-1
ponent of gas generators in automobile airbags.
Extensive work has also been carried out in the
field of medicinal chemistry, where tetrazoles are
frequently used as metabolically stable surro-
gates for carboxylic acids (Lin 2005; Pu
et al. 2008).
One of the recent researches in the develop-
ment of novel microporous organic polymers
(MOPs) represented that by the introduction of
tetrazole groups into highly microporous poly-
meric frameworks resulted the favorable CO2
sorption with superior affinity in gas mixtures
and selective CO2 transport by presorbed CO2
molecules that limit access by other light gas
molecules. This proves the importance of
tetrazole groups in designing MOP membrane
materials for economic CO2 capture processes
(Singh et al. 2006). Proton-conductive and par-
ticularly anhydrous proton conductivity of poly
(5-vinyltetrazole)-based composite membranes
were also evaluated and found to be efficient not
only for intermediate temperature fuel cells but
also in solid electrochromic devices (Vyas
et al. 1986).
2 Tetrazole Group
Tetrazole Group,
Fig. 1 Chemical structure
of tetrazole
References
Butler RN (1996) Tetrazoles. In: Katritzky AR, Rees CW,
Scriven 48 EFV (eds) Comprehensive heterocyclic
chemistry II, 49 vol 4. Pergamon Press, Oxford, p
621–678
Du N, Park HB, Robertson GP, Dal-Cin MM, Visser T,
Scoles L, Guiver MD (2011) Polymer nanosieve mem-
branes for CO2-capture applications. Nat Mater
10:372–375
Gomes ADS (2012) New polymers for special applica-
tions. InTech Publisher, Croatia
Herr RJ (2002) 5-Substituted-1H-tetrazoles as carboxylic
acid isosteres: medicinal chemistry and synthetic
methods. Bioorg Med Chem 10(11):3379–3393
Lin P, Clegg W, Harrington RW, Henderson RA (2005)
Synthesis and structures of 5-(pyridyl)tetrazole com-
plexes of Mn(II). Dalton Trans 2388–2394
Miyata Y, Date S, Hasue K (2004) Propellants, explos.
Pyrotechnics 29:247
Miyata Y, Kanou H, Date S, Hasue K (2005) Combustion
Characteristics of the Consolidated Mixtures of
5-Amino-1H-tetrazole and Sodium Perchlorate. Sci
Technol Energ Mater 66:233
Pu H, Wu J, Wan D, Chang Z (2008) Synthesis and
anhydrous proton conductivity of poly
(5-vinyltetrazole) prepared by free radical polymeri-
zation. J Membr Sci 322(2):392–399
Singh P, Verma RD, Meshri DT, Shreeve JM
(2006) Angew Chem Int Ed 45:3584
Vyas DM, Partyka RA, Doyle TW (1986) Bristol Myers
Co., USA, Ger. Offen. DE 3531453
T
Thermo-responsive Membrane
Surfaces
Liang-Yin Chu
Membrane Science and Functional Materials
Group, School of Chemical Engineering, Sichuan
University, Chengdu, Sichuan, China
Thermo-responsive membrane surfaces (also
called thermosensitive membrane surfaces) are
membranes with thermo-responsive/thermo-
sensitive surfaces prepared by grafting or coating
thermo-responsive/thermo-sensitive materials onto
the membrane surface by certain chemical or phys-
ical methods. The substrate membranes provide
mechanical strength and dimensional stability,
while the conformational changes of the grafted
thermo-responsive polymers on the membrane
surfaces result in the thermo-responsive character-
istics. The surface wettability characteristics and
the membrane resistance as well as transmembrane
permeability of such membranes can be controlled
or adjusted by self-regulation according to the
responsive conformational change of the grafted
or coated thermo-responsive materials on the mem-
brane surfaces. Because there are numerous cases in
which environmental temperature fluctuations
occur naturally, and the environmental temperature
stimuli can be easily designed and artificially con-
trolled, much attention has been focused on thermo-
responsive membrane surfaces. Such membranes
can be used for both controlled release and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_581-3
advanced separation by utilizing the thermo-
responsive conformational change of the functional
surface layer (Chu 2011).
Various grafting techniques, including chem-
ical grafting, plasma-induced grafting, radiation-
induced grafting, and so on, can be employed to
prepare thermo-responsive membrane surfaces
by grafting thermo-responsive polymers onto
the membrane surfaces. According to the location
of grafted polymers on the membranes, thermo-
responsive membrane surfaces can be classified
as surface-covering model (Fig. 1a), pore-
covering model (Fig. 1b, d), and pore-filling
model (Fig. 1c) (Chu et al. 2011). For the pore-
covering and pore-filling models (Fig. 1b–d), the
effective membrane pore sizes can be self-
regulatively adjusted by the thermo-responsive
volume phase transition behaviors of the grafted
thermo-responsive materials, i.e., the grafted
thermo-responsive materials can act as smart
valves that respond to environmental temperature
stimuli.
Poly(N-isopropylacrylamide) (PNIPAM) is a
popular thermo-responsive polymer. It shows a
distinct and reversible phase transition at the
lower critical solution temperature (LCST)
around 32  C. PNIPAM-based polymers are usu-
ally used to fabricate thermo-responsive mem-
brane surfaces (Fig. 1a–c). When the
environmental temperature is lower than the
LCST, the PNIPAM-based materials exhibit a
swollen and hydrophilic state; however, when
the temperature is higher than the LCST, the
2 Thermo-responsive Membrane Surfaces

Thermo-responsive
Membrane Surfaces,
Fig. 1 Schematic
illustration of thermo-
responsive membrane
surfaces grafted with
responsive materials
possessing thermo-induced
shrinking (a–c) and
thermo-induced swelling
behaviors (d). (a) Surface-
covering model, (b, d)
pore-covering model, and
(c) pore-filling model

PNIPAM-based materials show a shrunken and temperature (UCST) of the PAAM/PAAC-based

hydrophobic state. By such thermo-responsive
conformational change of the membrane surface
layer, the surface wettability characteristics and
the membrane resistance as well as transmem-
brane permeability of the membranes can be
self-regulatively controlled or adjusted according
to the environmental temperature change (Chu
2011).
Interpenetrating polymer networks (IPNs) of
poly(acrylamide) (PAAM) and poly(acrylic acid)
(PAAC) are featured with a thermo-responsive
volume phase transition characteristic that is the
reverse of that of PNIPAM, i.e., the swelling of
PAAM/PAAC-based IPNs is induced by an
increase rather than a decrease in temperature.
Therefore, the thermo-responsive membrane sur-
faces constructed from PAAM/PAAC-based
IPNs are featured with negatively thermo-
responsive characteristics (Fig. 1d) (Chu
et al. 2005). When the environmental tempera-
ture is lower than the upper critical solution
IPN gel, the IPN hydrogels retain a shrinking
state. On the other hand, when the environmental
temperature is higher than the UCST of the IPN
gel, the IPN hydrogels retain a swelling state. For
the pore-covering model (Fig. 1d), the effective
membrane pores change from an “open” situation
into a “closed” situation when the temperature
increases from one that is below the UCST to
another that is above the UCST.
References
Chu LY (2011) Smart membrane materials and systems.
Springer, Berlin
Chu LY, Xie R, Ju XJ (2011) Stimuli-responsive mem-
branes: smart tools for controllable mass-transfer and
separation processes. Chin J Chem Eng 19:891–903
Chu LY, Li Y, Zhu JH, Chen WM (2005) Negatively
thermoresponsive membranes with functional gates
driven by zipper-type hydrogen-bonding interactions.
Angew Chem Int Ed 44:2124–2127
T
Thin-Sheet Zeolite Membranes
Wei Liu
Energy and Environment Technology
Directorate, Pacific Northwest National
Laboratory, Richland, WA, USA
Zeolite materials possess some unique properties,
such as molecular-sieving functions, excellent
chemical and thermal stability, and low costs.
Today, zeolites are used in a variety of catalytic
reaction and adsorption separation processes.
They are a very attractive class of materials for
membrane usage. A large number of scientific
articles and patent applications have been
published on zeolite membranes for recent two
decades. The feasibility of making zeolite mem-
branes and their unique molecular-sieving func-
tions was demonstrated in the late 1990s and
early 2000s, which includes those common zeo-
lite frameworks consisting of SiO2, Al2O3, and
Na2O, such as NaA, X-type, Y-type, ZSM-5,
silicalite, and mordenite. For example, the flux
and selectivity of a zeolite membrane was
reported to be one to two orders of magnitude
higher than the polymeric membranes for solvent
dehydration (Morigami et al. 2001).
Zeolites are ceramic-type materials, and self-
supported zeolite membranes are too fragile to be
made as large sheets (or plates). Thus, zeolite
membranes are typically grown on a porous sup-
port structure. Ceramic disks and tubes have been
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_582-1
used in most literature studies so far. Occasion-
ally, sintered metal tubes and frits were used.
Those supporting materials serve well for the
purposes of fundamental studies and proof of
concept experiments. For actual membrane prod-
uct development, however, novel product designs
and manufacturing processes are needed to pro-
duce large zeolite membrane areas suitable for
industrial applications at a cost competitive with
existing separation technologies.
Ceramic tube-supported zeolite membranes
are now commercially available. These tubes
have a length about 1 m and outer diameter
from 1.0 to 3.0 cm. A number of membrane
tubes can be bundled together to form a mem-
brane module or separation device. Those zeolite
membranes are demonstrated at pilot and small-
scale commercial plants for dehydration of alco-
hols and organic solvents. However, their cost
(Caro and Noack 2009), which ranged from
$1,000 to 3,000/m2, is too high to be used widely.
In addition, a great number of membrane tubes
are required for large-scale industrial processes,
which present significant challenges to engineer-
ing and installation of membrane separation
equipment. For example, it is estimated that
about 70,000 of membrane tubes are needed for
ethanol dehydration in a medium-size ethanol
plant of 150 million liters per year production
capacity. Instead of a single hole, several holes
are made into one membrane tube to achieve
incremental improvement to the membrane area
packing density.
2 Thin-Sheet Zeolite Membranes
Thin (-μm) porous
support sheet:
• Permeable, strong
• Stable under membrane
growth conditions and
preparation conditions
• Uniform pore structures
at sub-micrometer
• Stable in organic solvents
and at elevated
temperatures
• Low cost
Thin-Sheet Zeolite Membranes, Fig. 1 Design concept of thin-sheet zeolite membranes
One approach to address the cost and mem-
brane area problems is to make zeolite mem-
branes like polymeric membrane sheets. Spiral
wound polymeric membranes are made at fairly
low costs and used in large-scale seawater desa-
lination. The design concept of thin-sheet zeolite
membranes is illustrated in Fig. 1. One critical
challenge is the support structure. Thinness of the
support sheet is necessary to reduce material con-
sumption, membrane weight, and transport resis-
tance. Thin sheets also enable package of large
membrane areas in a given volume, i.e., obtaining
high membrane area packing density.
As general requirements of a membrane sup-
port, the support sheet needs to be highly perme-
able so that mass transport through the support
would not present a significant resistance for
most separation applications, and the support
sheet needs to be sufficiently strong to provide
the mechanical strength for the membrane sheet
to withstand a pressure gradient under separation
conditions for a long time. The specific require-
ments pertinent to zeolite membrane preparation
are (i) stability under zeolite membrane growth
and preparation conditions, (ii) uniform surface
pore structures at micro- and sub-micrometer
levels, and (iii) stability under the zeolite mem-
brane separation conditions. The growth of a
Growth of an ultra-thin
zeolite membrane on the
support
Cross-sectional view of
an actual membrane
sample
zeolite membrane typically occurs in a strong
basic solution at temperatures ranging from
60
C to 180
C. After growth, posttreatment
sometimes is needed for the removal of templates
and opening of zeolite pores. The possible
posttreatment methods are oxidation in an O2
gas environment at high temperatures, oxidation
in plasma or ozone gas environment at moderate
or low temperatures, and solvent extraction. Hav-
ing a uniform surface pore structure at micro- and
sub-micrometer levels is necessary for deposition
of a thin, continuous zeolite membrane layer on
the support. It is obvious that a continuous zeolite
membrane less than 10 mm thick cannot be
formed on a support surface of pores or defects
larger than 10 mm. The zeolite membrane can
work under separation conditions that could be
problematic to polymeric materials, such as in
hydrocarbon and organic solvent media and at
high temperatures (relative to environment).
Thus, the support sheet needs to be stable under
separation conditions so that application and per-
formances of the zeolite membrane would not be
compromised by the support. Finally, the support
sheet needs to be low costs.
No commercially available materials could be
found yet when the above criteria were applied to
the selection of a suitable support sheet. Porous
Thin-Sheet Zeolite Membranes
Surface
texture
12cm x 12cm x 50µm porous
Ni support sheet
Thin-Sheet Zeolite Membranes, Fig. 2 NaA zeolite membrane grown on 50 mm-thick porous Ni sheet support
ceramic disks work well as a zeolite membrane
support but have not been made as thin, strong,
inexpensive sheets yet. Sintered metal plates
meet the requirements of mechanical strength
and chemical and thermal stability. But they are
too thick and too expensive. On the other hand,
metal foams and metal meshes have the pore
opening too large to be deposited with a thin,
continuous zeolite membrane layer. Micro- and
ultrafiltration polymeric membranes have ade-
quate surface pore structures but fall short of
chemical and thermal stability. No report on for-
mation of high-performance zeolite membranes
on a polymeric support has been found yet.
Thin porous metallic sheets have recently
been developed that can meet all the above
criteria (Liu et al. 2011a; Liu and Canfield
2012). The thin-metal sheets made of Ni, Ni
alloys, and steels possess the physical and chem-
ical properties of those metallic materials and
provide suitable pore structures for the prepara-
tion of a thin layer of zeolite membranes. These
metal sheets are made of inexpensive metal oxide
raw materials and have large potential for mass
production at low costs. As a reference, steel
sheets and plates are produced at a price as low
as $1/kg. It was demonstrated that zeolite mem-
branes can be directly prepared on such supports
3
Zeolite membrane
surface texture
NaA zeolite membrane grown on
the 50µm-thick porous Ni sheet
by secondary growth methods (Liu et al. 2011b).
The secondary growth consists of two basic pro-
cess steps: seeding and growth. The support sur-
face is first coated with a layer of small crystals of
targeted zeolite framework that act as a seed for
zeolite crystal growth. The seed coating also
helps smoothening of the support surface. Then,
a continuous layer of intergrown zeolite crystals
is formed by hydrothermal growth of the seeded
support under suitable conditions. Thin-sheet
zeolite membranes grown on such a support are
illustrated with a NaA membrane in Fig. 2. The
50 mm-thick porous Ni alloy sheet is strong
enough to be self-supported and flexible enough
to bend and shows uniform surface pore struc-
tures. After membrane growth, the sheet surface
changes its color from metallic gray to darken
glassy luster. A dense and continuous membrane
layer comprising intergrown zeolite crystals is
formed on the metallic support surface. No cracks
and pinholes are seen. Although there are differ-
ent sizes and shapes of crystals on the membrane,
a pure NaA crystal phase is confirmed by X-ray
diffraction analysis. It is worth noting that the
zeolite membrane shows excellent adhesion
onto the support, which is largely attributed to
the thinness of the zeolite membrane layer. The
zeolite membrane is so thin that the membrane-
4 Thin-Sheet Zeolite Membranes
A stack of 13cm x
13cm x 55 µm
zeolite membrane
sheets
Thin-Sheet Zeolite Membranes, Fig. 3 Package of thin membrane sheets into a working module for cross-flow
separation and mass transfer
grown sheet behaves similar to the bare metal
sheet, strong and flexible.
The thin-sheet design paves the way for mass
production of zeolite membranes at competitive
cost. Materials used to make the metal sheet
support and prepare zeolite membranes are typi-
cally inexpensive commodity products. By mak-
ing thin-sheet membranes, the raw materials
become a minor cost factor. The membrane cost
will be largely determined by the preparation
process costs. Current planar sheet or plate prod-
ucts, such as papers, metal foils, glass, and poly-
meric membranes, are manufactured in large bulk
quantities at fairly low costs. It is expected that
the thin-sheet zeolite membrane can be mass
produced by utilizing automated, high-
throughput sheet-to-sheet-type manufacturing
processes.
The thin sheet enables fabrication of mem-
brane modules or membrane separation equip-
ment with maximum membrane area and/or
minimal mass transfer resistance from bulk to
membrane surface. A cross-flow planar module
(Fig. 3) is used to illustrate the making of a
separation device with the thin-sheet zeolite
membrane. An array of membrane sheets is pack-
aged together to form respective feed and perme-
ate channels by the use of proper backing and
spacing materials. The sweep (or permeate) and
feed (or process) streams are separated by the
Process
stream in
Sweep
stream in
Membrane Process
core stream out
Sweep +
permeate out
membrane sheet and flow in perpendicular direc-
tions. The membrane surface per unit volume
(SAV) of the stack for this module design can be
estimated by the following equation:
1
SAV ¼
0:5LP þ 0:5LF þ Lm
where Lp, LF, and Lm are permeate (or sweep)
channel spacing, feed (or process) channel spac-
ing, and membrane thickness, respectively. If
Lp = 1 mm, LF = 1 mm, and Lm = 0.05 mm,
SAv can be 952 m2/m3. Using small channel spac-
ing reduces the mass transfer resistance from bulk
to membrane surfaces and increases the mem-
brane area packing density.
In summary, zeolite membranes supported on
a thin porous metal sheet are compared to other
membrane materials and products in Table 1.
This hybrid membrane technology is expected
to preserve unique properties possessed by the
zeolite and metallic materials and eliminate
their shortcomings at the same time. Thus, the
hybrid thin-sheet membrane can provide perfor-
mance and cost advantages that are not achiev-
able using individual materials alone. There is a
great opportunity to further develop this mem-
brane technology for various applications and to
expand the design concept to other material
systems.
Thin-Sheet Zeolite Membranes 5

Thin-Sheet Zeolite Membranes, Table 1 Comparison of thin-sheet zeolite membranes to other membrane products
Material Application Cost Characteristics
Polymer Various commercial products from microfiltration, Fair Working well in water medium
Hollow fiber ultrafiltration, and nanofiltration to molecular at ambient or room
Sheet separation temperatures
~$10 billion/year global market Stability issues at high
temperatures and in organic
solvents or oil
Ceramic Some specialized applications High Tolerance to organics
Excellent thermal stability
Tube A few hundred million $/year market Fragile
Monolith
Metal Some specialized applications with limited market High Ductile and strong
penetration Tolerant to organics
Tube Fair thermal stability
Thin-sheet Porous metal sheet as micro- and ultrafiltration Fair Advantages of metal and zeolite
zeolite/metal membrane materials
membrane Zeolite membranes for a number of important Module package like polymeric
molecular separation processes sheets

References Liu W, Canfield N, Li X (2011a) Thin, porous metal sheets

Caro J, Noack M (2009) Zeolite membranes – status and
prospective. In: Ernst S (ed) Advances in nano-porous
materials. Elsevier, Oxford
Liu W, Canfield N (2012) Development of thin porous
metal sheet as micro-filtration membrane and inor-
ganic membrane support. J Membr Sci
409–410:113–126
and methods for making the same, US20110155662
Liu W, Zhang J, Canfield J, Saraf N (2011b) Preparation of
robust, thin zeolite membrane sheet for molecular sep-
aration. Ind Eng Chem Res 50(20):11677–11689
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Technol 25:251
T
Traditional Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Traditional diafiltration (TD) is the most com-
mon type of batch diafiltration technique that
accomplishes the selective separation of a
macrosolute-microsolute mixture as well as the
concentration of macrosolute by employing a
constant-volume dilution mode step that is pre-
ceded and/or followed by concentration mode
operational steps.
Due to its straightforward concept and simple
configuration, TD is the most frequently used
batch diafiltration technique employed in various
pressure-driven membrane filtration systems
including reverse osmosis, nanofiltration, ultrafil-
tration, and microfiltration applications. TD pro-
cess normally consists of three consecutive
operational steps in the following order:
1. Pre-concentration step, to increase the concen-
tration of macrosolute up to an intermediate
level
2. Constant-volume dilution step, to “wash out”
microsolute by a diluant introduced into the
system in order to improve the recovery of the
material in the permeate or to improve the
purity of the retained phase
# Springer-Verlag Berlin Heidelberg 2014
E.Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_585-3
3. Post-concentration step, to further reduce the
volume and to concentrate macrosolute to the
final, desired level
In certain cases, if optimality requires, the
three-step TD is reduced to a two-step process
with either (1) or (2) omitted from the sequence.
Note that filtration in concentration mode
removes some of the microsolute but does not
reduces its concentration in the feed tank. Even
in case of freely permeable microsolute (i.e.,
rejection is equal to zero), the microsolute con-
centration remains constant in the feed tank.
Thus, concentration mode is to be coupled with
constant-volume dilution mode to achieve a high
level of macrosolute-microsolute separation.
The generalized process model for both con-
centration mode and dilution mode can be written
as
dci ci q
¼ ðRi  aÞ, ci ð0Þ ¼ ci0 ,
dt V
dV
¼ ða  1Þq, V ð0Þ ¼ V 0
dt
where ci is the solute concentration in the feed
tank, Ri stands for the rejection of component i,
V represents the volume in the feed tank, and a is
the proportionality factor defined as the ratio of
diluant flow to permeate flow q. By definition, in
concentration mode, a = 0 (i.e., no diluant is
added), while in constant-volume dilution mode,
a = 1. V0 and ci0 denote respectively the initial
2 Traditional Diafiltration
feed volume and the initial feed concentration of
the solute i. This initial value problem describes
the evolution in time of the feed volume and the
feed concentration of any solute under the
assumption that the diluant is free of component
i, and the feed tank is well mixed. Note that the
time-dependent variables (i.e., permeate flux and
the solute rejections) are, in a general case, a
function of feed concentrations and may vary
with operation conditions (temperature, pressure,
cross-flow velocity, etc.).
Assuming constant rejections and flux, the
differential equations can be reduced to simple
algebraic equations. The resulting exact solutions
are:
• For concentration mode, the actual concentra-
tion of component i at any time instant gives
ci ¼ ci0 nRi where n is the volume concen-
tration factor defined as the ratio of initial feed
volume to actual feed volume.
• And for constant-volume dilution mode, it
holds: ci ¼ ci0 eDðRi 1Þ where D is the dilution
factor given as the ratio of applied diluant
volume to feed volume.
The subject of optimization procedures is a
TD process that aims at increasing the
macrosolute concentration from c10 to c1f and
reducing the microsolute concentration from c20
to c2f (e.g., Beaton and Klinkowski 1983; Dutré
and Trägárdh 1994; Foley 1999; Wang
et al. 2007; Paulen et al. 2012). TD is character-
ized with a sequence a(t) = {0, 1, 0} with two
unknown switching times at the end of the first
and of the second process steps. In engineering
practice, process optimization is usually aimed at
finding optimum values for n and D. Note that it
poses a mathematically analogous problem to
finding switching times. The problem of deter-
mining optimum switching times for a given
technological objective has been the subject of
many optimization studies, most of them
considering process models with constant (i.e.,
concentration-independent) flux and rejections
and a few dealing with concentration-dependent
membrane response models (e.g., Bowen and
Mohammad (1998); Kovács et al. 2008). The
simplifying assumptions, when their appropriate-
ness is not carefully checked for the given sepa-
ration process, can easily result in suboptimal
process control.
Optimization procedures may consider differ-
ent objective functions, such as minimization of
operational time, diluant consumption, or a com-
plex economic index. This latter involves the
costs of utilized diluant and pump operation and
incorporates macrosolute loss-related costs. The
optimal solution is case specific varying with the
complexity of the permeation model (i.e., rejec-
tion and flux behavior), the initial and final
values, and the constraints involved in the model.
References
Beaton NC, Klinkowski PR (1983) Industrial ultrafiltra-
tion design and application of diafiltration processes.
J Sep Process Technol 4(2):1–10
Bowen WR, Mohammad AW (1998) Diafiltration by
nanofiltration: prediction and optimization. AIChE
J 44(8):1799–1812
Dutré B, Trägárdh G (1994) Macrosolute-microsolute sep-
aration by ultrafiltration: a review of diafiltration pro-
cesses and applications. Desalination 95:227–267
Foley G (1999) Minimisation of process time in ultrafil-
tration and continuous diafiltration: the effect of
incomplete macrosolute rejection. J Membr Sci
163:349–355
Kovács Z, Discacciati M, Samhaber W (2008) Numerical
simulation and optimization of multi-step batch mem-
brane processes. J Membr Sci 324(1–2):50–58
Paulen R, Fikar M, Foley G, Kovács Z, Czermak P (2012)
Optimal feeding strategy of diafiltration buffer in batch
membrane processes. J Membr Sci 411–412:160–172
Wang L, Yang G, Xing W, Xu N (2007) Mathematic
model of the yield for diafiltration processes. Sep
Purif Technol 59:206–213. doi:10.1016/j.
seppur.2007.06.007
T
Transparent Exopolymer Particle
Loreen O. Villacorte
FMC Technologies, Separation Innovation and
Research Center, Delta 101, The Netherlands
Introduction
Transparent exopolymer particles (TEPs) refer to
a variety of biopolymers or exopolymeric sub-
stances (EPS) in aquatic systems which can be
identified by Alcian blue staining. TEPs were first
described in 1993 by Alice Alldredge and
coworkers (1993) shortly after discovering these
materials by staining with Alcian blue dye – a
cationic dye known to specifically complex with
anionic groups of polysaccharides and glycopro-
tein (Ramus 1977). As the name suggests, TEPs
are transparent organic substances seasonally
abundant (e.g., algal bloom) in marine, brackish,
and nonsaline surface waters (Passow 2002a;
Emery et al. 1984). These substances mostly orig-
inate from exudates of phytoplankton and
bacterioplankton but may also originate from
macroalgae, oysters, mussels, scallops, and sea
snails (Passow 2002b; McKee et al. 2005;
Heinonen et al. 2007; Thornton 2004). They con-
sist of hydrophilic, negatively charged, and mostly
surface-active acidic polysaccharides containing
mostly half-ester sulfate (R-OSO3 ) and to the
lesser extent carboxyl (R-COO ) functional
groups (Mopper et al. 1995; Zhou et al. 1998).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_587-5
TEP has been reported to be in various forms
(e.g., strings, disks, sheets, or fibers) and sizes,
ranging from 3 nm in diameter up to 100 s of mm
long (Berman and Holenberg 2005; Passow 2000).
For the last two decades, the presence of trans-
parent exopolymer particles (TEPs) in seawater
and freshwater and their important role in the
carbon cycle in aquatic systems have been exten-
sively studied in the field of oceanography and
limnology (see review by Passow 2002a). How-
ever, their significance to membrane-based water
treatment technologies has only been investi-
gated recently. Berman and Holenberg (2005)
proposed monitoring TEP in desalination plants
after it was implicated as a potential cause of
fouling in membrane systems. Consequently, a
number of studies were conducted to investigate
their presence in feedwater sources and their pos-
sible link to membrane fouling (Bar-Zeev
et al. 2009; Villacorte et al. 2009a, b, 2010a, b).
Moreover, the presence of TEP has also been
reported in wastewater sources of membrane sys-
tems (de la Torre et al. 2008; Kennedy
et al. 2009).
Identification and Measurement
Although TEP has only been known for about
20 years, the presence of transparent microscopic
marine substances detectable only by staining
and electron microscope had been reported way
back in the 1970s (Gordon 1970; Winters
2 Transparent Exopolymer Particle
et al. 1983). However, the transparent character
of TEP complicated earlier studies to investigate
their abundance in aquatic systems. Currently,
TEP has been roughly defined as particles, rec-
ognizing that the first method used 0.4 um poly-
carbonate membranes to extract them from the
water (Alldredge et al. 1993). However, the cur-
rent understanding about TEP has been changing
through the years. TEPs are not real particles, as
its name suggests, but rather aggregates of
hydrogels which are highly deformable and can
vary in size from few nanometers to hundreds of
micrometers (Passow 2002a, b; Verdugo
et al. 2004). Majority of these substances were
formed abiotically from colloidal precursors by
spontaneous assembly of colloidal polymers in
surface water (Chin et al. 1998; Passow 2000).
Moreover, monitoring TEP in membrane treat-
ment plants proved to be a challenge because
MF/UF membranes can theoretically reject
these materials if measured with 0.4 um pore
size membranes but will not totally reject their
colloidal precursors which might spontaneously
assemble into measurable TEP downstream.
Therefore, it is increasingly important to incor-
porate this colloidal fraction in the TEP measure-
ments in order to sufficiently assess the rejection
by pretreatment systems. The use of liquid
chromatography-organic carbon detection
(LC-OCD) is a promising technique to estimate
the presence of these of colloidal fraction in
aquatic systems (Villacorte 2009a, b, 2010a, b;
Amy et al. 2011).
Currently, there are four established methods
to measure TEP. These methods either involve
direct counting (Alldredge et al. 1993) or spec-
trophotometric measurements (Passow and
Alldredge 1995; Arruda-Fatibello et al. 2004;
Thornton et al. 2007), all of which involve Alcian
blue staining. The spectrophotometric assay
developed by Passow and Alldredge (1995) is
currently the most widely used and accepted
method to measure TEP. In this method, TEPs
were collected through vacuum filtration on poly-
carbonate membrane filters (0.4 mm pore size),
stained with Alcian blue, and dissolved in sulfu-
ric acid, and then the absorbance Alcian blue
bound to TEP was measured
spectrophotometrically at 787 nm wavelength.
Those biopolymers which passed through the
filters are considered as TEP precursors or colloi-
dal TEP (<0.4 mm; Passow 2000).
Potential Impact on Membrane
Filtration and Control
TEPs comprise surface-active materials (e.g.,
half-ester sulfate groups) which is the main ingre-
dient of their high stickiness (Mopper et al. 1995;
Zhou et al. 1998; Dam and Drapeau 1995; Engel
2000). The relative stickiness of TEP is estimated
to be between two and four orders of magnitude
higher than most other suspended particulates in
surface water (Passow 2002a). TEPs may also
form large gel-like materials which may function
like a sponge capable of absorbing/retaining
nutrients and trace elements from surface water,
making them a nutritious platform and a good
refuge for bacteria to grow and multiply
(Alldredge et al. 1993; Berman and Holenberg
2005). Moreover, TEPs can be direct alternative
carbon nutrient for bacteria are they partially
biodegradable (Passow 2002a). Based on these
characteristics, Berman and company (Berman
and Holenberg 2005; Berman 2010; Berman
et al. 2011; Bar-Zeev et al. 2012) introduced the
concept of TEP as a major initiator of biofilm
development in reverse osmosis
(RO) membranes. Initially, the sticky TEP mate-
rial may accumulate on RO membranes
(including feed spacers) and create a conditioning
film conducive for bacterial attachment. Once the
bacteria are attached to the film, they can effec-
tively utilize the available dissolved nutrients
(C, P, N) in the feedwater and eventually grow
into large colonies. If nutrients are not limited in
the system, the initial TEP layer gradually trans-
forms into a biofilm as colonies of attached bac-
teria start to produce more exopolymeric
substances in addition to the further accumulation
of TEP from the feedwater. Current anti-
biofouling strategies are usually designed to
limit the influx of nutrients to the RO system by
pretreatment or by applying a biocide to control
bacterial population. Hence, limiting biological
Transparent Exopolymer Particle
activity in the system may not be enough to
prevent organic fouling, considering that TEP
may still accumulate on the RO membrane if
the pretreatment systems are not sufficiently
removing them.
Although initially TEPs were only implicated
as a potential problem in cross-flow NF/RO
membrane systems, they are likely major a prob-
lem in dead-end membrane filtration systems
(MF/UF), especially during algal blooms. With
their macromolecular size (up to hundreds of
micrometers), TEP can be largely (if not totally)
rejected during membrane filtration. TEP may
serve as a binding agent of rejected materials
(e.g., particles and other organic substances)
that can accumulate on membrane surfaces.
Since TEPs are negatively charged and surface-
active substances, they have the high tendency to
adhere to membrane surfaces than other foulants.
Additionally, abundant divalent ions (e.g., Ca2+)
in surface water can enhance gelation of TEP by
cationic bridge formation (Passow 2002). With
the binding and aggregation capability of TEP, it
can enhance accumulation of a cake layer on the
membrane with higher hydraulic resistance and
lower backwashability than other suspended
materials (including algal cells). This scenario
has been demonstrated in recent studies of a
pilot plant treating seawater impacted by algal
bloom which generated high concentrations of
TEP (Schurer et al. 2012; Villacorte
et al. 2010a, b). In these studies, it was also
found that inline coagulation can be an effective
pretreatment technique to minimize fouling of
MF/UF membranes during filtration of surface
of water with high concentrations of TEP.
Cross-References
▶ Algal Bloom
▶ Biological Fouling
▶ Extracellular Polymeric Substances (EPS)
▶ Liquid-Chromatography Organic Carbon
Detection (LC-OCD)
▶ Organic Fouling
3
References
Alldredge AL, Passow U, Logan BE (1993) The abun-
dance and significance of a class of large, transparent
organic particles in the ocean. Deep Sea Res
40(6):1131–1140
Amy GL, Salinas-Rodriguez SG, Kennedy MD, Schippers
JC, Rapenne S, Remize P-J, Barbe C, Manes CLDO,
West NJ, Lebaron P, Kooij DVD, Veenendaal H,
Schaule G, Petrowski K, Huber S, Sim LN, Ye Y,
Chen V, Fane AG (2011) Water quality assessment
tools. In: Drioli E, Criscuoli A, Macedonio F (eds)
Membrane-based desalination – an integrated
approach (MEDINA). IWA Publishing, New York,
pp 3–32
Arruda-Fatibello S, Vieira AAH, Fatibello Filho O (2004)
A rapid spectrophotometric method for the determina-
tion of transparent exopolymer particles (TEP) in
freshwater. Talanta 62(1):81–85
Bar-Zeev E, Berman-Frank I, Liberman B, Rahav E,
Passow U, Berman T (2009) Transparent exopolymer
particles: potential agents for organic fouling and bio-
film formation in desalination and water treatment
plants. Desalination Water Treat 3:136–142
Bar-Zeev E, Berman-Frank I, Girshevitz O, Berman
T (2012) Revised paradigm of aquatic biofilm forma-
tion facilitated by microgel transparent exopolymer
particles. Proc Natl Acad Sci U S
A 109(23):9119–9124
Berman T (2010) TEP: a major challenge for water filtra-
tion. Filtr Sep 47(2):20–22
Berman T, Holenberg M (2005) Don’t fall foul of biofilm
through high TEP levels. Filtr Sep 42(4):30–32
Berman T, Mizrahi R, Dozoretz CG (2011) TEP: a critical
factor in aquatic biofilm formation and fouling on
filtration membranes. Desalination 276(1–3):184–190
Chin WC, Orellana MV, Verdugo P (1998) Spontaneous
assembly of marine dissolved organic matter into poly-
mer gels. Nature 391:568–572
Dam HG, Drapeau DT (1995) Coagulation efficiency,
organic-matter glues, and the dynamics of particles
during a phytoplankton bloom in a mesocosm study.
Deep-Sea Res II 42:111–123
de la Torre T, Lesjean B, Drews A, Kraume M (2008)
Monitoring of transparent exopolymer particles (TEP)
in a membrane bioreactor (MBR) and correlation with
other fouling indicators. Water Sci Technol
58(10):1903–1909
Emery KO, Johns IA, Honjo S (1984) Organic films on
particulate matter in surface waters off eastern Asia.
Sedimentology 31:503–514
Engel A (2000) The role of transparent exopolymer parti-
cles (TEP) in the increase in apparent particle sticki-
ness (alpha) during the decline of a diatom bloom.
J Plankton Res 22:485–497
Gordon DC (1970) A microscopic study of organic parti-
cles in the North Atlantic Ocean. Deep-Sea Res
17:175–185
4 Transparent Exopolymer Particle
Heinonen KB, Ward JE, Holohan BA (2007) Production
of transparent exopolymer particles (TEP) by benthic
suspension feeders in coastal systems. J Exp Mar Biol
Ecol 341:184–195
Kennedy MD, Muñoz-Tobar FP, Amy GL, Schippers JC
(2009) Transparent exopolymer particle (TEP) fouling
of ultrafiltration membrane systems. Desalination
Water Treat 6(1–3):169–176
McKee MP, Ward JE, MacDonald BA, Holohan BA
(2005) Production of transparent exopolymer particles
by the eastern oyster Crassostrea virginica. Mar Ecol
Prog Ser 183:59–71
Mopper K, Zhou J, Ramana KS, Passow U, Dam HG,
Drapeau DT (1995) The role of surface-active carbo-
hydrates in the flocculation of a diatom bloom in a
mesocosm. Deep-Sea Res II 42:47–73
Passow U (2000) Formation of transparent exopolymer
particles (TEP) from dissolved precursor material. Mar
Ecol Prog Ser 192:1–11
Passow U (2002a) Transparent exopolymer particles
(TEP) in aquatic environments. Prog Oceanogr
55(3):287–333
Passow U (2002b) Production of transparent exopolymer
particles (TEP) by phyto-and bacterioplankton. Mar
Ecol Prog Ser 236:1–12
Passow U, Alldredge AL (1995) A dye-binding assay for
the spectrophotometric measurement of transparent
exopolymer particles (TEP). Limnol Oceanogr
40(7):1326–1335
Ramus J (1977) Alcian blue: a quantitative aqueous assay
for algal acid and sulfated polysaccharides. J Phycol
13:345–348
Schurer R, Janssen A, Villacorte L, Kennedy MD
(2012) Performance of ultrafiltration & coagulation
in an UF-RO seawater desalination demonstration
plant. Desalination Water Treat 42(1–3):57–64
Thornton DCO (2004) Formation of transparent
exopolymeric particles (TEP) from macroalgal detri-
tus. Mar Ecol Prog Ser 282:1–12
Thornton DCO, Fejes EM, DiMarco SF, Clancy KM
(2007) Measurement of acid polysaccharides in
marine and freshwater samples using alcian blue.
Limnol Oceanogr: Methods 5:73–87
Verdugo P, Alldredge AL, Azam F, Kirchman DL,
Passow U, Santschi PH (2004) The oceanic gel
phase: a bridge in the DOM–POM continuum. Mar
Chem 92(1–4):67–85
Villacorte LO, Kennedy MD, Amy G, Schippers JC
(2009a) Measuring transparent exopolymer particles
(TEP) as indicator of the (bio)fouling potential of RO
feed water. Desalination Water Treat 5:207–212
Villacorte LO, Kennedy MD, Amy G, Schippers JC
(2009b) The fate of transparent exopolymer particles
(TEP) in integrated membrane systems: removal
through pretreatment processes and deposition on
reverse osmosis membranes. Water Res
43(20):5039–5052
Villacorte LO, Schurer R, Kennedy MD, Amy G,
Schippers JC (2010a) Removal and deposition of
transparent exopolymer particles (TEP) in seawater
UF-RO system. IDA J 2(1):45–55
Villacorte LO, Schurer R, Kennedy MD, Amy G,
Schippers JC (2010b) The fate of transparent
exopolymer particles in integrated membrane systems:
a pilot plant study in Zeeland, The Netherlands. Desa-
lination Water Treat 13:109–119
Winters H, Isquith I, Arthur WA, Mindler A (1983) Con-
trol of biological fouling in seawater reverse osmosis
desalination. Desalination 47:233–238
Zhou J, Mopper K, Passow U (1998) The role of surface-
active carbohydrates in the formation of transparent
exopolymer particles by bubble adsorption of seawa-
ter. Limnol Oceanogr 43(8):1860–1871
T
Transport Mechanisms with Liquid
Membranes
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
The commonly accepted mechanism for the
transport of a solute in liquid membrane (LM) is
solution-diffusion. The solute species dissolve in
the liquid membrane and diffuse across the LM
due to an imposed concentration gradient. Differ-
ent solutes have different solubilities and diffu-
sion coefficients in LM. According to the
transport mechanisms, the LM techniques may
be divided into six basic mechanisms of trans-
port, schematically shown in Fig. 1.
In a simple transport (Fig. 1a), solute passes
through due to its solubility in LM. Permeation
stops when concentration equilibrium is reached.
The solute does not react chemically with LM
and is supposed to be in the same form in the
feed (F), LM (E), and receiving, R, phases. As an
example, some carboxylic and amino acids, phe-
nol transport through xylene, decanol LM may be
presented. Uphill transport and selectivity in the
simple mechanism can be achieved at reaction of
the solute with components of the stripping solu-
tion (see Fig. 1b). Some authors relate this tech-
nique to the facilitated transport.
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_588-1
The efficiency and selectivity of transport
across the LM may be markedly enhanced by
the presence of a mobile complexation agent
(carrier) in the liquid membrane. This process is
known as facilitated or carrier-mediated liquid
membrane separation. The transport can be
described by subsequent partitioning, complexa-
tion, and diffusion. The complex reverse reacts
on the LM-receiving side interface releasing the
solute which partitioning to the receiving (strip)
phase (see Fig. 1c). Carriers for the selective
transport of neutral molecules, anions, cations,
or zwitterionic species have undergone intensive
development in the last two decades.
In many cases, the facilitated transport is com-
bined with coupling counter- or cotransport (see
Fig. 1d, e) of different ions through LM. The
coupling effect supplies the energy for uphill
transport of the solute. Facilitated transport is
markedly enhanced by the efficiency and selec-
tivity of transport across the LM.
Active transport (see Fig. 1f) is driven by
oxidation-reduction, catalytic reactions, and bio-
chemical conversions on the membrane inter-
faces. As a rule, it is highly selective: no other
species are transported at this type of transport. In
many cases, chemical reactions in LM are irre-
versible in active transport. As examples, copper
transport by thioether and picrate anions by fer-
rocene as carriers may be presented.
The rates of chemical changes and/or rates of
diffusion may control all liquid membrane trans-
port kinetics. At least one of the chemical or
2 Transport Mechanisms with Liquid Membranes

c
a b
F E R
F E R F E R
SE A–
A–
S
S S S S S
E
SA
SA S S
A–

Simple transport Simple transport with Facilitated transport

chemical reaction
in strip solution
d e f
F E R F E R F E R

S2+ SE2 S2+ ESA red SEA2 αx 2+

S+ S+ S2+ S+ S+ S

A– A–
2H+ 2EH 2H+ E 2A– E 2A–

S2+ S+ S2+
2H+ A– 2A–

Coupled counter-transport Coupled cotransport Active transport

Transport Mechanisms with Liquid Membranes, anions cotransported, E is liquid membrane, F is feed
Fig. 1 Schematic mechanisms of solute transport through solution, R is stripping solution, red is reduction, ox is
the liquid membranes. S is solute to be separated, A are oxidation

diffusion steps is slow enough to control the rate
of the overall transport. So, analysis of mecha-
nisms and kinetics of the chemical and diffusion
steps of the overall LM transport system is
needed to find the rate-controlling ones.
A universal model for all these types of transport
does not exist, and the available knowledge
concerning the specific interfacial processes
should be taken into account in the description
of real membrane process.
The basic idea of the chemical kinetics-
diffusion method is that the solute presented in
the different phases is considered as different
chemical species obeying the laws of chemical
kinetics. The general assumptions of the transport
may be formulated as: (1) Steady-state conditions
of the solute transport through the phase inter-
faces: all fluxes are necessarily the same. (2) The
overall mass-transfer rate of solute can be con-
trolled by any of the chemical reaction–diffusion
resistances in the liquid phases. (3) The overall
mass-transfer resistance at steady state is the sum
of individual mass-transfer resistances at diffu-
sional regime through the boundary films and
chemical reactions resistances at the phases’
interface. (4) Membrane supports have uniform
pore size and wetting characteristics throughout
membrane. Hydrophobic membrane pore is
completely wetted by organic phase; hydrophilic
or ion-exchange membrane pore is completely
filled with aqueous phase. (5) Thermodynamic
local equilibrium at the uptake (feed-LM) and
release (LM-strip) interfaces. (6) The aqueous
or organic stagnant boundary films diffusion
resistances may be combined with the diffusion
resistances of the same liquid films (aqueous
or organic) inside the membrane pores
(taking into account the membrane porosity and
tortuosity) in one-dimensional series of diffusion
resistances.
Transport Mechanisms with Liquid Membranes
In all configurations (BLM, SLM, ELM) we
have: (1) diffusion steps in aqueous feed and strip
stagnant boundary layers, (2) diffusion of the
complex solute-carrier in the LM phase and/or
interdiffusion (diffusion in the filled membrane
support pores), (3) partitions between aqueous
feed and organic LM phases at feed-LM interface
(forward extraction) and between LM and aque-
ous strip phases at LM-strip interface (backward
extraction), and (4) kinetics of chemical interac-
tions with formation of solute-carrier complex
(complexation) and destruction of complex
3
(decomplexation). All these steps have mathe-
matical descriptions. (For details see BLM,
SLM, and ELM entries and Kislik 2010).
References
Kislik V (2010) Carrier-facilitated coupled transport
through liquid membranes: general theoretical consid-
erations and influencing parameters, Chapter 2. In:
Kislik V (ed) Liquid membranes: principles and appli-
cations in chemical separations & wastewater treat-
ment, 1st edn. Elsevier, Amsterdam, pp 17–72
U
Ultrahigh Molecular Weight
Polyethylene
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Pakistan
Ultrahigh molecular weight polyethylene
(UHMWPE), also known as high-modulus poly-
ethylene (HMPE), is a subset of the thermoplastic
polyethylene. Polyethylene is a polymer formed
from ethylene (C2H4), which is a gas having a
molecular weight of 28 g/mol. The generic chem-
ical formula for polyethylene is –(C2H4)n–,
where n is the degree of polymerization.
A schematic of the chemical structures for ethyl-
ene and polyethylene is shown in Fig. 1.
There are several kinds of polyethylene
(LDPE, LLDPE, HDPE, UHMWPE), depending
upon the degree of polymerization or molecular
weights and chain architectures. LDPE and
LLDPE refer to low-density polyethylene and
linear low-density polyethylene, respectively.
These polyethylenes generally have branched
and linear chain architectures, respectively, each
with a molecular weight of typically less than
50,000 g/mol. High-density polyethylene
(HDPE) is a linear polymer with a molecular
weight of up to 200,000 g/mol (Steven 2009).
For an ultrahigh molecular weight polyethyl-
ene, the molecular chain can consist of as many as
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_591-2
200,000 ethylene repeat units. Thus, molecular
weight ranges in the millions, usually between
two and six million. The longer chain serves to
transfer load more effectively to the polymer
backbone by strengthening intermolecular interac-
tions. This results in a very tough material, with
the highest impact strength of any thermoplastic
presently made (Stein 1999). UHMWPE is a
unique polymer with outstanding physical, chem-
ical, and mechanical properties. Most notable are
its chemical inertness, lubricity, impact resistance,
and abrasion resistance. Table 1 summarizes the
physical and mechanical properties of UHMWPE.
Owing to its excellent properties, UHMWPE is
widely used as a biomaterial such as in orthopedics
as a bearing material in artificial joints. One of the
major limiting factors of UHMWPE implant is its
wear and damage with time, thus having only a
finite lifetime. Cross-linking of the UHMWPE
chains is found to be the promising method to
dramatic reductions in wear, improving the perfor-
mance in biomedical applications (Steven 2004).
Recently, research has been conducted for the
modification of the UHMWPE surface by
grafting with different techniques such as radia-
tion, chemical, and plasma grafting. Since
UHMWPE is a semicrystalline polymer, its crys-
talline part normally remained unchanged, while
the amorphous part can be grafted. The
UHMWPE membrane has been evaluated as a
proton exchange membrane for fuel cells
(Sherazi et al. 2009, 2010).
2 Ultrahigh Molecular Weight Polyethylene

H H H H Ultrahigh Molecular Weight Polyethylene,

Table 1 Typical average physical properties of ultrahigh
molecular weight polyethylene (UHMWPE) (Li and
C C C C Burstein 1994)
n Property UHMWPE
H H
H H
Molecular weight (106 g/mol) 3.5–7.5
Ethylene Polyethylene Melting temperature ( C) 132–138
Poisson’s ratio 0.46
Ultrahigh Molecular Weight Polyethylene, Specific gravity 0.925–0.945
Fig. 1 Schematic of the chemical structure of ethylene
and polyethylene Tensile modulus of elasticitya (GPa) 0.5–0.8
Tensile yield strengtha (MPa) 21–28
Tensile ultimate strengtha (MPa) 39–48
References
Tensile ultimate elongationa (%) 350–525
Li S, Burstein AH (1994) Ultra-high molecular weight Impact strength, Izod (J/m of notch; >1070
polyethylene. The material and its use in total joint 3.175 mm thick specimen) (no break)
implants. J Bone Joint Surg Am 76:1080–1090 Degree of crystallinity (%) 39–75
Sherazi TA, Ahmad S, Kashmiri MA, Kim DS, Guiver Testing conducted at 23  C
a

MD (2009) Radiation induced grafting of styrene onto

ultra-high molecular weight polyethylene powder and
subsequent film fabrication for application as polymer
electrolyte membrane. II: sulfonation and characteri-
zation. J Membr Sci 333:59–67
Sherazi TA, Guiver MD, Kingston D, Ahmad S, Kashmiri
MA, Xue X (2010) Radiation-grafted membranes
based on polyethylene for direct methanol fuel cells.
J Power Sources 195:21–29
Stein HL (1999) Ultra high molecular weight polyethyl-
ene (UHMWPE). Guide to engineering plastics
families: thermoplastic resins. Materials Park: ASM
International. pp 167–171
Steven MK (2004) The UHMWPE handbook: ultra-high
molecular weight polyethylene in total joint replace-
ment. Elsevier Acadamic Press, London, UK
Steven MK (2009) UHMWPE, biomaterials handbook,
2nd edn. Elsevier Acadamic Press, Burlington, USA
V
Variable Volume Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Variable volume diafiltration (VVD) is a type of
batch diafiltration process in which fresh diluant
is continuously added to the feed tank at a rate
that is proportional but less than the permeate
flow. This causes a gradually diminishing feed
volume and a simultaneous concentration of
macrosolute and removal of microsolute. Thus,
this technique is more than a simple diafiltration
in its strict and traditional sense since it is not
designed only to wash out the microsolutes but
also enables the concentration of the process
liquor within a single-step operation.
The process is controlled by measuring the
permeate flow and adjusting the diluant flow
accordingly with a control valve. The proportion-
ality factor a, that is, the ratio of diluant flow d(t)
to permeate flow q(t), is then kept constant such
that 0 < a < 1.
For a given process, in which the macrosolute
concentration is to be increased from c1(0) to
c1(tf), while the microsolute concentration is to
be reduced from c2(0) to c2(tf), the proportionality
factor a can be calculated by the following for-
mula (Tekić et al. 2002):
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_593-5


c2 ð0Þ c1 t f
R1 ln
þ R2 ln
c2 t f c 1 ð 0Þ
a¼

c1 t f c 2 ð 0Þ
ln þ ln

c1 ð0Þ c2 tf
where R1 and R2 are the rejection of macrosolute
and microsolute, respectively, and are assumed to
be constants throughout the filtration process.
Variable volume diafiltration has been origi-
nally proposed by Jaffrin and Charrier (1994) for
a UF/DF process for albumin production from
human plasma. The proposed technique, how-
ever, has found to be suboptimal for that particu-
lar application as concluded by an in-depth
mathematical analysis based on optimal control
theory (Paulen et al. 2011).
Although variable volume diafiltration could
offer substantial advantages over constant vol-
ume diafiltration in terms of water usage (Krstić
et al. 2004), it compares unfavorable with an
optimally run traditional diafiltration process
(Foley 2006a). As a further improvement, Foley
(2006b) has suggested that the performance of
variable volume diafiltration under certain cir-
cumstances can be enhanced in terms of diluant
consumption and operational time by including a
pre-concentration step.
Variable volume diafiltration is a relatively
new concept, and only a few experimental inves-
tigations on its performance are available in the
literature. These include, for example, ethanol
removal from albumin (Jaffrin and Charrier
2 Variable Volume Diafiltration
1994), fructooligosaccharide separation
(Li et al. 2004), and whey desalination (Román
et al. 2011).
References
Foley G (2006a) Water usage in variable volume
diafiltration: comparison with ultrafiltration and con-
stant volume diafiltration. Desalination 196:160–163
Foley G (2006b) Ultrafiltration with variable volume
diafiltration: a novel approach to water saving in
diafiltration processes. Desalination 199:220–221
Jaffrin M, Charrier J (1994) Optimization of ultrafiltration
and diafiltration processes for albumin production.
J Membr Sci 97:71–81
Krstić D, Tekić M, Zavargó Z, Djurić M, Ćirić G (2004)
Saving water in a volume decreasing diafiltration pro-
cess. Desalination 165:283–288
Li W, Li J, Chen T, Chen C (2004) Study on nanofiltration
for purifying fructo-oligosaccharides: I. Operation
modes. J Membr Sci 245:123–129
Paulen R, Fikar M, Kovács Z, Czermak P (2011) Process
optimization of diafiltration with time-dependent
water adding for albumin production. Chem Eng Pro-
cess Process Intensif 50(8):815–821
Román A, Vatai G, Ittzés A, Kovács Z, Czermak P (2011)
Modeling of diafiltration processes for demineraliza-
tion of acid whey: an empirical approach. J Food Pro-
cess Eng. doi:10.1111/j.1745-4530.2010.00619.x
Tekić M, Zavargó Z, Krstić D, Djurić M (2002) Mathe-
matical model of variable volume diafiltration. Hung
J Ind Chem 30:211–214
V
Vibrating Membranes
M. R. Bilad and Ivo Vankelecom
Centre for Surface Chemistry and Catalysis, KU
Leuven, Leuven (Heverlee), Belgium
Applying shear at the membrane surface is the
most efficient way to control membrane fouling
in a membrane filtration process (Jaffrin 2008). It
is traditionally provided by coarse bubble aera-
tion and cross-flow velocity, respectively, in
dead-end and cross-flow systems. However,
shear rate can also be generated by moving the
membrane surfaces instead of the surrounding
fluid or by moving a mass very near to the mem-
brane surface. This type of technique is catego-
rized as dynamic filtration systems (DFSs), also
called shear-enhanced filtration. A summary of
the existing DFSs is given in Table 1.
Most DFSs decouple the generation of surface
shear rate from the feed velocity. Thus in theory,
the mechanical energy is more efficiently
directed toward the membrane surface by mem-
brane or liquid movement near the membrane
surface. Ideally, these systems offer reduced
energy consumption and more effective and effi-
cient fouling minimization. Only a limited num-
ber of reports mention the weakness of DFS
systems. General energy calculations in compar-
ison to conventional dead-end or cross-flow sys-
tems are scarce, making it difficult to verify the
claim of energy savings during operation
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_594-4
compared to conventional membrane filtration
systems. These systems also have other draw-
backs, such as apparatus complexity, high ten-
dency of the apparatus to breakdown at the
moving parts, and a low packing density, leading
to high costs per membrane area (Jaffrin 2008).
The latter seems to be the main restriction to
commercialize these technologies.
Vibrating membranes are categorized as DSFs.
They are known as an effective technique to pro-
vide shear rate on the membrane-feed interface in
order to control membrane fouling. It is relatively
new and only few versions exist and have been
tested for different applications, mainly for acti-
vated sludge filtration in membrane bioreactor
(MBR) applications. The vibrating membranes
include the vibrating hollow fiber modules
(VHFM) and magnetically induced membrane
vibrations (MMV). In the VHFM, the membrane
module consists of hollow fiber membranes placed
vertically. The skin layer is located at the outside
of the fibers. The membrane modules are vibrated
in a vertical motion at different frequencies
(0–30 Hz) and different amplitudes (0.2–4 cm)
(Beier et al. 2006; Genkin et al. 2006). The oscil-
lation of the membrane in a VHFM system can
also be performed in the transverse direction,
which also proved to maintain good performance.
This technique has proven to significantly increase
the achievable fluxes both for yeast broth and
activated sludge filtration (Beier and Jonsson
2007; Gomaa et al. 2011).
2 Vibrating Membranes

Vibrating Membranes, Table 1 Summary of existing DFSs (Beier 2008)

Application and
System Description commercial system
VSEP Membrane is oscillated at high frequency (around 60 Hz) in parallel motion UF, NF, RO (Pall Corp,
relative to the flat-sheet membrane surface. The vibration energy focuses shear New Logic)
waves directly at the membrane surfaces repelling solids and foulant, while
increasing the permeate rates.
RD Filtration module contains a disk, rotating around an axis, while the flat-sheet MF, UF, NF (Pall Corp)
membrane is stagnant. The module is sometimes installed with addition of
vanes.
CR Filtration module consists of a rotating motor sandwiched between stagnant MF, NF (Mesto Papper)
flat-sheet membranes.
RM The flat-sheet membrane is mounted onto a rotating hollow disk. The rotation MF, UF (SpinTek)
of the disk creates a centrifugal force across the membrane surface.
CMS The apparatus consists of a membrane head at the end of a rotor arm, containing RO
a plate and frame stack of membranes. It is placed inside housings.
MSD The filtration system consists of two parallel hollow shafts rotating at the same MF (Westfalia
speed, each bearing six ceramic membrane disks. Separator)
RD rotating disk system, CR cross-rotational filter systems, RM rotary membrane systems, CMS centrifugal membrane
separation systems, MSD multishaft disk systems, UF ultrafiltration, NF nanofiltration, RO reverse osmosis, MF
microfiltration

In MMV, the membrane (normally flat-sheet) fedora/objects/orbit:82470/datastreams/file_4977139/

is fixed onto a vibration frame that is directly
connected to an engine. The engine vibrates the
frame via a pull-and-push mode and the vibration
is derived from a programmable sonic device
(Bilad et al. 2012; Mezohegyi et al. 2012). Like
in the DSF systems, only the liquid-membrane
interface experiences shear stress and not the bulk
liquid, thus minimizing energy consumption and
limiting the impact of the movement on the bulk
feed. The movement orientation of the vibrating
parts faced the narrow face of the module in order
to both prevent the bumping of liquid onto the
membrane and minimize the associated energy
dissipation.
References
Beier SP (2008) Dynamic microfiltration – critical flux
and macromollecular transmission. PhD dissertation.
Technical University of Denmark. http://orbit.dtu.dk/
content
Beier SP, Jonsson G (2007) Separation of enzymes and
yeast cells with a vibrating hollow fiber membrane
module. Sep Purif Technol 53:111–118
Beier SP, Guerra M, Garde A, Jonsson G (2006) Dynamic
microfiltration with a vibrating hollow fiber membrane
module: filtration of yeast suspensions. J Membr Sci
281:281–287
Bilad MR, Mezohegyi G, Declerck P, Vankelecom IFJ
(2012) Novel magnetically induced membrane vibra-
tion (MMV) for fouling control in membrane bioreac-
tors. Water Res 46:63–72
Genkin G, Waite TD, Fane AG, Chang S (2006) The effect
of vibration and coagulant addition on the filtration
performance of submerged hollow fibre membranes.
J Membr Sci 281:726–734
Gomaa HG, Rao S, Taweel MA (2011) Flux enhancement
using oscillatory motion and turbulence promoters.
J Membr Sci 381:64–73
Jaffrin MY (2008) Dynamic shear-enhanced membrane
filtration: a review of rotating disks, rotating mem-
branes and vibrating systems. J Membr Sci 324:7–25
Mezohegyi G, Bilad MR, Vankelecom IFJ (2012) Direct
sewage up-concentration by submerged aerated and
vibrated membranes. Bioresour Technol 118:1–7
V
VOC Recovery
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Synonyms
Organic vapor recovery
Many industrial processes handling organic sol-
vents emit volatile organic compounds (VOCs).
These VOCs not only cause environmental pol-
lution but also represent an economic loss. The
VOC recovery has become a big issue that needs
to be addressed. Traditional techniques for VOC
removal include carbon adsorption, condensa-
tion, and absorption, and none is efficient enough
to meet every need. Membrane separation has
developed into an important technology for sep-
arating VOCs and other gaseous air pollutants
from gas streams. The membrane technology uti-
lizes a polymeric membrane that is more perme-
able to condensable organic vapors, such as C3
hydrocarbons and aromatics, than it is to
noncondensable gases such as methane, ethane,
nitrogen, and hydrogen. Because the technology
concentrates the VOC gas stream, it can be used
with a condenser to recover the VOC. It is best
suited for relatively low-flow streams containing
moderate VOC concentration (Fig. 1).
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_595-1
The typical overall VOC recovery process
consists of two steps: (1) compression and con-
densation and (2) membrane separation.
A mixture of vapor and air is compressed. The
compressed mixture is cooled and condensed
vapor is recovered. Uncondensed organics are
separated from the gas stream and concentrated
in the permeate by the membrane. The treated gas
is vented from the system and the permeate is
drawn back to the compressor inlet. The poly-
meric membrane consists of a layer of nonwoven
fabric that serves as the substrate, a solvent-
resistant microporous support layer for mechani-
cal strength, and a thin-film selective layer that
performs the separation. It is manufactured as flat
sheet and is wrapped into a spiral-wound module.
Membranes are best suited for treating VOC
streams that contain more than 1,000 ppmv of
organic vapor where recovered product has
value. Typical VOC recovery using membrane
separation ranges from 90 % to 99 % and can
reduce the VOC content of the vented gas to
100 ppmv or less. In Table 1, VOCs that can be
captured with the membrane separation tech-
nique are listed.
The separation of VOCs from nitrogen by
composite hollow fiber membranes is reported.
Microporous hollow fiber membranes were spun
from poly(vinylidene fluoride) (PVF2) using the
phase inversion method, and the hollow fibers
were coated with a thin layer of poly(ether
block amide) (PEBA), thereby forming compos-
ite membranes. PVF2 was chosen as the substrate
2 VOC Recovery

VOC Recovery, VOC in air Air

Fig. 1 Recovery
membrane model for VOCs

Sweep gas Hollow fiber membrane

Sweep gas out

Condense VOC for recovery

VOC Recovery, Table 1 Typical VOCs nitrogen was also investigated under various
Acetaldehyde BFC-134a operating conditions (e.g., feed concentration,
Acetone Hexane operating temperature). The PEBA/PVF2 com-
Acetonitrile Methanol posite hollow fiber membranes were effective
Carbon tetrachloride Methyl chloroform for the separation of hydrocarbon vapors from
CFC-11 Methyl isobutyl ketone nitrogen.
CFC-12 Methylene chloride PDMSvi was prepared from divinyl-
CFC-113 Propylene oxide terminated poly(dimethylsiloxane), platinum-
Chlorine Styrene divinyltetramethylsiloxane complex,
Chloroform Toluene oligosilylstyrene, and hexane. PDMSvi–Al2O3
Ethylene dichloride Trichloroethylene
composite hollow fiber membrane was developed
Ethylene oxide Vinyl chloride
by coating a PDMSvi-oligo film on the outer
HCFC-123 Xylenes
surface of an Al2O3 hollow fiber porous substrate.
Microstructures of the composite membranes
were examined using scanning electron micros-
material because of its excellent thermal and copy (SEM), displaying a uniform PDMSvi-oligo
chemical stabilities and good mechanical coating layer, free of defects with a thickness of
strength, and PEBA was selected as the active around 15 mm. Such composite hollow fiber
separating layer because of its good membranes are suitable for VOC recovery from
permselectivity and film forming properties. waste gas streams because of their high chemical
The membranes were tested for the recovery of stability. The separation performances of the
representative VOCs including hexane, heptane, PDMSvi–Al2O3 composite hollow fiber mem-
and cyclohexane, which are the main components brane were studied using chloroform in N2 as a
of gasoline, and dimethyl carbonate, ethanol, test vapor mixture. By analyzing the experimen-
methanol, and methyl t-butyl ether that are the tal data obtained at various conditions with a
oxygenates and octane number enhancers of gas- mathematical model derived, the permeabilities
oline. The separation of gasoline vapor from of chloroform and nitrogen in the PDMSvi
VOC Recovery 3

polymer membrane were obtained. The effects of References

temperature, feed flow rate, vacuum pressure on
the permeate side, and feed concentration on the Liu S, Teo WK, Tan X, Lib K (2005) Preparation of
PDMSvi–Al2O3 composite hollow fiber membranes
chloroform recovery were also investigated both
for VOC recovery from waste gas streams. Sep Purif
experimentally and theoretically. A high chloro- Technol 46:110
form recovery was recognized (Liu et al. 2005).
V
Volatile Organic Compounds
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Volatile organic compounds (VOCs) are organic
chemicals that have a high vapor pressure at
ordinary, room-temperature conditions. Their
high vapor pressure results from a low boiling
point, which causes large numbers of molecules
to evaporate or sublimate from the liquid or solid
form of the compound and enter the surrounding
air. Many VOCs are dangerous to human health
or cause harm to the environment. VOCs are
numerous, varied, and ubiquitous. They include
both human-made and naturally occurring chem-
ical compounds. VOCs play an important role in
communication between plants. Volatile organic
compounds (VOCs) are emitted as gases from
certain solids or liquids. VOCs include a variety
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_596-1
of chemicals, some of which may have short- and
long-term adverse health effects. Concentrations
of many VOCs are consistently higher indoors
(up to ten times higher) than outdoors. VOCs
are emitted by a wide array of products number-
ing in the thousands. Examples include paints and
lacquers, paint strippers, cleaning supplies, pesti-
cides, building materials and furnishings, office
equipment such as copiers and printers, correc-
tion fluids and carbonless copy paper, graphics
and craft materials including glues and adhesives,
permanent markers, and photographic solutions.
Organic chemicals are widely used as ingredients
in household products. Paints, varnishes, and wax
all contain organic solvents, as do many cleaning,
disinfecting, cosmetic, degreasing, and hobby
products. Fuels are made up of organic
chemicals. All of these products can release
organic compounds while you are using them
and, to some degree, when they are stored. Table 1
is listed some VOCs in WHO.
2 Volatile Organic Compounds

Volatile Organic Compounds, Table 1 Various volatile organic compounds

Compounds bp (oC) VOCs
Very volatile organic compounds 0  50–100 Propane, butane, methyl chloride etc.
(VVOC)
Volatile organic compounds (VOC) 50–100  Formaldehyde, toluene, acetone, ethanol,
240–260 isopropanol, etc.
Semivolatile organic compounds 240–260  Insecticide, plasticizer
(SVOC) 380–400
The emitted VOCs have to be removed by any method. Membrane separation technology is effective for the removal of
VOCs in air (see ▶ VOC recovery)
W
Water Gas Shift (WGS)
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
In the last decades, great attention has been paid
to hydrogen as a carrier to be used for the pro-
duction of clean energy by means of new tech-
nologies, designed to enhance efficiency and
environmental sustainability, especially for
power generation. Hydrogen is also utilized in a
large amount in the chemical and petrochemical
industry for ammonia synthesis, hydrocracking,
hydroreforming, etc. Currently, hydrogen is
mainly produced from fossil fuels (96 %): the
stream coming out from a reformer or a coal
gasification plant contains about 50 % H2 that
has to be recovered and 40–45 % CO which can
be utilized for producing more hydrogen. Thus,
an upgrading stage is required, and the water gas
shift (WGS) reaction is the most feasible one for
this purpose. The water gas shift reaction is
CO þ H2 O ¼ CO2 þ H2
DH0298 ¼ 41 kJ mol1
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_598-1
Low temperatures thermodynamically favors CO
conversion, but pressure (in a traditional reactor)
does not affect it since the reaction is exothermic
and characterized by no variation of the mole
number.
Kinetics is promoted by a high temperature
and slightly depends on the feed pressure.
WGS process is conventionally operated in
two fixed-bed adiabatic reactors, in series, with
a cooler interposed between them. So the WGS
traditional process consists of:
1. A first reactor operating at high temperatures
(300–450  C) and GHSV (20,000 h1, gas
hourly space velocity), using Fe2O3-Cr2O3
catalyst (Bustamante et al. 2004; Keiski
et al. 1996; Ullman’s Encyclopedia of Indus-
trial Chemistry & 5th Completely Revised
Edition 1995) which shows high kinetic activ-
ity when operated at a temperature higher than
300  C. Taking advantage of the high reaction
rate, this reactor converts the most of CO.
2. A heat exchanger for cooling the stream from
400–450  C down to 200  C ca.
3. A second reactor operating at lower tempera-
tures (210–300  C) and GHSV (2,000 h1) for
reducing the CO fraction in the gaseous stream
to less than 1 %. This reactor uses CuO-ZnO-
(Bustamante et al. 2004; Ullmann’s
2 Water Gas Shift (WGS)
Encyclopedia of Industrial Chemistry & 5th
Completely Revised Edition 1995; Amadeo
and Laborde 1995) or CuO-CeO2-based cata-
lysts and takes advantage of the low tempera-
tures displacing the equilibrium, since the
exothermic character of the WGS reaction.
H2O/CO feed molar ratio typically ranges
from 2 to 5 for shifting the thermodynamic equi-
librium conversion and increases the reaction rate
and thus hydrogen yield. The WGS is often
followed by a further step of remaining CO elim-
ination since CO is a poison for many industrial
catalysts. Thus, this H2-rich stream is usually
directed to a CO selective/preferential oxidation
reactor and then to a pressure swing adsorption
unit for separating H2 from the other gases.
For providing a better exploitation of raw
materials together with the reduction of the reac-
tion/separation/purification stages and related
loads, the use of membrane reactors (MRs) is a
promising approach, as they combine the reaction
and the H2 separation by means of a selective
membrane (Brunetti et al. 2012a; Shu
et al. 1991; Uemiya et al. 1991; Dittmeyer
et al. 2001; Brunetti et al. 2012b).
The presence of the membrane allows the
recovery of a hydrogen-rich/pure stream which
does not require any additional separation. More-
over, the removal of the hydrogen, which is a
product, from the reaction volume shifts the reac-
tion toward a further conversion.
The removal of hydrogen by a membrane
gives many advantages: the reverse reaction rate
is depleted owing to the lower H2 concentration;
the residence time of reactants is increased; the
thermodynamic equilibrium of a membrane reac-
tor exceeds that of a traditional reactor; the pres-
sure has a positive effect on conversion in a
membrane reactor, even if no variation in the
number of mole is involved in the WGS reaction
(Marigliano et al. 2003). Therefore, the use of a
membrane reactor allows obtaining a higher con-
version also at higher temperature where the ther-
modynamic conversion is low, acting positively
on the kinetics. Consequently, the amount of
catalyst necessary for a given conversion can be
significantly reduced (Barbieri et al. 2011). In
fact, one membrane reactor operating at high
temperature was demonstrated replacing the two
reactors of the traditional process (Fig. 1), giving
the same final conversion or higher.
Among the several membrane types, the
Pd-alloy membranes are the most used for the
selective removal of hydrogen in applications
such as dehydrogenation reactions, thanks to
their infinite H2 selectivity. An important aspect
in the use of Pd-alloy MR is the good exploitation
of whole the available membrane area, which
allows the improvement of the global perfor-
mance, with higher CO conversion and more H2
recovered in the permeate side (Barbieri
et al. 2008).
Currently, self-supported Pd-Ag membranes
are produced at commercial level, and, when
used to investigate experimentally the WGS reac-
tion at a laboratory scale, they showed a high
durability and performance stability for more
than 2 years operating at 330  C and up to
10 bar (Barbieri et al. 2008).
The results obtained at a laboratory scale con-
cretized in some cases in various patents. For
example, United Technologies Corp. patented
the use of a WGS MR, comprising a WGS reac-
tion region a permeate volume, separated by an
H2-separation membrane which allows H2
formed over a catalyst in the reaction region to
be passed selectively to the permeate region
(Gummalla et al. 2010).
Water Gas Shift (WGS) 3

b Pd-based MR Feed (e.g., reformer down-stream)

300 °C
Pd-based Membranes
Retentate stream Blind (upper end)

440 °C

440 °C
Pure hydrogen
-1
GHSV = 20 000 h
No sweep gas

a Traditional process

210 °C
Second stage LT-WGS
GHSV = 3 000 h-1 Feed (e.g., reformer down-stream)
LT-WGS Heat exchanger
First stage 300 °C
HT-WGS
GHSV = 20 000 h-1
LT-WGS
ca. 10 GHSV
380 °C
Converted stream
Containing Hydrogen
260 °C

Water Gas Shift (WGS), Fig. 1 Schemes of “Pd-based membrane reactor” and “traditional process” for WGS reaction
(Marigliano et al. 2003)

References Brunetti A, Caravella A, Drioli E, Barbieri G (2012b)

Amadeo NE, Laborde MA (1995) Hydrogen production
from the low temperature Water Gas Shift reaction:
kinetics and simulation of the industrial reactor. Int
J Hydrog Energy 20:949–958
Barbara E, Stephen H, William R (eds) (1995) Ullmann’s
Encyclopedia of industrial chemistry, 5th completely
revised edn. VCH, New York. ISBN 3-527-20126-2
Barbieri G, Brunetti A, Tricoli G, Drioli E (2008) An
innovative configuration of a Pd-based membrane
reactor for the production of pure hydrogen. Experi-
mental analysis of Water Gas Shift. J Power Sources
182(1):160–167. doi:10.1016/j.jpowsour.2008.03.086
Barbieri G, Brunetti A, Caravella A, Drioli E (2011)
Pd-based membrane reactors for one-stage process of
Water Gas Shift. RSC Adv 1:651–661. doi:10.1039/
c1ra00375e
Brunetti A, Drioli E, Barbieri G (2012a) Medium/high
temperature Water Gas Shift reaction in a Pd-Ag mem-
brane reactor: an experimental investigation. RSC Adv
2:226–233. doi:10.1039/C1RA00569C
Process intensification by membrane reactors: high
temperature WGS reaction as single stage for syngas
upgrading. Chem Eng Tech 35(7):1238–1248.
doi:10.1002/ceat.201100641
Bustamante F, Enick RM, Cugini AV, Killmeyer RP,
Howard BH, Rothenberger KS, Ciocco MV, Morreale
BD, Chattopadhyay S, Shi S (2004) High-temperature
kinetics of the homogeneous reverse Water-Gas Shift
Reaction. AIChE J 50(5):1028–1040
Dittmeyer R, Hollein V, Daub K (2001) Membrane reac-
tors for hydrogenation and dehydrogenation processes
based on supported palladium. J Mol Catal A Chem
173:135–184
Gummalla M, Vanderspurt TH, She Y, Dardas Z,
Olsommer B (2010) Power plant with membrane
water gas shift reactor system. US20100104903
Keiski RL, Salmi T, Niemisto P, Ainassaari J, Pohjola VJ
(1996) Stationary and transient kinetics of the high
temperature Water-Gas Shift Reaction. Appl Catal
A Gen 137:349–370
Marigliano G, Barbieri G, Drioli E (2003) Equilibrium
conversion for a palladium membrane reactor.
4 Water Gas Shift (WGS)

Dependence of the temperature and pressure. Chem Uemiya S, Sato N, Inoue H, Ando H, Kikuchi E (1991)
Eng Process 42:231–236. doi:10.1016/S0255- The water–gas shift reaction assisted by palladium
2701(02)00092-2 membrane reactor. Ind Eng Chem Res 30:585–589
Shu J, Grandjean BPA, Van Neste A, Kaliaguine S (1991)
Catalytic palladium-based membrane reactors: a
review. Can J Chem Eng 69:1036–1048
W
Wine aroma enhancement
Johannes De Bruijn
Department of Agroindustry, Food Engineering
Group, Universidad de Concepcion, Chillan,
Chile
Aroma-A primary wine aroma refers generally to
a pleasant smell of fruity, floral, herbal, mineral,
and/or woodsy flavors of young wine, unique to
each grape variety, which will be interpreted by
the olfactory bulb. Secondary wine aromas are
those flavors that arise from the chemical reac-
tions during fermentation and aging in barrels,
while tertiary aromas are those smells that are
developed by aging in the bottle. The term bou-
quet generally refers to both secondary and ter-
tiary aromas, while the term odor is related to an
unpleasant smell due to possible wine faults.
The typical aroma of wines is mainly due to
volatile compounds that come from the grape.
Apart from free flavor compounds, a significant
part of several aroma compounds is accumulated
in the grape berry as odorless nonvolatile glyco-
sides. Odorous volatiles come available after acid
or enzymatic hydrolysis from glycosides during
wine storage, arise after aging on lees or micro-
oxygenation, and can be enhanced by membrane
technology.
The glycosylated aroma fractions that can give
rise to odor-active compounds upon hydrolysis
include monoterpenes (e.g., linalool, nerol,
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_599-2
geraniol, a-terpineol, and citronellol),
benzenoid compounds (e.g., phenol, guaiacol,
4-vinylguaiacol, and 4-vinylphenol),
norisoprenoids (e.g., damascone, 3-hydroxy
damascone, and enyne diol), and aliphatic alco-
hols (e.g. 3-methylbutanol). Acid hydrolysis
occurs quite slowly in winemaking
conditions. Moreover, exogenous glycosidases
(b-glucosidase, a-rhamnosidase, a-arabinosidase,
and b-apiosidase) from yeast and filamentous
fungi may be used for enzymatic hydrolysis of
mono- and diglycosides to enhance wine aroma
(Cabaroglu et al. 2003). Wine aroma quality may
be further improved by micro-oxygenation with
increase of some aroma attributes (plum, currant,
spicy, and liquorice) and decrease of herbaceous
aroma (Cejudo-Bastante et al. 2011), while aging
on lees changes aroma balance by binding volatile
compounds, such as lactones, terpenoids, ketones,
aldehydes, and esters (Liberatore et al. 2010).
Membrane distillation is a relatively novel
membrane process, which can be applied for the
recovery of aroma compounds (Gryta 2005).
Dense hydrophobic membranes with pores filled
by gas phase are used in this process. The hydro-
phobic nature of the membrane prevents penetra-
tion of the wine into the pores. Therefore, only
volatile components of the wine may be
transported through the membrane. The concen-
tration gradient of some particular volatile spe-
cies in the gas phase at both ends of the
membrane pores causes their transport across
the membrane. The composition of the gas
2 Wine aroma enhancement
Wine aroma Retentate
enhancement,
Fig. 1 Aroma recovery by
pervaporation
Wine
phase above the liquid surface is often expressed
by the partial pressure, and thus the partial pres-
sure difference can be used as a driving force of
the membrane distillation process. The value of
this driving force depends upon the temperature
and composition in the layers adjacent to the
membrane surface. When the driving force is
obtained by partial pressure reduction on the per-
meate side by applying vacuum or blowing a
sweep inert gas on this side, the membrane sepa-
ration process is called pervaporation (Fig. 1).
Usually the pressure of the permeant components
is lower than their saturation pressure, and these
components are therefore removed as vapor. Per-
meate should be collected in traps, which are
normally cooled by using cold water or liquid
nitrogen.
Aroma
Vacuum
Cooling
Permeate
References
Cabaroglu T, Selli S, Canbas A, Lepoutre JP, G€ unata
Z (2003) Wine flavour enhancement through the use
of exogenous fungal glycosidases. Enzyme Microb
Technol 33:581–587
Cejudo-Bastante MJ, Pérez-Coello MS, Hermosín-Guti-
érrez I (2011) Effect of wine micro-oxygenation treat-
ment and storage period on colour-related phenolics,
volatile composition and sensory characteristics.
LWT- Food Sci Technol 44:866–874
Gryta M (2005) Osmotic MD and other membrane distil-
lation variants. J Membr Sci 246:145–156
Liberatore MT, Pati S, Del Nobile MA, La Notte E (2010)
Aroma quality improvement of chardonnay white
wine by fermentation and ageing in barrique on lees.
Food Res Int 43:996–1002
W
Wine Aroma Enhancement,
Membrane Operations of
Johannes De Bruijn
Department of Agroindustry, Food Engineering
Group, Universidad de Concepcion, Chillan,
Chile
Wine aroma enhancement – The aroma profile of
wine is made up by a subtle ratio between com-
pounds of widely varying sensory properties.
During wine making, several components are
lost due to their high volatility in aqueous solu-
tions. These compounds are rather important for
the sensorial quality of wines and might therefore
be recovered and added back to the wines. Com-
plete aroma recovery before dealcoholization and
adding back to dealcoholized wine is another
application (Catarino and Mendes 2011).
Pervaporation, osmotic distillation or evaporative
perstraction, reversed osmosis, and nanofiltration
may constitute promising membrane processes
for recovering aroma compounds from wines.
Pervaporation – This separation process is
based on selective transport inside a dense hydro-
phobic membrane associated with the evapora-
tion of the permeant. Aroma compounds
permeate through the membrane due to the vac-
uum on the downstream side of the membrane.
Once the aroma compounds leave the membrane
as vapor, they will be condensed and collected
under cryogenic temperature. Poly-octyl-methyl-
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_600-2
siloxane/polyetherimide composite asymmetric
membrane or poly-dimethyl-siloxane flat sheet
or spiral wound membranes may be used for the
aroma recovery from wine by pervaporation.
Osmotic distillation or evaporative
perstraction – This process involves the use of a
microporous hydrophobic membrane to separate
two circulating aqueous solutions at different sol-
ute concentrations. The wine phase containing
the volatile components circulates through a hol-
low fiber membrane contactor, while the strip-
ping liquid, e.g., degassed water, flows along
the downstream side of the membrane. When
operating pressure is kept below the capillary
penetration pressure of liquid into the pores, the
membrane is not wetted by the circulating solu-
tions, and air gaps are formed within the pores of
the membrane. Process will be performed at room
temperature, causing no thermal degradation of
volatile compounds. Solubility of wine aroma
compounds is higher in the wine phase than in
pure water, so their transfer into the stripping
phase is limited. On the other hand, ethanol is
preferentially transferred across the membrane
pores into the stripping phase due to the vapor
pressure gradient between the feed and stripping
phase (Diban et al. 2008).
Nanofiltration and reversed
osmosis – Concentration of specific aroma com-
pounds such as diethyl succinate (wine aging),
2-phenyl-ethanol (floral note), cis-3-hexenol
(herbaceous note), and isovaleric acid
(undesired note) of model white wine can be
2 Wine Aroma Enhancement, Membrane Operations of

Wine Aroma Enhancement, Membrane Operations of, Table 1 Solute rejection by RO and NF membranes
(Labanda et al. 2009)
Compound Rejection (%)
Osmonics – SE Toray – UB70 Osmonics – DK
Diethyl succinate 99 96 97
2-Phenyl-ethanol 97 95 95
cis-3-Hexenol 80 77 85
Isovaleric acid 86 76 65

achieved by reversed osmosis and nanofiltration References

using flat sheet polymeric membranes in a batch
retentate-recycling mode. High solute rejection
values indicate enhanced aroma concentration
in the retentate stream phase (Table 1) (Labanda
et al. 2009).
Catarino M, Mendes A (2011) Dealcoholizing wine by
membrane separation processes. Innov Food Sci
Emerg Technol 12:330–337
Diban N, Athes V, Bes M, Souchon I (2008) Ethanol and
aroma compounds transfer study for partial dealcoho-
lisation of wine using membrane contactor. J Membr
Sci 311:136–146
Labanda J, Vichi S, Llorens J, López-Tamames I (2009)
Membrane separation technology for the reduction of
alcoholic degree of a white model wine. LWT Food
Sci Technol 42:1390–1395
W
Wine Clarification by Microfiltration
Johannes De Bruijn
Department of Agroindustry, Food Engineering
Group, Universidad de Concepcion, Chillan,
Chile
Wine clarification – Crude wine is a complex
medium with a turbid aspect. This latter is not
well accepted by the consumer, and wine needs to
be clarified removing particles such as microor-
ganisms (yeast and bacteria), cell debris, colloi-
dal aggregates (tannin, pectin, and
mannoprotein), and potassium tartrate crystals
by microfiltration. Thus, the key roles of clarifi-
cation are to provide limpidity and microbiolog-
ical stabilization of wines.
Microfiltration – Cross-flow microfiltration
could be an alternative for traditional solid–liquid
separation technologies such as centrifugation,
filtration on sheets, diatomaceous earth filtration,
and the use of exogenous additives during wine
making. It offers several advantages such as no
health and environmental problems because of
the elimination of diatomaceous earth use, as
well as the combination of clarification, stabili-
zation, and sterile filtration in one single contin-
uous unit operation without significantly
modifying sensory quality of wines. The wine to
be filtered flows parallel to the membrane surface
and solutes and salts pass through the membrane
by mean of a pressure drop. The shear exerted by
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_601-2
the feed solution flowing parallel to the mem-
brane surface may sweep deposited particles
toward the retentate side, and so the deposited
layer of particles and colloids remains relatively
thin (Fig. 1).
The correct choice of operating conditions and
membrane plays a key role to minimize mem-
brane fouling. Microfiltration performance is
governed by colloids and small particles, where
these constituents result into a sharp initial flux
decline related to both internal and external foul-
ing. Therefore wine filtration should be done
below critical flux above which an irreversible
deposit appears at the membrane surface.
Applied pressure should be smaller than the crit-
ical pressure, where the particles brought to the
membrane surface by the permeate flow are
transported back into the bulk suspension by dif-
fusion and flow out of the membrane. Transmem-
brane pressure is generally in the range between
1 and 3 bars. Moreover, cross-flow velocity
affects mass transport of particles nearby mem-
brane surface by increasing shear stress and shear
induced diffusion. A cross-flow velocity of 2 m/s
is usually applied, which insures sufficient shear
stress and preserves wine quality. A major prob-
lem of increasing cross-flow velocity is the rise of
wine temperature. Temperature should not
exceed 25  C in order to not modify sensorial
characteristics of wine. Furthermore, organic
membranes of cellulose acetate, polypropylene,
polyethersulfone, and polyvinylidene difluoride
and ceramic membranes of zirconium oxide,
2 Wine Clarification by Microfiltration

Pressure alumina, and titanium oxide with an average pore

diameter of 0.2 mm for red wines and
Feed Concentrate 0.1–0.22 mm for white wines show fair results in
terms of permeate flux and wine quality
(El Rayess et al. 2011).

References

El Rayess Y, Albasi C, Bacchin P, Taillandier P, Raynal J,

Mietton-Peuchot M, Devatine A (2011) Cross-flow
microfiltration applied to oenology: a review.
J Membr Sci 382:1–19

Permeate

Wine Clarification by Microfiltration, Fig. 1 Cross-

flow microfiltration
Z
Zeolite A Type
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Zeolite A, also known as LTA (Linde Type A),
belongs to the family of aluminosilicate molecu-
lar sieves. It is characterized by the formula
|(Na+12(H2O)27|8[Al12Si12O48]8 which corre-
sponds to its most common hydrated sodium
form (International Zeolite Association -IZA).
Sodium ions in zeolite A can be exchanged with
other cations such as lithium (Li-LTA), potas-
sium (K-LTA), or calcium (Ca-LTA)
(Townsend and Coker 2001). The principal build-
ing units of zeolite A are sodalite cages which are
connected by four-membered rings forming a
three-dimensional (3D) network (Fig. 1). These
cages consist of central cavities of 11.4 Å in
diameter (supercage) interconnected by eight-
ring openings with a 4.1 Å aperture, thus forming
a remarkably open zeolite framework with a high
void volume fraction of 47 % (McCusker and
Baerlocher 2001). The structure is cubic,
represented by ao = 11.919 Å and the space
group Pm-3m. When Na+ is exchanged with the
larger K+, the pore opening is reduced to approx-
imately 3 Å (K-LTA or 3A zeolite). In the case
that Ca2+ replaces 2Na+, the pore opening
increases to approximately 5 Å (Ca-LTA or 5A
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_604-1
zeolite). Due to aperture size, the Na-LTA zeolite
is also called 4A zeolite.
Zeolite A does not occur in nature and must be
prepared synthetically by hydrothermal crystalli-
zation of reactive alkali metal aluminosilicate
gels at low temperatures (100  C) and pressures
(autogenous) under alkaline condition
(pH typically higher than 12) (Yu 2007). Since
its discovery at the Union Carbide Corporation
Laboratories (Linde Division-Union Carbide) in
the 1950s (Reed and Breck 1956), zeolite A has
been largely investigated and applied at large
scale for a variety of separations and purifications
(Flanigen 1980). Due to its high water adsorption
capacity, LTA zeolite has been first used as a
desiccant for technical gases and liquids. In
1959 Union Carbide marketed the IsoSiv process
for normal isoparaffin separation, representing
the first major bulk separation process using true
molecular sieving selectivity. The supercage
structure revealed also useful for spacio-specific
catalysis, such as paraffin cracking. Owing to its
active ion exchange properties, zeolite A is also
widely used in detergents since the mid 1970s,
particularly as a replacement for the environmen-
tally harmful phosphates for water softening. In
1999, Mitsui Engineering and Shipping Co. Ltd.
manufactured the first LTA membranes to the
market for the dehydration of ethanol, which
was a milestone in the commercialization of zeo-
lite A as a continuous selective barrier (Morigami
et al. 2001).
2 Zeolite A Type

International Zeolite Association (IZA). http://www.iza-

online.org. Accessed December 2015
McCusker LB, Baerlocher C (2001) Zeolite structures. In:
van Bekkum H, Flanigen EM, Jacobs PA, Jansen JC
(eds) Introduction to zeolite science and practice, stud-
ies in surface science and catalysis, vol 137. Elsevier,
London, pp 37–67
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Technol 25:251–260
Reed TB, Breck DW (1956) Crystaline zeolites. II. Crystal
structure of synthetic zeolite, type A. J Am Chem Soc
78:5972–5977
Townsend RP, Coker EN (2001) Ion exchange in zeolites.
Stud Surf Sci Catal 137:467–491
Yu J (2007) Synthesis of zeolites. In: Cejka J, van
Bekkum H, Corma A, Schueth F (eds) Introduction to
zeolite molecular sieves, studies in surface science and
Zeolite A Type, Fig. 1 The type A zeolite catalysis, vol 168. Elsevier, Amsterdam, pp 39–104
structure – view along [100] direction (International Zeo-
lite Association (IZA))

References

Flanigen EM (1980) Molecular sieve zeolite technology-

the first twenty-five years. Pure Appl Chem
52:2191–2211
Z
Zeolite Membrane
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Synonyms
Zeolite membrane – synthesis
Zeolite membranes are selective barriers, which
can be supported or not, and prepared with well-
defined aluminosilicate crystalline structures
having a uniform and well-defined porous frame-
work. Zeolites are attractive molecular sieve
materials which have been used for a long time
as adsorbents, catalysts, and softeners in deter-
gents (ion-exchange properties). Since the early
1990s, zeolite membranes attracted considerable
attention in many research and industrial groups,
exploring their potential for the continuous sepa-
ration of liquids, gas, and vapors, for chemical
synthesis, pollution abatement, catalytic reactors,
micro-reactors, sensors, electrodes, and optoelec-
tronic devices (Caro and Noack 2008; Julbe
2007). Among the 229 currently known zeolitic
framework type codes assigned to date by the
International Zeolite Structure Commission
(www.iza-online.org), less than 10 % have been
prepared in a form of membrane. The most studied
membrane structures are LTA, MFI, CHA, SOD,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_605-1
DDR, FER, MEL, MFI, ERI-OFF, MOR, FAU,
and BEA types (www.iza-online.org).
Several strategies have been developed for
preparing zeolite membranes (supported or self-
supported), such as embedding methods, in situ
hydrothermal synthesis or seeding, and second-
ary growth (Julbe 2007). Embedding is typically
used for the preparation of composite membranes
(often referred as mixed matrix membranes)
containing zeolite particles dispersed in a bulk
matrix, generally a polymer. Zeolite membranes
are usually supported, anchored, or grown on/in a
porous supports with adapted mechanical, ther-
mal, and chemical resistance (typically ceramics
or metals). The seeding and secondary growth
strategy is now considered as the most attractive
method for preparing a variety of zeolite (e.g.,
LTA, MFI, SOD, FAU, CHA, DDR) and zeolite-
type (e.g., MCM, MOF) membranes. It confers
improved flexibility for controlling crystal
growth and film microstructure with high repro-
ducibility and scalability compared to direct in
situ hydrothermal synthesis (Motuzas
et al. 2006). Supported MFI membrane prepared
by secondary growth from a layer of silicalite-1
seeds is shown in Fig. 1. Concerning zeolite
membrane industrialization, LTA membranes
were the first to be prepared at large scale by
Mitsui Engineering and Shipbuilding Co. for the
dehydration of ethanol (Kodo et al. 1997). Other
companies or research centers, including IKTS/
Inocermic in Germany, ECN and Pervatech in the
Netherlands, K€uhni in Switzerland, and Hitachi
2 Zeolite Membrane
Zeolite Membrane,
Fig. 1 MFI zeolite
membrane obtained by
secondary growth on a
porous a-Al2O3 support
(Motuzas et al. 2006)
Zosen in Japan as well as Mitsubishi Chemical
Corporation, also developed zeolite-based
pervaporation or vapor permeation dehydration
systems (Pina et al. 2011). Recently, upscaling of
SAPO-34 (Li et al. 2010) and all-silica DDR
membranes (Makiko and Kenji 2012) has been
considered, respectively, by Shell and NGK Insu-
lators Ltd. for CO2/CH4 separation. Other types
of zeolite membranes, including MFI, FAU
(NaX, NaY), MOR, and T-type membranes, are
considered for various applications of high indus-
trial impact. Bussan Nanotech Research Institute
Inc., namely, reported on mass production of
tubular NaY zeolite membranes for ethanol dehy-
dration (Sato et al. 2008).
References
Caro J, Noack M (2008) Zeolite membranes – recent
developments and progress. Microporous Mesoporous
Mater 115:215–233
International Zeolite Association. http://www.iza-online.
org. Accessed December 2015
Julbe A (2007) Zeolite membranes—synthesis, character-
ization and applications. In: van Bekkum H, Cejka J,
Corma A, Schuth F (eds) Introduction to zeolite sci-
ence and practice, studies in surface science and catal-
ysis. Elsevier, Amsterdam, pp 181–219
Kondo M, Komoriki M, Kita H, Okamoto KI
(1997) Tubular-type pervaporation module with zeo-
lite NaA membrane. J Membr Sci 133:133–141
Li S, Carreon MA, Zhang Y, Funke HH, Noble RD,
Falconer JL (2010) Scale-up of SAPO-34 membranes
for CO2/CH4 separation. J Membr Sci 352:7–13
Makiko N, Kenji Y (2012) Process for the production of
DDR-type zeolite membranes. US Patent 8,497,223
Motuzas J, Julbe A, Noble RD, van der Lee A,
Beresnevicius ZJ (2006) Rapid synthesis of oriented
silicalite-1 membranes by microwave-assisted hydro-
thermal treatment. Microporous Mesoporous Mater
92:259–269
Pina P, Mallada R, Arruebo M, Urbiztondo M,
Navascués N, de la Iglesia O, Santamaria J (2011)
Zeolite films and membranes. Emerging applications.
Microporous Mesoporous Mater 144:19–27
Sato K, Sugimoto K, Nakane T (2008) Mass-production of
tubular NaY zeolite membranes for industrial purpose
and their application to ethanol dehydration by vapor
permeation. J Membr Sci 319:244–255
Z
Zeolite T Type
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Zeolite T (Linde type T) is a crystalline alumino-
silicate with hexagonal symmetry. Its typical for-
mula is 0.3Na2O-0.7K2O-Al2O3-6.9SiO2-
7.2H2O. It corresponds to a disordered inter-
growth of erionite and offretite structures in
which the more open offretite (12-ring main
channels parallel to the c-axis and 8-ring
sub-channels normal to the c-axis with pore
sizes of 0.67  0.68 nm and 0.36  0.49 nm,
respectively) (Fig. 1) is interspersed at intervals
with the tighter erionite units (8-ring channels
parallel to the c-axis with pore size of
0.36  0.51 nm) (Spivey et al. 1992). The frame-
work structures of offretite and erionite are
closely related, and the synthesized zeolite T is
mainly composed of the offretite phase with only
small amounts of erionite sheets. Due to the spe-
cific position of single erionite unit cells at the
end of the large pore of offretite, erionite controls
the diffusion path by forcing the molecules to
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_606-1
pass through the small 8-rings erionite rings.
Pure erionite and offretite phases can be obtained
only in the presence of an organic template,
whereas intergrowth-type zeolite T can be synthe-
sized without any template. Zeolite T, with inter-
mediate Si/Al ratio of 3–4, is acid resistant and
thermally stable while remaining hydrophilic. Its
high acid resistance often overpasses other more
common zeolites such as A, X, and Y. Zeolite
T can be used for the selective adsorption or dry-
ing of acid gases and liquids at high temperatures.
Both erionite and intergrowth offretite/erionite
zeolite types have been reported as very attractive
materials for catalysis or selective barriers appli-
cable in conversion of methanol to C2–C5 olefins,
selective catalytic dewaxing, and molecular siev-
ing of n-butane (Yang and Evmiridis 1996). Zeo-
lite T membranes have enormous potential for
industrial dehydration processes, e.g., separating
water from organic liquids in acidic environment,
such as esterification hybrid process (Zhoua
et al. 2009). Due to their molecular sieving prop-
erties, zeolite T membranes have been also con-
sidered for gas separation applications, namely for
separating CO2/N2 and CO2/CH4 mixtures up to
473K (Cui et al. 2004, see also Zhang et al. 2013).
2 Zeolite T Type

Zeolite T Type, Fig. 1 (a) The erionite-type zeolite, (b) the offretite-type zeolite – view along [001] direction
(International zeolite association (IZA))

References Yang S, Evmiridis NP (1996) Synthesis and characteriza-

Cui Y, Kita H, Okamoto K (2004) Preparation and gas
separation performance of zeolite T membrane.
J Mater Chem 14:924–932
International zeolite association (IZA) http://www.iza-
online.org. Accessed Jul 2013
Spivey J, Froment GF, Dehertog WJH, Marchi AJ
(1992) Zeolite catalysis in the conversion of methanol
into olefins. In: Spivey J (ed) Catalysis, vol 9. The
Royal Society of Chemistry, Cambridge, pp 1–64
tion of an offretite/erionite type zeolite. Microporous
Mesoporous Mater 6:19–26
Zhang XL, Qiu LF, Ding MZ, Hu N, Zhang F, Zhou RF,
Chen XS, Kita H (2013) Preparation of Zeolite T
Membranes by a Two-Step Temperature Process for
CO2 Separation. Ind Eng Chem Res 52:16364–16374
Zhoua H, Li Y, Zhua G, Liua J, Yang W (2009)
Microwave-assisted hydrothermal synthesis of a&b-
oriented zeolite T membranes and their pervaporation
properties. Sep Purif Technol 65:164–172
Z
Zeolite X: Type
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Zeolite X, together with zeolite Y, belongs to the
family of aluminosilicate molecular sieves with a
faujasite-type structure (FAU). It is characterized
by the formula |(Ca, Mg, Na2)29 (H2O)240|
[Al58Si134O384]– FAU (International zeolite
association (IZA)). Faujasite is a rare zeolite,
although its synthetic counterparts Linde X and
Linde Y are largely used as sorbents and cata-
lysts. Zeolite X differs from zeolite Y by its Si/Al
atomic ratio which is typically in the range from 1
to 1.5 for the X and higher for the Y-type zeolite.
High Si/Al ratio is desirable towards thermal
stability, a property that is less favorable to zeo-
lite X. The 24 tetrahedra cuboctahedral units
(sodalite cages) in the FAU framework type are
arranged in the same way as the carbon atoms in
diamond. They are connected via hexagonal
prisms (double six rings) forming a three-
dimensional porous channel structure along
[110], characterized by 12 oxygen ring window
openings with the aperture of 8 Å and supercages
of approximately 12 Å (McCusker and
Baerlocher 2001). The FAU-type zeolite
supercage viewed along [111] is shown in Fig. 1
(International zeolite association (IZA)).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_607-1
The combination of large void volumes and
large pore openings in a three-dimensional chan-
nel system makes FAU molecular sieve ideal for
many catalytic applications. This zeolite is also
attractive for its ion exchange and adsorptive
properties.
The combination of Si4+ and A13+ results in a
deficiency of positive charge which is balanced
by exchangeable cations. Due to its very low
Si/Al ratio, the zeolite X framework provides a
large number of cation exchange sites balancing
the framework aluminum, thus leading to high
cation contents and exchange capacities. Zeolite
X is generally synthesized by hydrothermal crys-
tallization of reactive alkali metal aluminosilicate
gels or clear solutions at low temperature
(70–300  C, usually 100  C) and pressure
(autogenous) under alkaline conditions. Starting
typically from sodium aluminate and sodium sil-
icate, zeolite X is obtained in its Na+ form. Zeo-
lite NaX is a metastable phase, meaning that other
types of zeolites such as P, A, or sodalite may
form if the recipe is not followed carefully
(Balkus and Ly 1991). For specific catalytic
applications, the incorporation of various metal
cations into the structure can be carried out by
impregnation or ion exchange. This results in the
modification of the number and nature of acid
sites influencing the diffusion of reactants and
products. A large variety of cationic species has
been introduced into FAU frameworks. X-type
zeolite has a wide range of industrial applications
for gas or vapor adsorption, separation, and as
2 Zeolite X: Type
Zeolite X: Type, Fig. 1 The FAU type zeolite
supercage – view along [111] direction (www.iza-online.
org)
catalyst. Examples of applications in chemical
reactions include isomerization of 1-butene,
alkylation of toluene with ethylene or methanol,
and cycloaddition of carbon dioxide to ethylene
oxide (Ribeiro et al. 1984). X-type zeolites can be
used to adsorb an unwanted compound during
decomposition reactions such as removal of
alkyl hydroperoxides from ethers and olefins
during hydrobromination of alkenes (Wortel and
van Bekkum 1980). Alcohol dehydration by
pervaporation is a potential application for
X-type membranes (Zhou et al. 2012). However,
in many large-scale industrial applications, its
chemical analogue with Si/Al ratio higher than
1.5 (zeolite Y) has superseded zeolite X because
of its higher chemical and thermal stability.
References
Balkus KJ, Ly KT (1991) The preparation and character-
ization of an X-Type zeolite, an experiment in solid-
state chemistry. J Chem Educ 68:875–877
International zeolite association (IZA) http://www.iza-
online.org. Accessed July 2013
McCusker LB, Baerlocher C (2001) Zeolite structures. In:
van Bekkum H, Flanigen EM, Jacobs PA, Jansen JC
(eds) Introduction to zeolite science and practice,
vol 137, Studies in surface science and catalysis.
Elsevier, London, pp 37–67
Ribeiro FR et al (1984) Zeolites: science and technology.
Martinus Nijhoff, The Hague
Wortel TM, van Bekkum H (1980) Removal of peroxide
impurities by zeolites. J Org Chem 45:4763–4764
Zhou H, Korelskiy D, Leppäjärvi T, Grahn M,
Tanskanen J, Hedlund J (2012) Ultrathin zeolite
X membranes for pervaporation dehydration of etha-
nol. J Membr Sci 399–400:106–111
Z
Zeolite Y: Type
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Zeolite Y, together with zeolite X, belongs to the
family of aluminosilicate molecular sieves with a
faujasite-type structure (FAU), which is charac-
terized by the basic formula |(Ca, Mg, Na2 )29
(H2O)240 |[Al58 Si134 O384 ]– FAU (Baerlocher
2007). Faujasite is a rare zeolite, although its
synthetic counterparts Linde X and Linde Y are
largely used as sorbents and catalysts. Zeolite Y
has a higher Si/Al atomic ratio than zeolite X
(typically in the range 1–1.5). Therefore, the
higher content of silica confers zeolite Y with
higher thermal stability. The 24-tetrahedracuboc-
tahedral units (sodalite cages) in the FAU frame-
work type are arranged in the same way as the
carbon atoms in diamond. They are connected via
hexagonal prisms (double 6-rings) forming a
3-dimensional porous channel structure along
[110], characterized by 12-oxygen ring window
openings with the aperture of 8 Å and supercages
of approximately 12 Å (McCusker and
Baerlocher 2001). The FAU-type zeolite
supercage viewed along [111] is shown in Fig. 1
The combination of large void volume and
large pore openings in a 3-dimensional channel
system makes this thermally stable FAU molec-
ular sieve ideal for many catalytic applications.
# Springer-Verlag Berlin Heidelberg 2016
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_608-2
This zeolite is also considered for its ion-
exchange and adsorptive properties. Zeolite Y is
generally synthesized by hydrothermal
crystallisation of reactive alkali metal alumino-
silicate gels or clear solutions at low temperature
(70–300 ˚C, usually 100 ˚C) and pressure (autog-
enous) under alkaline conditions. Starting typi-
cally from sodium aluminate and sodium silicate,
the Y zeolite is obtained in its Na+ form (Blatter
and Schumacher 1991) and a replacement of the
Na+ cations by protons (leading to the H-zeolite
form) is required for applications in acid cataly-
sis. Due to the poor stability of the FAU structure
in acidic media, this conversion is done indirectly
via an ammonium exchange resulting in NH4+ Y,
where the cation is decomposed into ammonia
and protons, thus yielding a highly crystalline
H-FAU structure. Dealumination of the Y zeolite
framework results in the formation of ultra-stable
Y zeolite (USY) with high (hydro)thermal stabil-
ity. USY prepared by thermal, hydrothermal, or
chemical dealumination of zeolite Y is one of the
most widely employed zeolite material in the
petrochemical industry. Zeolite Y is essentially
used as a Fluid Cracking Catalyst (FCC) of heavy
petroleum distillates, for increasing the yield of
gasoline and Diesel fuel from crude oil (Kung
at al. 2000). It is also used to increase the aro-
matic content of refinery products in hydrocrack-
ing units, when it is associated with platinum or
palladium species, deposited by either impregna-
tion or ion exchange (Ribeiro 1984). A large
variety of other applications have been reported
2 Zeolite Y: Type
Zeolite Y: Type, Fig. 1 The FAU type zeolite
supercage – view along [111] direction (International zeo-
lite association (IZA))
for the Y zeolite, including the dealcoholization
of beer, the removal of toxic preservatives in the
pharmaceutical preparation of insulin, the slow-
release of drugs, or the encapsulation of specific
ions for electrocatalytic applications (Pavelic and
Hadzija 2003), also in addition to simple gas
phase or liquid phase separations and treatments,
including membranes (Morooka et al. 1998).
Bussan Nanotech Research Institute Inc., namely,
reported on mass-production of tubular NaY zeo-
lite membranes for ethanol dehydration (Sato et
al. 2008).
References
Baerlocher C, McCusker L, Olson DH (2007) Atlas of
zeolite framework types, 6th revised edn. Elsevier,
Amsterdam
McCusker LB, Baerlocher C (2001) Zeolite structures. In:
van Bekkum H, Flanigen EM, Jacobs PA, Jansen JC
(eds) Introduction to zeolite science and practice.
Studies in surface science and catalysis, vol 137.
Elsevier, London, pp 37–67
International zeolite association (IZA) http://www.iza-
online.org. Accessed July 2013
Blatter F, Schumacher E (1991) The preparation of pure
zeolite NaY and its conversion to high-silica faujasite,
an experiment for laboratory courses in inorganic
chemistry. J Chem Educ 68:519–521
Kung HH, Williams BA, Babitz SM, Miller JT, Haag WO,
Snurr RQ (2000) Enhanced hydrocarbon cracking
activity of Y zeolites. Top Catal 1–2:59–64
Ribeiro FR et al (1984) Zeolites: science and technology.
Martinus Nijhoff Publishers, The Hague
Pavelic K, Hadzija M (2003) Medical applications of
zeolites. In: Auerbach SM, Carrado KA, Dutta PK
(eds) Handbook of zeolite science and technology
(chap. 24). Marcel Dekker, New York
Morooka S, Takahiro K, Katsuki K (1998) Carbon dioxide
separation from nitrogen using Y-type zeolite mem-
branes. In: Inui T, Anpo M, Izui K, Yanagida S,
Yamaguchi T (ed) Studies in surface science and catal-
ysis. Advances in chemical conversions for mitigating
carbon dioxide, vol 114. Elsevier, Amsterdam, pp
665–668
Sato K, Sugimoto K, Nakane T (2008) Mass-production of
tubular NaY zeolite membranes for industrial purpose
and their application to ethanol dehydration by vapor
permeation. J Membr Sci 319:244–255
Z
Zeolite-Embedded Membrane
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
Zeolite-embedded membranes belong to the fam-
ily of composite selective barriers (also referred
as mixed matrix membranes (MMMs)), which
are typically obtained by dispersing zeolite crys-
tals in a bulk matrix, usually a polymer film
(Bastani et al. 2013). Zeolite-filled MMMs have
been intensively studied from the early 1970s as a
strategy to overcome the permeability/selectivity
trade-off of conventional polymeric membranes.
The basic idea was to obtain a synergic effect by
combining the high selectivity and permeability
of zeolites with the attractive mechanical proper-
ties and economical processability of polymers.
These membranes were intensively considered
for difficult gas separations or pervaporation but
also as interface contactors and in fuel cell appli-
cations (Jeong et al. 2010; Zornoza et al. 2011;
Tricoli and Nannetti 2003). The key point of
membrane efficiency bears on the selection of a
relevant zeolite/polymer coupling, thus providing
a good quality interfacial contact between the
inorganic filler and the matrix (nonselective dif-
fusion pathways). Several zeolite surface
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_609-1
modification strategies, such as silanation,
annealing, or Grignard treatments, have been
considered to improve and optimize interfaces.
Nanosize zeolite particles embedded in MMMs
generally outperform MMMs prepared with
micron size particles, when optimized loading
and dispersion are used. Preparation of zeolite-
embedded membranes (Fig. 1) is adapted from
classical methods used for polymeric mem-
branes, although membrane processing steps
and solvents that can “clog” the zeolites should
be avoided. Early attempts at designing MMMs
focused on gas separation using rubbery poly-
mers such as polydimethylsiloxane (PDMS).
Nowadays, glassy polymers such as polyimide
(PI), polyethersulfone (PES), or copolymers are
preferably used together with semicrystalline
polyvinylidene fluoride (PVDF). The latter pos-
sesses excellent mechanical properties, thermal
stability, and high chain movements, enabling
preparation of membranes with high inorganic
filler content. Typical zeolite filles in MMMs
are silicalite-1, ZSM-5, L, 3A, 4A, 5A, 13X,
KY, H-SSZ-13 b-type, or SAPO-34 (Julbe
2007). Zeolite-type materials (e.g., MCM-41,
MCM-48, SBA-15, ZIF) have been also consid-
ered, and highly attractive results were also
obtained with the MOF (metal-organic frame-
works) fillers which provide better interfacial
contact with polymers (Bastani et al. 2013).
2 Zeolite-Embedded Membrane
Zeolite-Embedded Membrane, Fig. 1 MMM with
MFI zeolite particles (22 wt%) embedded in a PVDF
polymer matrix (Drobek et al. 2015)
References
Bastani D, Esmaeili N, Asadollahi M (2013) Polymeric
mixed matrix membranes containing zeolites as a filler
for gas separation applications: a review. J Ind Eng
Chem 19:375–393
Drobek M, Figoli A, Santoro S, Navascués N, Motuzas J,
Algieri C, Gaeta N, Barbieri G, Mallada R, Julbe A,
Drioli E (2015) PVDF-MFI mixed matrix membranes
as VOCs adsorbers, Micropor Mesopor Mat
207:126–133
Jeong D, Oh J, Yum I, Lee Y (2010) Removal of VOC
from their aqueous solution by pervaporation with
PDMS-zeolite composite membrane. Desalination
Water Treat 17:242–247
Julbe A (2007) Zeolite membranes—synthesis, character-
ization and applications. In: van Bekkum H, Cejka J,
Corma A, Schuth F (eds) Introduction to zeolite sci-
ence and practice, Studies in Surface Science and
Catalysis. Elsevier, Amsterdam, pp 181–219
Tricoli V, Nannetti F (2003) Zeolite-Nafion composites as
ion conducting membrane materials. Electrochim Acta
48:2625–2633
Zornoza B, Esekhile O, Koros WJ, Téllez C, Coronas
J (2011) Hollow silicalite-1 sphere-polymer mixed
matrix membranes for gas separation. Sep Purif
Technol 77:137–145
Z
Zeta Potential
Paul Melvyn Williams
Swansea University, College of Engineering,
Swansea, UK
Zeta potential: When two phases are placed in
contact, there develops in general a difference in
potential between them (Hunter 1981). The term
zeta potential is an abbreviation for the electroki-
netic potential in colloidal systems. In the colloi-
dal chemistry literature, it is usually represented
using the Greek letter zeta (z). The zeta potential
is commonly associated with particulate systems
but can also be measured for surfaces such as
membranes. The zeta potential does not occur
exactly at the interface, but is in fact the electric
potential in the interfacial double layer at the
location of the slipping plane (or outer Helmholtz
plane) (Hunter 1981) versus a point in the bulk
fluid away from the interface (see Fig. 1).
The zeta potential is used in DLVO theory
(Hunter 1989) to describe the magnitude of the
electrostatic forces (usually repulsive for liked
charged particles/surfaces) and give the potential
stability of a colloidal system. For colloidal sys-
tems, a high zeta potential will confer stability,
i.e., the solution or dispersion will resist aggrega-
tion/flocculation. When the zeta potential is low,
# Crown 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_612-1
attraction exceeds repulsion and the dispersion
will flocculate. A value of 25 mV (positive or
negative) is usually taken as the arbitrary value
that separates low charged surfaces from highly
charged surfaces. Colloids with a high magnitude
of the zeta potential (positive or negative) are said
to be electrically stabilized.
The zeta potential, however, is not measurable
directly but can be calculated using theoretical
models and experimentally determined values
such as the electrophoretic mobility or the
streaming potential. Electroacoustic phenomena
may also be used for the calculation of zeta
potential. The most known and widely used the-
ory for calculating zeta potential from experi-
mental data is that developed by Smoluchowski
(1903). This theory was originally developed for
electrophoresis; however, an extension to elec-
troacoustics is now also available (Dukhin and
Goetz 2002). Smoluchowski’s theory is powerful
because it is valid for dispersed particles of any
shape and any concentration. Smoluchowski’s
theory does have limitations in that it is only
valid for thin double layers and surface conduc-
tivity is neglected. More modern, rigorous elec-
trokinetic theories that are valid for any zeta
potential have been developed and are available
in the literature (Dukhin and Semenikhin 1970;
O’Brien and White 1978).
2 Zeta Potential

References
Slipping plane
Dukhin AS, Goetz PJ (2002) Ultrasound for characteriz-
ing colloids. Elsevier
Particle with negative Dukhin SS, Semenikhin NM (1970) Theory of double
surface charge layer polarization and its effect on the electrokinetic
and electrooptical phenoma and the dielectric constant
of dispersed systems. Kolloidn Zh 32:360–368
Hunter RJ (1981) Zeta potential in colloid science: prin-
ciples and applications. Academic, London
Hunter RJ (1989) Foundations of colloid science,
vol 1. Oxford University Press, Oxford
Stern layer Diffuse layer
Malvern Instruments Ltd (2001) Zeta potential—an intro-
−100 duction in 30 minutes (technical note MRK654-01).
Surface potential Zetasizer Nano series technical note
Stern potential O’Brien RW, White LR (1978) Electrophoretic mobility
mV of a spherical colloidal particle. J Chem Soc Faraday
Zeta potential
Trans 2(74):1607–1626
von Smoluchowski M (1903) Contribution to the theory of
0 electro-osmosis and related phenomena. Bull Int Acad
Distance from particle surface Sci Cracovie 3:184–199

Zeta Potential, Fig. 1 Illustration of slipping plane for a

spherical particle (MRK654-01)
Z
ZSM-5 Zeolite Membrane
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
ZSM-5 (Zeolite Socony Mobil-5, patented by
Mobil oil company in 1975) is a high silica zeo-
lite with a MFI framework structure (Mobil Five)
characterized by the formula |(Nax(H2O)16|
[AlxSi96 xO192], where x < 27 (International
Zeolite Association-IZA). It is composed of
pentasil units which are linked to form pentasil
chains connected via oxygen bridges to form
corrugated sheets with 10-ring holes (Fig. 1).
Oxygen bridges between these sheets result in a
3-dimensional system with straight 10-ring chan-
nels parallel to the corrugations (along y) and
sinusoidal 10-ring channels perpendicular to the
sheets (along x). The MFI 3D framework,
consisting of straight and zigzag channels, is a
rather complex zeolite framework type. The
structure is orthorhombic (space group Pnma) at
high temperatures, but a phase transition to the
monoclinic space group occurs on cooling below
the transition temperature, i.e., between 300 and
350 K. Because the pore openings are 10-rings
(straight channels have circular openings of
0.54–0.56 nm and sinusoidal channels have ellip-
tical openings of 0.51–0.55 nm), the shape
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_615-1
selectivity for sorption and catalysis resulted in
many applications of this zeolite in refinery and
petrochemical industry, including for hydrocar-
bon isomerization and alkylation of hydrocar-
bons (McCusker and Baerlocher 2001). ZSM-5
does not occur in natural rocks and must be pre-
pared synthetically in basic media at high pres-
sures (autogenous) and temperatures (typically
120–200  C) from alumina and silica sources
and eventually in the presence of structure
directing agents such as tetrapropylammonium-
based compounds. Seeds with the MFI structure
can also be used to fasten the synthesis kinetics
and generate uniform supported layers/mem-
branes. The type of the raw materials and the
presence/absence of template are of the utmost
importance on the crystal morphology and the
distribution of aluminum atoms in the frame-
work, leading to the formation of zeolite catalyst
with acidic properties which could be effectively
controlled during the synthesis. The acidity is
proportional to the Al content and a number of
positive charges (e.g., Na+ or H+) attached to the
framework which tends to keep the zeolite charge
neutral. Due to its high acidity, ZSM-5 is an
active heterogeneous catalyst for acid-catalyzed
reactions. ZSM-5 membranes have been largely
investigated in the literature, for gas separation
(e.g., CO2 (Bernal et al. 2004)), pervaporation
(organic dehydration or removal of organics
from water), and applications in catalytic reactors
2 ZSM-5 Zeolite Membrane
ZSM-5 Zeolite Membrane, Fig. 1 The MFI type
structure – view along [010] direction (International Zeo-
lite Association-IZA)
(Julbe 2007). Xylene isomerization favoring
paraxylene production is a typical example
where molecular sieving through ZSM-5 leads
to a faster diffusion of the latter. A series of
additives has been introduced within the ZSM-5
membranes, either by postsynthetic modification
or directly during the synthesis, to modify either
the surface properties or the channel size of the
zeolite membrane. Catalytic cracking of
methyldiethoxysilane is an example of postmodi-
fication, yielding attractive H2 separation proper-
ties for the modified ZSM-5 membranes, up to
500  C (Wang and Lin 2012; Hong M et al.
2005).
References
Bernal MP, Coronas J, Menendez M, Santamaria J (2004)
Separation of CO2/N2 mixtures using MFI-type zeolite
membranes. AlChE J 50:127–135
Falconer JL, Noble RD (2005) Modification of
zeolite membranes for H2 separation by catalytic
cracking of methyldiethoxysilane, Ind Eng Chem Res
44(11):4035–4041
International Zeolite Association (IZA), http://www.iza-
online.org. Accessed December 2015
Julbe (2007) Zeolite membranes—synthesis, characteri-
zation and applications. In: van Bekkum H, Cejka J,
Corma A, Schuth F (eds) Introduction to zeolite sci-
ence and practice, studies in surface science and catal-
ysis. Elsevier, Amsterdam, pp 181–219
McCusker LB, Baerlocher C (2001) Zeolite structures. In:
van Bekkum H, Flanigen EM, Jacobs PA, Jansen JC
(eds) Introduction to zeolite science and practice, stud-
ies in surface science and catalysis, vol 137. Elsevier,
London, pp 37–67
Wang H, Lin YS (2012) Synthesis and modification of
ZSM-5/silicalite bilayer membrane with improved
hydrogen separation performance. J Membr Sci
396:128–137
Hong M, Falconer JL, Noble RD (2005) Modification of
zeolite membranes for H2 separation by catalytic
cracking of methyldiethoxysilane, Ind Eng Chem Res
44(11):4035–4041
A
Ab Initio Calculation
Giorgio De Luca
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rende (CS), Italy
Although the term ab initio usually indicates cal-
culations based on first principles, either they are
related to classical or to quantum mechanics, this
term is generally used when it refers to calcula-
tions based on quantum mechanics first principles
(Szabo and Ostlund 1994). Thus, if the
d’Alembert equation is used to describe a force
balance, in which the expression of the forces is
only expression of chemical-physical average
properties (values obtained as average of micro-
scopic properties) without any use of empirical
adjustable parameters, the calculation can also be
defined ab initio. As mentioned, in general, the
term ab initio is used when the calculations are
performed by using the Schrödinger equation or
rather an eigenvalue equation for the quantum
system. However, attention must be paid to the
quantities or potential operators that define the
eigenvalue equations. In fact, if the operators in
the Hamiltonians are defined using experimental
data or by means of fitting procedure, then the
calculation should not be defined ab initio but
semiempirical (Clementi and Corongiu 1995).
The density functional theory (Parr and Yang
1989) is a controversial case, since in principle,
it is an ab initio theory, but various potentials
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_616-1
defining the quantum system are obtained by
using empirical data. For example, hybrid poten-
tials are linear combinations of pure potentials.
The coefficients of the linear combinations are
obtained using experimental data. Nevertheless,
other potentials are obtained from the thermody-
namic theory of electron gas (statistical thermo-
dynamics); thus the latter can be considered ab
initio. For this reason also the density functional
theory is considered an ab initio methodology.
Summarizing, two broad theoretical methods
can be identified: those that make use of adjust-
able parameters that should be to be defined each
time, ad hoc, depending on the system studied
and those that do not use ad hoc parameters which
only refer to the first principles and are known as
the ab initio methods.
Particular attention should be given on
multiscale simulations in which paramters
provided by sub and nanoscales are used in
meso and macro scales without resort of empiri-
cal-adjustable parameters. Even these types
of calculations can be defined ab initio.
(De Luca et al. 2014) recently, have used differ-
ent approaches, ranging from quantum mechan-
ics to macroscopic models, to simulate the
formation of the protein cake on a membrane
surface and the conseguent decay of water flux.
Although various parameters were calculated ab-
initio others have not yet been assessed in this
way; however, this work represents one of the
first attempts of an ab-initio simulation of a mem-
brane process.
2 Ab Initio Calculation

References Parr RG, Yang W (1989) Density functional theory of

atoms and molecules. Oxford University Press, New
Clementi E, Corongiu G (eds) (1995) Methods and tech- York
niques in computational chemistry METECC-95. Szabo A, Ostlund NS (1994) Modern quantum chemistry.
STEF, Cagliari Macmillan Publishing Co., New York
De Luca G, Bisignano F, Paone F, Curcio S (2014) Multi-
scale modeling of protein fouling in ultrafiltration pro-
cess. J Membr Sci 452:400–414
M
Membrane Aging
Donald R. Paul
Department of Chemical Engineering, Texas
Materials Institute, Austin, TX, USA
The term membrane aging as used here refers to
the physical aging process that occurs over time
for a membrane based on a glassy polymer. As
polymers are cooled through the region of the
glass transition temperature, Tg, the time scale
of motions of the polymer chain segments
becomes much longer than the time scale of the
observation; thus, the material is no longer able to
maintain an equilibrium structure like it does
above Tg. Thus, glassy polymers exist in a
nonequilibrium state that has a higher specific
volume (or lower density) than it would have if
it could have maintained an equilibrium state.
This situation is illustrated in Fig. 1 that shows a
plot of polymer-specific volume versus tempera-
ture. The actual state achieved below Tg depends
on how the glass was formed and all its prior
history. The extra fractional free volume, FFV,
the glass has owing to being trapped in this
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_622-5
nonequilibrium state affects many properties
such as gas permeability, P, as seen by the
relationship:
P ¼ AeB=FFV (1)
At temperatures below Tg, the material continues
to proceed toward its equilibrium (see arrow in
Fig. 1), albeit at a very slow rate. This densifica-
tion process is called physical aging or structural
relaxation (Kovacs et al. 1977). This process of
aging is thermally reversible meaning that the
original state can be restored by heating above
Tg. As a result of this densification process or
physical aging, all properties like permeability
also evolve over time.
It has been observed that the rate of physical
aging of glassy polymer films depends strongly
on thickness and that this effect is particularly
pronounced below thicknesses of less than about
1 mm, which can be tracked by measuring gas
permeability, as seen in Fig. 2 for polysulfone
(Huang and Paul 2004). A convenient summary
of the experimental techniques used to study
these effects of thickness for thin films and
2 Membrane Aging

contemporary interpretations of the observations

has been given by Rowe et al. including the
effects of prior history (Rowe et al. 2011).
Polymer Specific Volume

Tg
Glassy Since gas separation membranes must have a
State very thin, thicknesses 100 nm, skin or separat-
ing layer to achieve high fluxes, they are expected
to exhibit similar effects when the polymer is
Equilibrium State glassy. This may be manifested as a decline in
productivity over the lifetime of the module. Of
course, much of this aging may have already
occurred prior to the membrane being put into
service. Even so, this means that the actual per-
Temperature meability of the active layer may be much lower
than estimated by thick film (tens of microns in
Membrane Aging, Fig. 1 Illustration of the specific
volume versus temperature above (rubbery state) and thickness) tests.
below (glassy state) the glass transition temperature of a
polymer. The arrow indicates the path of slow densifica-
tion of the glass over time

Membrane Aging, 2.4

Fig. 2 Effect of physical
aging on the oxygen
PSF
permeability for a series of 2.2
polysulfone films (at 35  C)
(Huang and Paul 2004)
2.0
O2 permeability (barrer)

(Reproduced with
permission of Elsevier
(Copyright 2004)) `=
1.8
61.2 µm
35.6 µm
1.6 8.50 µm
3.60 µm
1.4 1.85 µm
0.99 µm
0.72 µm
1.2
0.41 µm

1.0
1 10 100 1000 10000
Aging time (hr)
Membrane Aging
References
Huang Y, Paul DR (2004) Physical aging of thin glassy
polymer films tracked by gas permeability. Polymer
45:8377–8393
Kovacs AJ, Hutchinson JM, Aklonis JJ (1977) In: Gaskell
PH (ed) The structure of non-crystalline materials.
Taylor and Francis, London, pp 153–163
3
Rowe BW, Freeman BD, Paul DR (2011) Physical aging
of membranes for gas separations, Chapter 3. In:
Drioli E, Barbieri G (eds) Membrane engineering for
the treatment of gases. Gas-separation problems with
membranes, vol 1. Royal Society of Chemistry,
pp 58–83
A
Air Gap Membrane Distillation
(AGMD)
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Szczecin, Poland
AGMD is a configuration of membrane distilla-
tion (MD) in which an air layer is interposed
between a porous hydrophobic membrane and
the condensation surface (Fig. 1). In the process,
volatile compounds (including water) present in a
warm feed evaporate at the liquid/vapor interface
formed at the membrane surface. The vapor is
transferred through the membrane pores and the
gas gap and finally condenses on a cold surface
inside the membrane module. The driving force
of the mass transfer in AGMD is the difference in
vapor pressure on both sides of the membrane
The air gap significantly reduces the heat loss
by the membrane material, therefore the perme-
ate flux could increase. On the other hand air gap
forms a barrier for the vapor, and due to the mass
transfer resistance the permeate flux decreases
with an increase of the air gap width (Table 1)
(Alkhudhiri et al. 2012). When the gap width is
changed, the mechanism of heat transfer may be
changed from pure conduction and diffusion to
natural convection. The optimum of air gap width
should be determined to achieve the best perfor-
mance of the AGMD system taking into account a
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_623-2
reduction of the heat loss and the value of the
permeate flux.
Since in AGMD the permeate is condensed on
the cold surface, the liquid permeate is separated
from the membrane surface, which prevents the
membrane wetting. Thus an important advantage
of the process is the ability to remove the organic
compounds from aqueous solutions.
The permeate flux in AGMD can vary from
ca. 0.3 to 26 kg/m2h, depending on the operating
conditions and feed composition. The rejection
coefficient of nonvolatile species, e.g., NaCl,
usually amounts close to 100 %. Generally, in
AGMD the nonvolatile species present in a feed
are almost completely retained, whereas volatile
compounds are partially transferred through the
membrane. The separation of compounds present
in aqueous solutions using AGMD is based not
only on the vapor/liquid equilibrium, but also the
diffusion rate of the feed components through the
gas filling the membrane pores and the air gap
between the membrane and the condensation
surface.
The air entrapped within the membrane pores
and in the air gap can be considered as a stagnant
film, thus the mass transfer in AGMD is generally
described according to the ordinary molecular
diffusion including both the air and
noncondensable gases in the membrane pores
and in the air gap. The air gap width is usually
10–100 times greater than the membrane thick-
ness; therefore the membrane characteristics are
usually neglected. In AGMD, the heat transfer
2 Air Gap Membrane Distillation (AGMD)

includes the heat transfer through the feed bound-
ary layer, through the membrane and the gas gap,
condensation at the cold surface, and heat transfer
through the condensate liquid boundary layer and
to the cooling water. To optimize the AGMD
systems, the effects of operating parameters
should be taken into account (Khayet and
Matsuura 2011).
The feed temperature strongly affects the per-
meate flux. Since the vapor pressure of aqueous
solutions grows exponentially with temperature,
the driving force increases for both water and
Feed Tf,in
vapor
Tf,m Tc
Important condition:
Tf,m > Tc
air gap
volatile compounds present in a feed. Thus, the
total permeate flux Jt (a sum of the water vapor
flux Jw and the volatile compounds flux Jv)
increases, but the selectivity of volatile solutes
decreases with a feed temperature. The heat loss
by conduction through the membrane material is
lower at higher feed temperature which also
explains the higher permeate flux.
An increase in the concentration of nonvola-
tile compounds in a feed reduces the Jt due to a
decrease in the Jw. In the case of an increase of
concentration of volatile compounds in a feed,
the Jt and Jv increase, whereas the Jw decreases. It
is associated with changes of the partial pressure
of dissolved species and water. The selectivity of
volatile compounds can be different depending
on their properties and concentration in the feed
and can be improved by an increase of their
partial pressure by salt addition into a feed. Gen-

erally, a higher feed flow rate diminishes the

effects of both temperature and concentration
membrane polarization and AGMD permeate flux increases.
Different spacers can be applied to improve the
Tf,in > Tf,out
hydrodynamic conditions. The effect of coolant
temperature is not very significant because the
Tf,out cooling liquid heat transfer coefficient in the air gap dominates
Liquid the overall heat transfer coefficient (Khayet and
permeate
Matsuura 2011).
Air Gap Membrane Distillation (AGMD),
Fig. 1 Schema of AGMD

Air Gap Membrane Distillation (AGMD), Table 1 Air gap effect on the permeate flux (reprinted from Alkhudhiri
et al. (2012), copyright (2012) with permission from Elsevier)
Membrane Pore size Tin Air gap Permeate flux
Ref material (mm) Feed ( C) (mm) kg/m2.h
[5] PVDF 0.45 Artificial seawater 60 1.9–9.9 5–2.1
[6] PTFE 0.2 Isopropanol 50 1.62–0.55 5.1–6.3
[108] PVDF 0.22 Sucrose 25.8 1–4 1.7–0.8 l/m2h
[18] PTFE 0.2 NaCl (3.8 %) 60 0.3–9 19–1.5
[120] PTFE 0.22 HNO3 (4 M) 80 0.5–2 5.3–4.25 l/m2h
[123] PTFE 0.45 HCl/water 60 4–7 3.7–2.4
[123] PTFE 0.2 Propionic acid/ 60 4–7 7.4–4.6
water
Comments – the references can be found in the original paper
Air Gap Membrane Distillation (AGMD) 3

References Khayet M, Matsuura T (2011) Membrane distillation.

Principles and applications. Elsevier, Amsterdam
Alkhudhiri A, Darwish N, Hilal N (2012) Membrane
distillation: a comprehensive review. Desalination
287:2–18
A
Air Gap Membrane Distillation
(AGMD), Applications of
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Poland
The separation using AGMD is based not only on
vapor/liquid equilibrium but also on the diffusion
rates of the feed components through the gas
trapped in the membrane pores and the air gap
between the membrane and the condensation sur-
face. Nonvolatile compounds are rejected by a
membrane in almost 100 %. Therefore, AGMD
can be applied for desalination and production of
high-purity water. A permeate with electrical
conductivity as low as 4 mS/cm can be obtained
from a solution with composition similar to sea-
water. Moreover, AGMD can be applied for the
separation of volatile compounds. Since the
vapor is condensed on the cold surface and the
liquid permeate does not come into contact with a
hydrophobic membrane, even the organic solutes
can be separated without a risk of the membrane
wetting. The air gas reduces considerably the heat
loss and the temperature polarization which
improve the separation efficiency of AGMD;
however, this leads simultaneously to a signifi-
cant decrease in the permeate flux. The decrease
depends strongly on the width of the air gap. The
air gap is about 10–100 times thicker than the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_624-2
membrane, so the effect of air inside the mem-
brane can be neglected. AGMD creates the
opportunity for the separation of species forming
the azeotropic solutions. It is attributed to the
difference in the diffusion coefficients of volatile
compounds present in a feed through the gas gap
(Khayet and Matsuura 2011). Thus, AGMD can
find the application in water and wastewater
treatment, biotechnology, food industry,
etc. (Table 1).
The plate and frame, tubular, capillary, and
very frequently spiral wound modules equipped
with porous hydrophobic membranes are used
in AGMD.
The main area of AGMD application is desa-
lination. The desalination pilot plants combining
AGMD with solar energy collectors were devel-
oped, especially for operation in arid and semi-
arid remote regions with a lack of electricity and
drinkable water but with high solar radiation
(Table 2). The production of potable water, e.g.,
from plants installed in Jordan was of 100 L/day
(utilizing brackish water) and 1 m3/day (Fig. 1)
(utilizing untreated seawater from the Red Sea).
The installations were equipped with AGMD spi-
ral wound modules with area of 10–40 m2,
respectively. Long-term experiments have dem-
onstrated that the average salt rejection was 98 %
(Qtaishat and Banat 2012; Khayet and Matsuura
2011). Distillate conductivity of 3–5 mS/cm can
be obtained for brackish water feeding. Despite
the advantages such as the ability to desalinate
high saline feedwater, fitness for intermittent
2 Air Gap Membrane Distillation (AGMD), Applications of
Air Gap Membrane Distillation (AGMD), Applications of, Table 1 Application of air gap membrane distillation
Area Membrane material
Desalination PTFE, PVDF
Modified ZrO2, modified Al2O3,
modified TiO2, modified
aluminosilicate
Food industry PVDF, PTFE
Biotechnology PTFE, PVDF
Others PTFE, PVDF
PTFE polytetrafluoroethylene, PVDF polyvinylidene fluoride
energy supply, and the ability to use direct solar
heat without heat storage, the plants have not
been commercialized or implemented in a large
scale. This is mainly because reverse osmosis
(RO) is considered as more economical and
energy-efficient desalination process (Saffarini
et al. 2012). However, the AGMD/solar energy
systems are still in progress and find a growing
interest.
Another field of AGMD application is food
processing. Figure 2 presents the possibility of
juice concentration by AGMD to achieve much
higher feed concentration than using RO. Low
processing temperature allows to concentrate
the solutions sensitive to high temperature and
provides a good quality of juice concentrate
(Kimura and Nakao 1987). The concentration of
milk demonstrated that the membranes were eas-
ily fouled by milk fat and the permeate flux
decreased very fast (Khayet and Matsuura 2011).
Ethanol preferentially vaporizes from the
aqueous feed and is concentrated in the permeate.
Since in AGMD the liquid ethanol does not come
into contact with a membrane, it can be separated
from a fermentation broth and concentrated
Application
Water and wastewater treatment, production of pure water,
solar-powered desalination, geothermal wastewater
treatment
Fruit and vegetable juice concentration, milk
concentration, sugar and gelatine solution concentration,
ethanol concentration
Ethanol separation from a broth
Methanol, isopropanol concentration, separation of
azeotropic mixtures HCl/water, propionic acid/water,
formic acid/water, separation of radioisotopes 18O and 18F,
concentration of wastewater containing isotopes, HI and
H2SO4 concentration
Separation/removal of HNO3, HCl, formic acid, acetic
acid, propanone from aqueous solutions
without a risk of the membrane wetting. It was
found that a salt addition into diluted ethanol
increases alcohol selectivity (Khayet and
Matsuura 2011).
AGMD can be useful in breaking the
azeotropic mixtures of water and hydrochloric
or propionic acids. This phenomenon was asso-
ciated with the differences in the acid-air and
water-air diffusion rates in the air gap. In
AGMD the hydrochloric acid/water azeotrope
was shifted to higher acid concentration, and the
azeotrope was eliminated in the propionic acid/
water system. It was found that the heavy gases
such as SF6 help more in eliminating the
azeotropic point than the lighter ones as air or
He (Khayet and Matsuura 2011).
AGMD was successfully used for the concen-
tration of a mixture of HI and H2SO4, compounds
of great interest for H2 generation in thermo-
chemical water-splitting cycle (Khayet and
Matsuura 2011). AGMD has also a great potential
in the application in the environment protection
area. Therefore, this technique requires more
studies, devoted especially to a long-term perfor-
mance and membrane life.
Air Gap Membrane Distillation (AGMD), Applications of 3

Air Gap Membrane Distillation (AGMD), Applications of, Table 2 Timeline of solar-powered membrane distil-
lation systems and their general features (Adapted from Saffarini et al. 2012)
Energy system type Solar
Membrane Feedwater collector
Year Location MD type type/material type Thermal Electrical type
1991 New South DCMD Hollow fiber/ N/A Solar Grid N/A
Whales, N/A collector
Australia
1995 New South AGMD Spiral wound/ N/A Solar Grid VPC
Wales, Australia PTFE collector
1997 Tokyo, Japan N/A N/A/N/A N/A Solar PV N/A
collector
1999 Texas, USA AGMD N/A/N/A N/A Solar Grid N/A
pond
1999 Irbid, Jordan DCMD N/A/PTFE Brackish Solar Grid N/A
still
2003 Freiburg, AGMD Spiral wound/ Freshwater Solar Grid FPC
Germany PTFE collector
2004 Texas, USA AGMD N/A/N/A NaCl Solar Grid N/A
solution pond
2007 Irbid, Jordan AGMD Spiral wound/ Brackish Solar PV FPC
PTFE collector
2007 Aqaba, Jordan AGMD Spiral wound/ Seawater Solar PV FPC
PTFE collector
2008 Alexandria, AGMD Spiral wound/ Brackish Solar PV FPC
Egypt PTFE collector
2008 Mexico DCMD Hollow fiber/ N/A Solar Grid FPC
N/A collector
2009 Almeria, Spain AGMD Flat sheet/ Seawater Solar Grid CPC
PTFE collector
2009 Hangzhou, VDM Hollow fiber/ Brackish Solar Grid N/A
China PP collector
2009 Nevada, Reno, Vacuum N/A/N/A N/A Solar N/A N/A
USA enhanced pond
DCMD
2009 Gran Canaria, AGMD Spiral wound/ Seawater Solar PV Double
Spain PTFE collector glass FPC
2011 Marina Barrage, VMEMD Flat sheet/ Seawater Solar PV N/A
Singapore PTFE collector
DCMD direct contact membrane distillation, VMD vacuum membrane distillation, PP polypropylene, N/A not available,
PV photovoltaic panels, VPC vacuum plate collector, FPC flat plate collector, CPC concentrated parabolic collectors,
VMEMD vacuum multi-effect membrane distillation
4 Air Gap Membrane Distillation (AGMD), Applications of

Solar
irradiation Brine

Collector
feild
Feed
Storage pump
tank
Heat
exchanger

Distillate MD modules

Battery PV
Expansion
vessel
Control
unit DC PV
AC
PV array

Air Gap Membrane Distillation (AGMD), Applica- powdered (Reprinted from Qtaishat and Banat (2012),
tions of, Fig. 1 Schema of the large system (two-loop copyright (2012) with permission from Elsevier)
desalination system) of desalination using AGMD solar

Air Gap Membrane 400

Distillation (AGMD),
Applications of, – RO, ΔP = 5 MPa
350 – AGMD, Tf = 321 K
Permeate flux, J [kg m–2d–1]

Fig. 2 The comparison of

the permeate flux during
concentration of the 300
mandarin orange juice
using RO and AGMD
(Adapted from Kimura and 250
Nakao 1987)
200

150

100
1 1.5 2 2.5 3
Concentration ratio, CV

References Qtaishat MR, Banat F (2012) Desalination by solar pow-

Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
Kimura S, Nakao SI (1987) Transport phenomena in
membrane distillation. J Membr Sci 33:285–298
dered membrane distillation systems. Desalination.
doi:10.1016/desal2012.01.021
Saffarini RB, Summers EK, Arafat HA, Lienhard VJH
(2012) Technical evaluation of stand-alone solar
powered membrane distillation systems. Desalination
286:332–341
A
Air Products
Pushpinder S. Puri
PuriMem, LLC, Emmaus, PA, USA
The majority of air separation is done by cryo-
genic distillation; however, for several small
applications a gas separation membrane is desir-
able. The key commercial gaseous products made
from air by membranes are nitrogen, oxygen
enriched air, and dry air. Further, gas separation
membranes in hybrid system with a cryogenic
process is used to produce Argon (Agrawal and
Xu 1996) and with an adsorption process to pro-
duce high concentration oxygen enriched air
(Choe et al. 1997).
In membrane nitrogen production systems
(Drioli and Barbieri 2011), the compressed air is
fed on one side of the membrane; oxygen, argon,
carbon dioxide, and water which have higher per-
meation than nitrogen, permeate through the
membrane leaving nitrogen behind. A schematic
of the membrane nitrogen generation system is
shown in Fig. 1.
The compressed air at a temperature of
80–100  C and a pressure of about 1000 kPa
(135–150 psi) is purified by the use of coalescing
filter and fed to the membrane module. The pro-
ductivity and purity of the nitrogen produced is
controlled by the use of a product pressure valve.
Membrane systems produce nitrogen at a concen-
tration ranging from 95 % to 99.9 %. However,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_625-7
due to the modest selectivity (<8) of air separa-
tion membranes, production of high purity nitro-
gen is not economically favorable. Key producers
of nitrogen separation membranes are Air Prod-
ucts, Air Liquide, and Ube. Other nitrogen mem-
brane producers are: Generon Systems, Aquillo
and Parker Heniffin.
Dry air with dew point up to 40  C ( 40  F)
is produced by removing moisture from the atmo-
spheric air using a water permeable membrane
which are either made of glassy polymers
(polysulfone, polyimide, etc.) or fluorine
containing ionomers. Schematic of a typical air
drying system is shown in Fig. 2.
In air drying system, clean wet air is fed under
pressure on one side of the membrane module and
dry air at slightly reduced pressure is recovered as
retentate. In some systems, an internal or external
dry air sweep is used to prevent water buildup on
the membrane in permeate, which retards mem-
brane performance (Morgan et al. 1996).
In some instances, membrane systems are used
to produce oxygen enriched air with oxygen con-
centration <30 % O2. Mostly, rubbery mem-
branes of modest selectivity (2–3) and high
oxygen flux are used for this application3. The
membrane system used is similar to that used for
nitrogen production described above. Sometimes,
use of vacuum on the permeate side is preferred
over the use of a compressor for the production of
oxygen enriched air.
2 Air Products

VENT TO AIR
ATMOSPHERE
COMPRESSOR WASTE GAS

NITROGEN

ELECTRIC NITROGEN TO
HEATER CUSTOMER

OXYGEN NITROGEN
CONDENSATE ANALYSER BUFFER
NITROGEN VESSEL
PRODUCTION
X
MEMBRANE

Air Products, Fig. 1 Schematic of nitrogen generation system (Reproduced with permission from Air Products)

Purging Valve
Purging Air

Drain Filter
Compressor Cooler
Separetor Product
Dry Air

SUNSEP-WTM Dryer
Drain

Air Products, Fig. 2 Typical air drying system (Courtesy: AGC Chemicals Americas)

References Drioli E, Barbieri G (eds) (2011) Membrane engineering

Agrawal R, Xu J (1996) Gas-separation membrane cas-
cades utilizing limited numbers of compressors. AIChE
J 42:2141
Choe JC et al (1997) Process for separating components of
a gas stream. US Patent 4,701,187
for the treatment of gases. Gas-separation problems
with membranes, vol 1. RSC Publishing, Cambridge.
Chapter 8,
Morgan WH, Bleikamp LK, Kalthod DG (1996) Hollow
fiber membrane dryers with internal sweep. US Patent
5,525,143
A
Annealing of Polymer Membranes
Maria Luisa Di Vona
Dip. Di Scienze Technologie Chimiche,
University of Rome Tor Vergata, Rome, Italy
Annealing can be defined as a process where a
material undergoes a heat treatment to a certain
temperature, is kept there for a definite time, and
is then cooled to room temperature in order to
alter the material properties. The annealing pro-
cess is time and temperature dependent.
Annealing of polymers is a heating of a poly-
meric part to below its glass transition tempera-
ture in order to relieve the internal stresses
introduced during its fabrication (molding,
cooling after molding, machining, welding, etc.).
Annealing of conjugated polymers and poly-
mer blend films is a widely used process that
achieves optimal film morphology and therefore
improves material properties, such as electrical
mobility for photovoltaic devices and other appli-
cations. Annealing of ion-conducting polymers
reduces the excessive swelling observed in pres-
ence of water.
In particular, annealing is used (Young and
Lovell 1991):
(a) To increase the melting point of some poly-
mers because it facilitates the melting of
small and irregular crystals in favor of larger
and better formed ones
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_627-1
(b) To reduce or cancel deformations previously
provoked at higher temperature which
remain as frozen (permanent) deformations
when the material is cooled to room
temperature
(c) To increase crystallization
(d) To decrease the free volume between poly-
meric chains thus inducing a mechanical sta-
bilization of polymeric materials
Annealing of liquid crystalline polymers
between the glass transition temperature and the
melting temperature leads to an increased level of
crystallinity and increased crystalline perfection
analogous to the behavior of conventional semi-
crystalline polymers. Annealing at or above the
melting point also leads to enhanced crystallinity
and crystalline perfection.
The annealing of semicrystalline polymers
may change the crystal structure, the degree of
crystallinity, the perfection of the crystals, the
orientation of both crystalline and amorphous
phases, their contiguous structural morphology,
and the number of tie chains between the crystal-
lites. Morphological changes are also observed
on annealing bulk-crystallized samples. Poly-
morphism may result due to annealing crystalline
polymers as its one crystalline form transforms
into another. The concept that mechanical stabi-
lization was due to a generic decrease of the free
volume between ionomer chains when thermally
treated was abandoned and replaced by the con-
sideration that the mechanical stabilization was
2 Annealing of Polymer Membranes
induced by an increased crystallization of a
preexisting semicrystalline phase (Alberti
et al. 2013).
Thermal annealing is a simple route for stabi-
lizing glassy polymers via the densification of
their polymer chains and is accomplished through
thermal treatment of the glassy thermoplastics.
For amorphous polymers, the thermal treatment
can play a very important role in changing the
morphology. If the temperature is lower than the
glass transition temperature Tg, the polymer
chains are mainly immobile, thereby maintaining
the existing morphology; however, if the
annealing temperature is greater than the Tg, the
polymer chains will relax. It has been found that
the morphology can be modified upon annealing
at a temperature higher than the Tg, thus changing
the physical properties of the polymers.
A certain amount of molecular rearrangement
must take place during crystallization but this
rearrangement cannot arise through large-scale
molecular diffusion as the process is occurring
in the solid state. Thermal treatments were
believed to be more and more efficient as the
temperature increases and therefore empirical
short treatments were performed at high temper-
atures. Thus, the annealing temperature (Tann)
was connected with the crystallization tempera-
ture (Tc) and it became clear that the annealing
temperature cannot be higher than the melting
temperature (Tm) of the semicrystalline phase.
References
Alberti G, Narducci R, Di Vona ML, Giancola S (2013)
Annealing of Nafion 1100 in the presence of an
annealing agent: a powerful method for increasing
ionomer working temperature in PEMFCs. Fuel Cells
13:42–47
Young RJ, Lovell PA (1991) Introduction to polymers,
2nd edn. CRC Press, Boca Raton
B
Blood Filtration
A. Higuchi
Department of Chemical and Materials
Engineering, National Central University,
Taoyuan, Taiwan
Blood filtration is performed by hemodialysis
membranes, leukocyte removal filter, and plasma
separation membranes.
Blood is composed of plasma solution and
blood cells. Several valuable proteins such as
immunoglobulin, factor VIII, factor IX, albumin,
vitronectin, etc. are contained in plasma solution.
Blood cells are erythrocytes (RBC, red blood
cells), lymphocytes (T cells, B cells, and NK
(natural killer) cells), monocytes, macrophages,
neutrophils, basophils, eosinophils, megakaryo-
cytes/platelets and dendritic cells, and hemato-
poietic stem cells (HSCs). HSCs are found in the
bone marrow of adults, which includes femurs,
hip, ribs, sternum, and other bones.
In hemodialysis, the patient’s blood is pumped
through the blood compartment of a dialyzer,
exposing it to a dialysis membrane. The dialyzer
is composed of thousands of tiny synthetic hol-
low fibers. The fiber wall acts as the semiperme-
able membrane. Blood flows through the fibers,
dialysis solution flows around the outside of the
fibers, and water and wastes move between these
two solutions. The cleansed blood is then
returned via the circuit back to the body.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_630-3
Ultrafiltration occurs by increasing the hydro-
static pressure across the dialyzer membrane.
This usually is done by applying a negative pres-
sure to the dialysate compartment of the dialyzer.
This pressure gradient causes water and dissolved
solutes to move from blood to dialysate and
allows the removal of several liters of excess
fluid during a typical 3- to 5-h treatment. Hemo-
dialysis treatments are typically given in a dialy-
sis center three times per week.
Hemodialysis membranes are typically pre-
pared from cellulose materials or polysulfone-
polyvinylpyrrolidone (PVP)-blended materials.
Cellulose is hydrophilic and can be used as a
hemocompatible material, whereas polysulfone
is one of engineering plastics and needs to add a
hydrophilic and hemocompatible material as a
blending material. PVP shows relatively good
hemocompatibility, and a more important fact is
that PVP can be blended well with polysulfone.
PVP is also used as a porogen in dialysis mem-
branes of polysulfone. There is a recent demand
for hemodialysis membranes that remove the low
molecular weight proteins such as b2-myoglobin
(MW 11500) and endotoxin (subunit of
MW = 5,000–20,000), and useful albumin in
the plasma should be recovered by the mem-
branes. Polysulfone hollow fibers blended with
PVP have been widely used as suitable hemodi-
alysis membranes which satisfy this requirement
(Higuchi et al. 2002).
Leukocyte removal filter: White blood cells
(leukocytes) generate many adverse reactions
2 Blood Filtration
during blood-transfusion therapy, which are
graft-versus-host disease (GVHD), platelet
refractoriness, nonhemolytic febrile transfusion
reaction, and infection of viruses, such as
human T-lymphotropic virus (HTLV), cytomeg-
alovirus (CMV), and human immunodeficiency
virus (HIV) (Higuchi 2010). It was found that
most of the viruses infect specific type of leuko-
cytes, such as granulocytes, monocytes, lympho-
cytes, B lymphocytes, T-helper cell (CD4+ cell),
and suppressor/cytotoxic T cells (CD8+ cell)
(Higuchi 2010). Therefore, removal of leuko-
cytes in RBC and platelet concentrates as well
as whole blood components is essential to prevent
the adverse effect of contaminated leukocytes.
Leukocytes can be removed using a filter com-
prised of nonwoven fabric or sponge materials as
a filter medium. The mechanism of leukocyte
removal on the filters comprised of nonwoven
fabric is based on the adsorption of leukocytes,
while that comprised of sponge materials is based
on the sieving effect and adsorption.
Plasma separation membrane: Plasma-
exchange therapy has been increasingly applied
clinically over the past few years. Membrane
plasma separation has been used since 1979,
which is similar to hemodialysis and
hemofiltration. Plasma separation from whole
blood is now performed routinely.
The materials of plasma separation mem-
branes are typically made of nitrocellulose,
polysulfone, and polypropylene.
Cross-References
▶ Blood Cell Origins
▶ Blood Separation
▶ Blood Treatment Membranes
▶ Filtration
References
Higuchi A (2010) Separation and purification of stem and
blood cells by porous polymeric membranes. In:
Driolli E, Giorno L (eds) Comprehensive membrane
science and engineering. Elsevier, Cambridge
Higuchi A, Shirano K, Harashima M, Yoon BO, Hara M,
Hattori M, Imamura K (2002) Chemically modified
polysulfone hollow fibers with vinylpyrrolidone hav-
ing improved blood compatibility. Biomaterials
23:2659–2666
S

Solubility Coefficient (S) solubility and corresponding penetrant activity,

if the vapor phase is ideal.
Maria Grazia De Angelis The solubility coefficient at fixed
Dipartimento di Ingegneria Civile, Chimica, fugacity represents the slope of the straight line
Ambientale e dei Materiali, Università di connecting a point on the solubility isotherm to
Bologna, Bologna, Italy the origin (See Fig. 1b); S0 is the slope of the
tangent to the gas solubility isotherm in the zero-
pressure limit (see Fig. 1a).
The solubility coefficient, Si, of a gas i in a mem- In the solution diffusion transport of solute
brane is the ratio between its solubility Ci in the i through membranes, Fick’s law holds true for
membrane and its fugacity fi or partial pressure pi the gas flux inside the membrane at steady state:
in the gas phase at constant temperature:
DCi
J i ¼ Di (3)
Ci l
Si ¼ (1)
fi
On the other hand, the permeability of gases in
For gas sorption in polymer membranes, a com- membranes is defined with respect to the pressure
mon unit is cm3(STP)/(cm3(pol) atm). The solu- gradient of penetrant i, in steady state:
bility coefficient of a low-pressure gas in a liquid
is the reciprocal of Henry’s law coefficient H. Df i
J i ¼ Pi (4)
In the case of gas sorption in polymer mem- l
branes, of particular interest is the infinite dilution
solubility coefficient, S0, that is evaluated in the Therefore, one has that
limit of infinite dilution or zero pressure of pen-
etrant in the gaseous phase. Ci, up  Ci, down fi, up  fi, down
Di ¼ Pi ! Pi
l l
Ci, up  Ci, down
Ci Ci ¼ Di Di Si, AVE
Si0 ¼ lim ¼ lim (2) fi, up  fi, down
p!0 f i p!0 pi
(5)
For vapor solubility in polymer membranes, the
activity-based solubility coefficient is sometimes where Si,AVE is the slope of the straight line
also used, Si pSAT, that is the ratio between connecting the upstream and downstream points
on the solubility isotherm (see Fig. 1c). In the

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_631-1
2 Solubility Coefficient (S)

a b

Solubility

Solubility
C

θ0 θ

Fugacity f Fugacity

c
Solubility

Graphical determination of the solubility

CUP
coefficient from the solubility isotherm:
θAVE
CDOWN
a S0 = tgq0
b S = tgq
c SAVE = tgqAVE

fDOWN fup Fugacity

Solubility Coefficient (S), Fig. 1 Graphical determination of the solubility coefficient from the solubility isotherm:
(a) infinite dilution solubility coefficient, (b) solubility coefficient, (c) average solubility coefficient

figure, the case of a concave down solubility
isotherm has been taken as an example to repre-
sent the graphical meaning of S (here and in the
following the pedix i is omitted for simplicity
sake).
Correlations for the Solubility
Coefficient
The sorption of a gas in a membrane requires
condensation of the gas, followed by mixing
with the membrane molecules. Therefore, the
higher the condesability of the membrane and
its compatibility with the membrane material,
the larger its solubility in the membrane at fixed
temperature. A convenient measure of the pene-
trant condensability is the critical temperature,
and empirical correlations of the following kind
have been proposed in the literature for data
relative to an homologous set of penetrants in a
given polymer at fixed temperature (Bondar
et al. 1999; Stern et al. 1969):
lnðS0 Þ ¼ a þ bT C at constant temperature (6)
lnðS0 Þ ¼ a0 þ b0 T 2C at constant temperature (7)
lnðS0 Þ ¼ M þ N ðT C =T Þ2 (8)
For rubbery polymers, the above correlation can
be retrieved using Flory-Huggins theory and a
Solubility Coefficient (S) 3

Solubility Coefficient (S), Table 1 Experimental and predicted values of correlation coefficients for the solubility
coefficient of gases in glassy membranes (De Angelis et al. 2007)
 
lnðS0 Þ ¼ a þ bT C , S0 in cm3gas ðSTPÞ= cm3pol atm
Experimental value Predicted, NELF model
35  C a b a b
PC 0.0192 4.0994 0.0226 5.0123
PSf 0.0209 4.2394 0.0215 4.5165
PPO 0.0238 3.6305 0.0242 4.0788
PMMA 0.0212 5.0132 0.0219 4.8131

a 1.6 b 1.E+04

1.2
S0 psat (cm3(STP))/(cm3pol)
log10 So (cm3/ (cm3 atm))

C3H8
0.8
1.E+03
C2H6
0.4

0 CO2
CH4 C3F8
1.E+02
–0.4
O2
C2F6 Experimental data, AF2400
–0.8 N2 Experimental data, PTMSP
CF4 Experimental data, PTMSN
NELF model
–1.2 1.E+01
100 150 200 250 300 350 400
0.E+00 1.E+05 2.E+05 3.E+05 4.E+05 5.E+05
TC (K)
TC2 (K2)

Solubility Coefficient (S), Fig. 2 Solubility coefficient et al. 1999). (b) Activity-based solubility coefficient of
of gases in: (a) rubbery PDMS membrane – fluorocarbon vapors in membranes can follow different trends with the
penetrants follow a different trend with respect to the other vapor critical temperature: increasing, constant, or
ones due to lower solubility (Adapted from De Angelis decreasing (Adapted from Galizia et al. 2012)

few assumptions (Gee 1947). For glassy poly- lower interaction with the polymer (De Angelis
mers, the correlation can be reproduced effi- et al. 1999) (Fig. 2a).
ciently by the NELF model (De Angelis The activity-based solubility coefficient of
et al. 2007), as it can be seen in Table 1. gases can increase or decrease with critical tem-
Other authors correlate the values of S0 to perature (Galizia et al. 2012) (see Fig. 2b)
other condensability-related parameters, such as because, being normalized for the different
the Lennard-Jones parameter (Van Krevelen condensability of penetrants, accounts only for
1990), critical volume, surface area (Yampolskii the mixing effects, which can be positive or neg-
et al. 2000), etc. It must be noticed that, when ative depending on the gas-polymer interactions.
different series of penetrants are considered, the
solubility data may fall on separate correlating
lines. This is the case of fluorocarbon penetrants
in PDMS which show lower solubility than the
other gases of similar critical temperature, due to
4 Solubility Coefficient (S)
Solubility Coefficient (S),
Fig. 3 Solubility
coefficient at infinite
dilution of CO2 in PC as a
function of reciprocal
S0 (cm3(STP) / cm3(pol) atm )
temperature. Model results
are also reported: SAFT
equation-of-state and
nonequilibrium SAFT
model (Adapted from
Giacinti et al. 2005)
Dependence on Temperature
The sorption of a gas or vapor into a solid mem-
brane is usually an exothermic process in which
the most important thermal effect is the negative
heat of condensation of the fluid in the membrane
phase. In addition, there is a mixing term which
can be positive or negative depending on the
solute-membrane couple, but is usually lower,
in absolute value, than the condensation term.
Therefore, the solubility coefficient values for
gases and vapors in polymer membranes decrease
with temperature, usually according to an Arrhe-
nius type of dependence, as follows:
 
DH S
S ¼ SðT 0 Þexp 
RT
The heat of sorption assumes a different value for
the rubbery and glassy state; in particular the
higher value is observed in the glassy phase of
the same amorphous polymer. This behavior can
be seen, for instance, by reporting S0 values as a
function of 1/T (Fig. 3): the change of slope
occurs at the membrane glass transition
temperature.
For liquid solutes, there is no condensation
term and the thermal effect associated to sorption
in the membrane can be positive or negative.
10.0
exp. data
SAFT prediction [ k (PC-CO2) = 0 ]
SAFT correlation [ k (PC-CO2) = 0.05 ]
NE-SAFT model [ k (PC-CO2) = 0.05 ]
1.0
0.1
0.0015 0.0020 0.0025 0.0030 0.0035
1/ T (K–1)
References
Bondar VI, Freeman BD, Yampol’skii Yu P (1999) Sorp-
tion of gases and vapors in an amorphous glassy
perfluorodioxole copolymer. Macromolecules
32:6163–6171
De Angelis MG, Merkel TC, Bondar VI, Freeman BD,
Doghieri F, Sarti GC (1999) Hydrocarbon and fluoro-
carbon solubility and dilation in poly(dimethyl-
siloxane): comparison of experimental data with
predictions of the Sanchez-Lacombe Equation of
State. J Polym Sci B 37:3011–3026
De Angelis MG, Sarti GC, Doghieri F (2007) NELF model
prediction of the infinite dilution gas solubility in
glassy polymers. J Membr Sci 289:106–122
Galizia M, De Angelis MG, Sarti GC (2012) Sorption of
hydrocarbons and alcohols in addition-type poly
(trimethyl silyl norbornene) and other high free
volume glassy polymers. II: NELF model predictions.
(9) J Membr Sci 405-406: 201–211
Gee G (1947) Some thermodynamic properties of high
polymers and their molecular interpretation. Q Rev
(Lond) 1:265–298
Giacinti Baschetti M, De Angelis MG, Doghieri F, Sarti
GC (2005) Solubility of gases in polymeric mem-
branes. In: Galan MA, Martin Del Valle E (eds) Chem-
ical engineering – trends and developments. Wiley,
Chichester, pp 41–62
Stern SA, Mullhaupt JT, Gareis PJ (1969) The effect of
pressure on the permeation of gases and vapors
through polyethylene. Usefulness of the corresponding
states principle. AIChE J 15:64–73
van Krevelen DW (1990) Properties of polymers: their
correlation with chemical structure; their numerical
estimation and prediction from Additive Group Con-
tributions, 3rd edn. Elsevier, Amsterdam
Solubility Coefficient (S) 5

Yampolskii Yu P, Wiley D, Maher C (2000) Novel corre- molecular surface area of gases. J Appl Polym Sci
lation for solubility of gases in polymers: effect of 76:552–556
C
Chemical Cleaning of Membranes
C. V. Vedavyasan
Department of Technology, Annamalai
University, Chidambaram, Tamil Nadu, India
Introduction
Cleaning of membranes is carried out to enhance
its permeability followed by performance in a
membrane-based treatment plant. The Pareto
principle – 80/20 rule – that 80 % of effects result
from 20 % of the causes best describes the dis-
cussion, where membrane fouling is the cause
(the 20 %) and cleaning is the effect (the 80 %).
Fouling in membrane filtration is problematic
but inevitable as it occurs with the retention of
contaminants that accumulate on the membrane
surface. The causes of fouling are often specific,
depending upon feed water constituents, the
membrane, and the operating regime. Cleaning
protocols are typically recommended by the
membrane manufacturers with some cleaners
being proprietary. We can minimize the rate of
fouling, but we cannot eliminate fouling, unless
very extensive pretreatment is applied. Types of
fouling are presented along with cleaning, phys-
ical and chemical conditions that have significant
impacts on cleaning efficiency, and compatibility
of membrane materials with cleaning agents.
Membrane fouling is a complicated phenom-
enon and results from numerous causes. In spite
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_633-4
of its complexity, electrostatic and hydrophobic/
hydrophilic interactions that involve both mem-
brane and fouling materials are recognized to
have significant bearing. This is especially for
more-difficult-to-clean membrane fouling domi-
nated by natural organic matter (NOM) and
microbes. Membrane fouling is referred to the
flux decline of a membrane filter caused by the
accumulation of certain constituents in the feed
on the surface of the membrane or in membrane
matrix. Certain fouling materials can be removed
hydraulically (backwash or scrubbing); however,
most can be removed by chemical means such as
clean-in-place (CIP) or chemical cleaning.
The technique of investigating a fouled
membrane – “membrane autopsy”– identifies
the cause of poor membrane performance and
hence gives the opportunity to rectify or mitigate
the problem and improve future plant design.
Membrane Fouling and Chemical
Cleaning
Chemical cleaning is an integral part of mem-
brane process operation that has a marked effect
on the performance and economics of the pro-
cess. A decline in RO membrane performance
can be caused by fouling (organic and inorganic
fouling and biofouling), operational mishaps, and
membrane element quality. The behavior and
frequency of RO system fouling are affected by
feed water source and quality, pretreatment
2 Chemical Cleaning of Membranes
requirements, pretreatment chemicals, and sys-
tem design and operation. During normal opera-
tion over a period of time, RO membrane
elements are subject to fouling by suspended or
sparingly soluble materials in the feed water.
According to the type of foulants, five categories
of membrane fouling are presented.
• Inorganic fouling/scaling
• Particle/colloid fouling
• Biological fouling (bacterial bioslime, algae,
mold, or fungi)
• Organic fouling
• Sulfate scale of calcium, barium, or strontium
Generally RO membrane suppliers recom-
mend membrane cleaning when:
• Normalized permeate flow declines by 10 %
• Pressure drop declines by 10 %
• Normalized salt passage increases by 10 %
Well-designed, well-operated RO systems are
usually cleaned one to four times per year. Irre-
versible membrane element performance decline
such as membrane compaction and intrusion con-
tributes to the 0.7 flow factor. Based on this
permeate flow profile, the system’s stabilized
performance is a flow factor of 0.7. Cleaning
criteria should be based on actual stabilized
membrane element performance. The typical
cleaning criteria (10 % normalized permeate
flow decline or 0.9 flow factor) are not applicable,
because true membrane element performance is a
permeate flow factor of 0.7. Cleaning performed
at a 0.7 flow factor has no effect but increases the
OPEX (operating expenses).
Therefore, RO system cleaning criteria must
be customized to actual stabilized element per-
formance. The criteria can be customized to site
conditions. For instance, calcium carbonate is a
foulant that can be easily and effectively removed
with a hydrochloric acid solution at pH 2. For
sites with low energy costs, cleaning may be
carried out when the normalized permeate flow
decline is 20 %.
For difficult-to-remove foulants – silicates and
organics – cleaning should be performed when
the normalized permeate flow decline is
10–15 %. In many cases, commercial membrane
cleaners are required but they increase OPEX.
Inorganic Fouling/Scaling
Inorganic fouling or scaling is caused by the
accumulation of inorganic precipitates such as
metal hydroxides and “scales” on membrane sur-
face or within pore structure. Precipitates are
formed when the concentration of chemical spe-
cies exceeds their saturation limits. Scaling is a
major concern for reverse osmosis (RO) and
nanofiltration (NF) membrane processes. RO
and NF membranes reject inorganic species.
These species, if allowed to build up, form a
concentrated layer of concentration polarization.
For microfiltration (MF) and ultrafiltration (UF),
inorganic fouling due to concentration polariza-
tion is much less; however, they can exist due to
interactions between ions and foulants (organic
polymers) via chemical bonding. Coagulation
and oxidation, if not designed or operated prop-
erly, might introduce metal hydroxides on mem-
brane surface or within pore structure. Inorganic
fouling and scaling can be a significant problem
for makeup water of caustic solution used for
chemical cleaning.
Particulate/Colloidal Fouling
Accumulation of particulate material (dirt, sand)
on the membrane surface – plugging – leads to
particulate fouling. Algae, bacteria, and certain
natural organic matters fall into this category.
However, they are different from inert particles
and colloids such as silts and clays. In most cases,
particles and colloids do not really foul the mem-
brane because the flux decline is largely revers-
ible by hydraulic cleaning measures such as
backwash and air scrubbing.
Microbial/Biological Fouling
Microbial fouling is a result of formation of
biofilms on the membrane surface. Once bacteria
get attached to the membrane, they start to multiply
and produce extracellular polymeric substances
(EPS) to form a viscous, slimy, hydrated gel. The
Chemical Cleaning of Membranes
Chemical Cleaning of Membranes, Fig. 1 Fouled RO
membrane
severity of microbial fouling is intrinsically related
to the quality of feed water like environmental
conditions for microbial growth, availability of
nutrients, and abundance of microbes. Organic-
based deposits resulting from bacterial slimes,
fungi, molds, etc. can be difficult to remove, if the
feed is plugged. Plugging of the feed makes it
difficult to introduce and distribute the cleaning
solutions. To inhibit additional growth, it is impor-
tant to clean and sanitize not only the RO system
but also the pretreatment, piping, dead legs.
Bacteria present a significant fouling problem
in most of the RO plants. As they grow and
multiply, they normally produce biofilm, organic
films of lipopolysaccharides, to encase and pro-
tect the bacteria. These biofilms cover the mem-
brane surface resulting in fouling.
Figure 1 is a photograph of fouled reverse
osmosis membranes. Deposits of silt are com-
posed of suspended particulates of all types that
accumulate on the membrane surface. Sources of
silt are organic colloids, iron corrosion products,
precipitated iron hydroxide, algae, and fine par-
ticular matter. Silt density index(SDI) testing is a
widely accepted method for estimating the rate at
which colloidal and particle fouling will occur in
water purification systems, especially using
reverse osmosis (RO) or nanofiltration
(NF) membranes.
Shown in Fig. 2 are scanning electron micro-
graphs of the surface of the RO membrane after
4 and 16 days. (A) Rod-shaped gels embedded in
3
an extracellular fibrillar material structure
(square 1). Compact aggregates are visible on
top of this biofilm (square 2). The RO membrane
surface is visible at the bottom (under the biofilm
layer) as a rough-appearing texture. (B) Typical
microcolony formed on the surface of the mem-
brane after 16 days (Fig. 3).
Shown above are series of photographs of
fouled reverse osmosis membranes (A) and their
feed-side spacers (B). The membranes and
spacers were removed from the flow cells after
4 (column 4 d), 8 (column 8 d), 16 (column 16 d),
and 32 (column 32 d) days of operation. The
direction of the feed water flow along the length
of each flow cell was from left to right.
Organic Fouling
Organic fouling is significant in membrane filtra-
tion with source water containing relatively high
natural organic matters (NOM). Surface water
(lake, river) typically contains higher NOM than
groundwaters, with exceptions. For source water
high in NOM, organic fouling is the most signif-
icant factor in flux decline. NOM typically con-
tains about 50 % humic substances. Some organic
molecules (oils, greases, humic/fulvic acids, sur-
factants), occurring either naturally or synthetic,
coat and plug the membrane pores.
The effects of various operating strategies
against different types of fouling are summarized
in Table 1. As indicated, chemical cleaning is the
most effective strategy for all types of membrane
fouling.
Chemical Cleaning of Silica Fouling
Chemicals for silica fouling control can be
divided into three categories:
• Chemicals for silica inhibition
• Chemicals for silica dispersion (Neofotistou
and Demadis 2004)
• Chemicals for silica scale removal from mem-
brane surfaces
4 Chemical Cleaning of Membranes

Chemical Cleaning of Membranes, Fig. 2 SEM imaging of biofilms

4d 8d 16d 32d
a

Feed flow

Chemical Cleaning of Membranes, Fig. 3 Fouled membranes

Silica inhibitors can retard the polymerization
of silica, which exceeded its solubility, i.e.,
phosphonate-based chemicals. Dispersants can
work by placing a surface charge on the polymer-
ized silica and cause repulsion and dispersion of
these polymerized structures into water phase
(Dudley and Baker 1999).
Polymerization of dissolved silica (i.e., super-
saturation and catalyzed by hardness) can be dif-
ficult to remove. This type of silica fouling is
different from colloidal and particulate silica,
which may be associated with either metal
hydroxides or organic matter. It might be difficult
to remove polymerized silica by typical chemical
cleaning process. However, polymerized silica
scales removed with a high pH cleaning solution
(pH of 10–11) were reported. Caustic (sodium
hydroxide) at maximum pH allowed by the
membrane manufacturer will remove polymer-
ized silica scales but it will take many hours to
remove a silica scale. Colloidal silica and partic-
ulate silica coating, not associated with either
metal hydroxides or organic matter, can be
removed from membrane surface by physical
flushing.
MF and UF membranes can be of organic
polymers or inorganic materials, whereas NF
and RO membranes are all organic
polymers only.
Membrane Cleaning Chemicals
Selection and Use of Cleaning Chemicals
The first time cleaning is performed, it is
recommended to contact the manufacturer of the
Chemical Cleaning of Membranes
Chemical Cleaning of Membranes, Table 1 Effects of operating strategies on fouling
Type of fouling Hydraulic cleaning Feed chlorination
Inorganic
Particulate ++
Microbial + ++
Organic + ++
No effect or negative effects
+Some positive effects
++Always positive effect
a
In conjunction with feed chlorination
equipment, the RO element manufacturer, and
service supplier. The cleaning chemicals can be
generic or proprietary.
It is not unusual to use a number of different
cleaning chemicals in a specific sequence to
achieve optimum cleaning. A high pH cleaning
is used to remove foulants like mineral scale or
metal hydroxides/oxides. The order of high and
low pH cleaning solution could be reversed or
only one solution is required under the situation.
Detergents are added to aid in the removal of
heavy biological and organic matter, while other
foulants need a chelating agent like EDTA for the
removal of colloidal material, organic and bio-
logical material, and sulfate scale. An improper
selection of cleaning chemical or the protocol
thereof can make the entire cleaning exercise
worse.
Iron deposits and scaling require a simple low
pH cleaning. For most complex fouling, the
sequence below may be followed:
• Flushing with permeate and with nonoxidizing
biocide at the end of flushing
• High pH CIP (clean-in-place) with tempera-
ture versus pH
• Flushing with permeate till pH on the brine
side <8.5
• Low pH CIP (clean-in-place)
• Acid flushing with permeate and nonoxidizing
biocide
Once the cause of membrane fouling is iden-
tified, various cleaning chemicals can be used to
remove foulants from the membrane and to
5
Feed acidification Chemical cleaning
++ ++
++
+a ++
restore the membrane flux. Chemicals commonly
used for cleaning MF and UF membranes in
water industry fall into five categories, as shown
in Table 2.
Caustic
Caustic is used to clean membranes fouled by
organic and microbial foulants. The function of
caustic is twofold: (1) hydrolysis and (2) solubili-
zation. There are a number of organic materials
including polysaccharides, and proteins that can
be hydrolyzed by caustic. Cellulose-based mem-
branes based on polysaccharides hydrolyze;
hence, such membranes are to be used in a limited
pH range. This is due to the hydrolysis of
cellulose – a simple polysaccharide – consisting
of thousands of glucose linked by 1,4–bglucoside
bonds . Fats and oils also react with caustic
through saponification, generating water-soluble
soap micelles.
An important function of caustic is to increase
negative charges of humic substances. Hence,
they are easier to be removed from membranes.
Humic substances contain functional groups that
are organic acids. Their acidity ranges from pKa
(negative logarithm of the dissociation constant)
of 1.2 (oxalic) to 13 (phenol), with an average
pKa of 4.2 (Thurman 1985). During caustic
cleaning, pH of cleaning solution can be as high
as 13.
Acids and Chelating
Acids are used primarily for removing scales and
metal dioxides from fouling layers. When mem-
brane is fouled by iron oxides, citric acid is quite
effective because it not only dissolves iron oxide
6 Chemical Cleaning of Membranes
Chemical Cleaning of Membranes, Table 2 Categories of membrane cleaning chemicals
Category Functions
Caustic Hydrolysis, solubilization
Oxidants/ Oxidation, disinfection
disinfectants
Acids Solubilization
Chelating agents Chelation
Surfactants Emulsifying, dispersion, surface
conditioning
precipitates but also forms complex with iron.
The removal of divalent cations by either acids
or chelating reagent such as EDTA improves the
cleaning of membranes fouled by organic
foulants.
Surfactants
Surfactants are compounds that have both hydro-
philic and hydrophobic structures. They can form
micelles with fat, oil, and proteins in water and
help to clean the membranes fouled by these
materials. One interesting but less clear aspect is
how surfactants affect membrane fouling domi-
nated by NOM (natural organic matter). As the
surfactant is nonionic, the interaction between the
membrane and the surfactant is dominated by
hydrophilic and hydrophobic reaction. Since the
membrane is hydrophobic, hydrophilic tail of the
surfactant is preferably adhered to the membrane
surface and hydrophilic head is orientated toward
aquatic phase. Soaking in surfactant has been
used as a method for surface modification to
improve hydrophilicity or wettability of certain
membranes.
Operating Parameters Affecting
Cleaning Efficiency During Chemical
Cleaning
Because membrane cleaning is essentially
conducted through chemical reactions between
cleaning chemicals and fouling materials, factors
that affect the mass transfer and chemical reac-
tions such as concentration, temperature, length
Typical chemicals
NaOH
NaOCl, H2O2, peroxyacetic acid
Citric acid, nitric acid
Citric acid, EDTA
Surfactants, detergents (SDS, sodium dodecyl
sulfate)
of cleaning period, and hydrodynamic conditions
affect the efficiency of cleaning.
When selecting cleaning conditions, ensure
the compatibility of cleaning chemicals with
membrane media and filters and systems. Chem-
ical compatibility of membrane and filter compo-
nents limits the type and the maximum allowable
concentration of a chemical to be used during
cleaning.
Concentration of cleaning chemicals can
affect both the equilibrium and the rate of reac-
tion. The concentration profile of cleaning
chemicals within the fouling layer is a function
of the concentration of cleaning chemicals in the
bulk liquid phase. Therefore, the concentration of
cleaning chemicals not only need to maintain the
reasonable reaction rate (kinetics need) but also
need to overcome mass transfer barrier imposed
by the fouling layer. In practice, the concentra-
tions of cleaning chemicals are usually high
enough to satisfy the kinetic need. It is the mass
transfer that sets the lower boundary for the con-
centration of cleaning chemicals.
Temperature can affect membrane cleaning
by:
• Changing the equilibrium of a chemical
reaction
• Changing the reaction kinetics
• Changing the solubility of fouling materials
and/or reaction products during the cleaning
From mass transfer point of view, dynamic
cleaning involving circulating cleaning solutions
through the system can be more effective than
simply static cleaning such as soaking.
Chemical Cleaning of Membranes
RO Membrane Element Cleaning
and Flushing Procedures
The RO membrane elements can be cleaned in
place in the pressure tubes by recirculating the
cleaning solution across the high-pressure side of
the membrane at low pressure and high flow.
A cleaning unit is needed to do this. RO cleaning
procedures may vary depending on the situation.
The time required to clean a stage can range from
4 to 8 h.
A general procedure for cleaning the RO
membrane elements is:
• Perform a low-pressure flush at 60 psi (4 bar)
by pumping clean water from the cleaning
tank through the pressure tubes to drain for
several minutes. Flush water should be clean
water of RO permeate or DI (deionized) qual-
ity water and be free of hardness, transition
metals, and chlorine.
• Mix a fresh batch of the selected cleaning
solution in the cleaning tank. The dilution
water should be clean water of RO permeate
or DI quality and free of hardness, transition
metals, and chlorine.
• Circulate the cleaning solution through the
pressure tubes for about 1 h or as required.
At the start, send the displaced water to drain
so you do not dilute the cleaning chemical and
then divert up to 20 % of the most highly
fouled cleaning solution to drain before
returning the cleaning solution back to the
RO cleaning tank. For the first 5 min, slowly
throttle the flow rate to one third of the max-
imum design flow rate. This is to minimize the
potential plugging of the feed path with a large
amount of dislodged foulant. For the second
5 min, increase the flow rate to two third of the
maximum design flow rate and then increase
the flow to two third of the maximum
design flow.
• An optional soak and recirculation sequence
can be used, if necessary. The soak time can be
from 1 to 8 h depending on the manufacturer’s
recommendations but not to exceed maximum
pH and temperature limits for specific
elements.
7
• Upon completion of the chemical cleaning
steps, a low-pressure cleaning rinse with
clean water (RO permeate or DI quality and
free of hardness, transition metals, and chlo-
rine) is required to remove all traces of chem-
ical from the cleaning skid and the RO skid.
Drain and flush the cleaning tank; then
completely refill the cleaning tank with clean
water for the cleaning rinse. Rinse the pressure
tubes by pumping all of the rinse water from
the cleaning tank through the pressure tubes to
drain.
• Once the RO system is fully rinsed of cleaning
chemical with clean water from the cleaning
tank, a final low-pressure cleanup flush can be
performed with pretreated feed. The permeate
line should be open to drain. Feed pressure
should be less than 60 psi (4 bar). This final
flush continues till the flush water is clean and
is free of any foam or residues. This flush goes
for 15–60 min. A conductivity meter can be
used to test for removal of cleaning chemicals,
such that the flush water to drain is within
10–20 % of the feed conductivity. A pH
meter can also be used to compare the flush
water to drain to the feed pH.
• Once all the stages of a train are cleaned, and
the chemicals flushed out, the RO plant can be
restarted and placed into a service rinse. The
RO permeate should be diverted to drain until
it meets the required quality of the process. It
normally takes few hours to few days for the
RO permeate quality to stabilize, especially
after high pH cleanings.
Conclusion
As the water treatment industry grows at a
remarkable pace, the ability to treat aggressive
surface and waste waters that are notorious for
having high organics, colloids, and biological
fouling potential continues to be challenging.
Using a generic or commercial alkaline
cleaning chemical significantly affects OPEX,
while the payback primarily depends on the
chemicals used. Cleaning to reduce a facility
OPEX depends on water temperature, energy
8 Chemical Cleaning of Membranes
costs, and chemical costs. Establish a cleaning
strategy that is most effective and well tested;
analyze the foulants followed by an autopsy pro-
tocol. Selection of an appropriate pretreatment
with good operation and maintenance practices
will lead to cost-effective cleaning regime. The
cleaning efficiency depends on the type of
cleaning agent and its concentration. The net
effect is that the efficiency increases with increas-
ing chemical concentration. Operating parame-
ters such as cross-flow velocity, turbulence in
the vicinity of membrane surface, temperature,
pH, and duration of cleaning affect the cleaning
process. Analyze the right cleaning strategy on a
case-by-case basis. It is recommended that the
MSDS (Material Safety Data Sheet) of the
cleaning chemicals be procured from the chemi-
cal supplier and knowledge be applied in the
handling and storage of the chemicals.
Cross-References
▶ Cleaning Cycles of Fouled Membranes
▶ Cleaning Effectiveness
▶ Cleaning Efficiency
▶ Fouling Control in Drinking Water Membrane
Filtration
▶ Fouling Index
▶ Fouling in Membranes
▶ Fouling Release
▶ Fouling Release Membranes
▶ Membrane Cleaning
▶ Natural Organic Matter Removal and Fouling
Further Readings
Baker, J.S; Dudley, L.Y (1999) Biofouling in membrane
systems: a review. Water supply 17(1):173–81
Hijos G, Artal J, Gogeascoa IA, Bidaurrazaga JA
(2012) Adelaide desalination plant process design:
energy use optimization. IDA J 4(2):52–56
Johnson J, Mercer G (2012) Seawater desalination plant
optimization based on membrane replacement and
cleaning. Desalination Water Reuse 4(2):34–38
Liu C, Caothein S, Hayes J, Caothuy T (2012) Membrane
chemical cleaning: from art to science. http://www.
membranecleaning.com/pdf
Nghiem LD, Schaefer AI (2006) Fouling autopsy of
hollow-fibre MF membranes in wastewater reclama-
tion. Desalination 188:113–121
Technical Services Bulletin 107.20. Selection and use of
cleaning chemicals. Resource document.
Hydranautics. http://www.membranes.com.pdf.
Accessed 6 July 2010.
C
CO Selective Oxidation
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
Hydrogen purification is a critical technology for
many chemical and petrochemical processes and
power generation by PEM-FCs (proton exchange
membrane fuel cells) as well. Carbon monoxide
is, in fact, a poisoning or inhibitor for most cata-
lysts such as the Fe3O4 one involved in ammonia
synthesis or the platinum-based one used at a low
temperature in PEM-FCs. In the latter case, in
order to avoid cell performance degradation, car-
bon monoxide concentration must be kept below
10 ppm in the hydrogen feed streams.
CO selective or preferential oxidation is the
primary method used for hydrogen deep purifica-
tion (Avgouropoulos and Ioannides 2003), and
different research groups (Manasilp and Gulari
2002; Souza et al. 2007; Bissett and Oh 2005;
Wootsch et al. 2004; Sirijaruphan et al. 2004;
Kotobuki et al. 2005) work on this topic. The
involved reactions are:
2CO þ O2 ! 2CO2
2H2 þ O2 ! 2H2 O
Therefore, a catalyst active for CO oxidation in
the presence of high concentrations of H2, CO2,
and steam is required to avoid H2 consumption,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_635-1
nor should it have a strong preference to the
water-gas shift reaction since in these conditions
of temperature and gas composition, the equilib-
rium gives ca. 0.5–2 %mole of CO.
Both alumina-supported Pt and Au catalysts
have been found to be active for CO Selox
(Luengnaruemitchai et al. 2004). Pt-based cata-
lysts require high temperatures (about 170  C)
and a high feed molar ratio O2/CO (about 1.5)
for complete CO depletion, with a corresponding
loss of selectivity (typically 34 %). Water vapor
has a positive effect on these catalysts, increasing
the conversion without changing the selectivity;
instead CO2 has a detrimental effect
(Avgouropoulos et al. 2002). Au-based catalysts
are more active than platinum catalysts at rela-
tively low temperatures (<120  C) but not so
resistant toward deactivation by CO2 and
H2O. Promoted Pt/Al2O3 catalysts (e.g., with Ru
or Rh) have also been investigated. Values of
ca. 15 ppm of CO in the reactor outlet are
reported for a microreactor (Pt–Ru/a-Al2O3 cat-
alyst) operated with a O2/CO feed molar ratio of
1.5 and 4 (Delsman et al. 2004; Cominos
et al. 2005). Whereas, values of CO less than
10 ppm were reported for a fixed bed reactor
using a O2/CO feed molar ratio of 2.5 (Dudfield
et al. 2000). Other interesting active and very
selective catalysts are CuO–CeO2 mixed oxides
(Avgouropoulos and Ioannides 2006; Zou
et al. 2006); however, the presence of H2O and
CO2 in the feed causes a significant decrease in
their activity (Avgouropoulos et al. 2005).
2 CO Selective Oxidation
Apart from the improvement of the catalyst,
new reactor concepts are being studied. Mono-
liths present different advantages over particulate
catalysts, including pressure drop reduction, ease
of handling, structural robustness, and possibly
increased heat transfer. Interesting new engineer-
ing devices such as catalytic membranes and
catalytic membrane reactors were investigated
in a few papers for CO selective oxidation
(Hasegawa et al. 2001, 2002; Bernardo
et al. 2006). The concept of using Pt in zeolite
catalysts was applied for this reaction by
Watanabe et al. (1995; Igarashi et al. 1997). In a
recent paper (Kotobuki et al. 2005), a significant
improvement of CO conversion and selectivity
with high Pt dispersion in the zeolite (ZSM-5)
pores was demonstrated. Zeolites play host to
noble-metal clusters for numerous catalytic
applications, and well-defined clusters of narrow
size distribution down to 1 nm have been
obtained under suitable conditions (Pan
et al. 1990; de Graaf et al. 2001). Investigations
on the use of large-pore diameter zeolite such as
Pt-loaded FAU-type membranes (Bernardo
et al. 2006) show also the possibility of collocat-
ing a membrane reactor CO selective oxidation
stage (operating at 200–220  C and with a feed
ratio O2/CO = 1) after the low-temperature
water-gas shift reactor in a reforming plant. One
of the findings of this study was the possibility of
improving CO removal by increasing the operat-
ing pressure.
A zeolite catalytic membrane provides cata-
lytically active and nano-sized particles
entrapped in a thin zeolite layer (a few microns
thick), resulting in:
• Efficient reactant/catalytic phase contact,
reducing bypassing and misdistribution gener-
ally shown in a packed bed
• Short and narrow distributed contact time
• Hot spot control that is beneficial since a local
temperature increase can lead to promotion of
reverse water-gas shift reaction (Ouyang and
Besser 2005; Ouyang et al. 2005)
With this aim, catalytic Pt-loaded zeolite
membranes were utilized as an effective device
for CO selective oxidation in a single-stage mem-
brane reactor operating in a continuous flow-
through configuration at ca. 200  C and a low
feed molar ratio O2/CO = 1 and 1.5 (Bernardo
et al. 2008). This new model reactor design leads
to improved and really interesting performance in
terms of CO conversion and limited hydrogen
consumption.
References
Avgouropoulos G, Ioannides T (2003) Selective CO oxi-
dation over CuO-CeO2 catalysts prepared via the
urea–nitrate combustion method. Appl Catal
A 224(1):155–167
Avgouropoulos G, Ioannides T (2006) Effect of synthesis
parameters on catalytic properties of CuO-CeO2. Appl
Catal B 67:1–11
Avgouropoulos G, Ioannides T, Papadopoulou C,
Batista J, Hocevar S, Matralis HK
(2002) A comparative study of Pt/g-Al2O3, Au/-
Fe2O3 and CuO-CeO2 catalysts for the selective oxi-
dation of carbon monoxide in excess hydrogen. Catal
Today 75(1–4):157–167
Avgouropoulos G, Ioannides T, Matralis H (2005) Influ-
ence of the preparation method on the performance of
CuO-CeO2 catalysts for the selective oxidation of
CO. Appl Catal B 56:87–93
Bernardo P, Algieri C, Barbieri G, Drioli E (2006) Cata-
lytic (Pt–Y) membranes for the purification of H2–rich
streams. Catal Today 118:90–97
Bernardo P, Algieri C, Barbieri G, Drioli E (2008) Hydro-
gen purification from carbon monoxide by means of
selective oxidation using zeolite membranes. Sep Purif
Technol 62:629–635. doi:10.1016/j.
seppur.2008.03.024
Bissett EJ, Oh SH (2005) PrOx reactor model for fuel cell
feedstream processing. Chem Eng Sci 60:4722–4735
Cominos V, Hessel V, Hofmann C, Kolb G, Zapf R,
Ziogas A, Delsman ER, Schouten JC (2005) Selective
oxidation of carbon monoxide in a hydrogen–rich fuel
cell feed using a catalyst coated microstructured reac-
tor. Catal Today 110:140–153
de Graaf J, van Dillen AJ, de Jong KP, Koningsberger DC
(2001) Preparation of highly dispersed Pt particles in
zeolite Y with a narrow particle size distribution: char-
acterization by hydrogen chemisorption, TEM,
EXAFS spectroscopy, and particle modelling. J Catal
203:307–321
Delsman ER, De Croon MHJM, Pierik A, Kramer GJ,
Cobden PD, Hofmann CH, Cominos V, Schouten JC
(2004) Design and operation of a preferential
CO Selective Oxidation
oxidation microdevice for a portable fuel processor.
Chem Eng Sci 59(2004):4795–4802
Dudfield CD, Chen R, Adcock PL (2000) A compact CO
selective oxidation reactor for solid polymer fuel cell
powered vehicle application. J Power Sources
86:214–222
Hasegawa Y, Kusakabe K, Morooka S (2001) Selective
oxidation of carbon monoxide in hydrogen–rich mix-
tures by permeation through a platinum–loaded
Y–type zeolite membrane. J Membr Sci 190:1–8
Hasegawa Y, Ueda A, Kusakabe K, Morooka S (2002)
Oxidation of CO in hydrogen–rich gas using a novel
membrane combined with a microporous SiO2 layer
and a metal–loaded –Al2O3 layer. Appl Catal
A 225:109–115
Igarashi H, Uchida H, Suzuki M, Sasaki Y, Watanabe
M (1997) Removal of CO from H2-rich fuels by selec-
tive oxidation over platinum catalyst supported on
zeolite. Appl Catal A 159:159–169
Kotobuki M, Watanabe A, Uchida H, Yamashita H,
Watanabe M (2005) Development of Pt/ZSM5 catalyst
with high CO selectivity for preferential oxidation of
carbon monoxide in a reformed gas. Chem Lett
34(6):866–967
Luengnaruemitchai A, Osuwan S, Gulari E (2004) Selec-
tive catalytic oxidation of CO in the presence of H2
over gold catalyst. Int J Hydrog Energy 29:429–435
Manasilp A, Gulari E (2002) Selective CO oxidation over
Pt/Al2O3 catalyst. Appl Catal Environ 37:17–25
3
Ouyang X, Besser RS (2005) Effect of reactor heat trans-
fer limitations on CO preferential oxidation. J Power
Sources 141:39–46
Ouyang X, Bednarova L, Besser RS, Ho P (2005) Prefer-
ential oxidation (PrOx) in a thin-film catalytic
microreactor: advantages and limitations. AIChE
J 51(6):1758–1771
Pan M, Cowley JM, Chan IY (1990) HREM imaging of
small pt clusters dispersed in Y-zeolites. Catal Lett
5:1–12
Sirijaruphan A, Goodwin JG Jr, Rice RW (2004) Investi-
gation of the initial rapid deactivation of platinum
catalysts during the selective oxidation of carbon mon-
oxide. J Catal 221:288–293
Souza MMVM, Ribeiro NFP, Schmal M (2007) Influence
of the support in selective CO oxidation on Pt catalysts
for fuel cell applications. Int J Hydrog Energy
32:425–429
Watanabe M, Uchida H, Igarashi H, Suzuki M (1995) Pt
catalyst supported on zeolite for selective oxidation of
CO in reformed gases. Chem Lett 1:21–22
Wootsch A, Descorme C, Duprez D (2004) Preferential
oxidation of carbon monoxide in the presence of
hydrogen (PROX) over ceria–zirconia and alumina-
supported Pt catalysts. J Catal 225:259–266
Zou H, Dong X, Lin W (2006) Selective CO oxidation in
hydrogen-rich gas over CuO/CeO2 catalysts. Appl Surf
Sci 253:2893–2898
C
Continuous Diafiltration: Cocurrent
and Countercurrent Modes
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Continuous diafiltration is a type of diafiltration
that accomplishes the selective separation of mul-
tiple solutes in a continuous fashion by mixing the
feed stream with diluant and pumping it across the
membrane with permeate and retentate being
removed. The role of diluant addition is to facili-
tate the separation of membrane-permeating
microsolutes from the retained macrosolutes.
This strategy is generally applicable to a variety
of microfiltration, ultrafiltration, nanofiltration,
and reverse osmosis systems and commonly
employed in plants that require large throughputs.
Its simplest configuration, known as single-pass
diafiltration, is schematically shown in Fig. 1a.
Continuous diafiltration, as opposed to batch
diafiltration, realizes a steady-state separation in
which the product (i.e., the final retentate) is not
formed in the feed vessel as filtration progresses,
but being continuously withdrawn from the system
during the entire course of filtration. In practice,
continuous processing employs feed-and-bleed
configuration to enhance separation as shown in
Fig. 1b. Here, the retentate is split, and a portion of
it is recycled back to the cartridge inlet.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_638-5
Large-scale continuous diafiltration systems
operate in multistage arrangement in which a
portion of the retentate generated in one stage is
used as the feed to the next. These systems can
reach higher system recoveries, without exceed-
ing the single element recovery limits. Each stage
may consist of several membrane elements
arranged in feed-and-bleed configuration. The
two basic concepts of multistage arrangement
are the cocurrent (also called crosscurrent) and
the countercurrent configurations (Dutré and
Trägárdh 1994). The former applies fresh diluant
at each stage, while the latter uses recycled per-
meate as diluant as shown in Fig. 2.
Continuous membrane plants are usually
designed for both concentration and fractionation
purposes. To achieve the twin objectives of con-
centrating and purifying a multicomponent feed,
the combined application of both concentration
mode and diafiltration mode operation is
required. Traditional continuous membrane sys-
tems consist of a number of stages in series in
which consecutive stages are assigned to perform
the tasks of pre-concentration, diafiltration, and
final concentration (Madsen 2001). Many design
variations exist in practice that are primarily
achieved by the manipulation of the arrangement
of stages within the plant, the number of stages
and filtration areas assigned to the various tasks,
the amount and the place of fresh diluant addition
in the process train, the introduction of bypasses
and manifolds, the alteration of permeate recycle
ratios, and the appointment of the stages in which
2 Continuous Diafiltration: Cocurrent and Countercurrent Modes

a b
Retentate Retentate
Diluant Diluant
Booster
pump

Feed Permeate Permeate

Feed
High-pressure
pump

Continuous Diafiltration: Cocurrent and Countercurrent Modes, Fig. 1 (a) Single-pass continuous diafiltration
and (b) continuous diafiltration with partial retentate recycle (feed and bleed)

Diluant

Feed Retentate
Stage 1 Stage 2 Stage i Stage N

Permeate

Diluant

Feed Retentate
Stage 1 Stage 2 Stage i Stage N

Permeate

Continuous Diafiltration: Cocurrent and Countercurrent Modes, Fig. 2 Simplified flow diagram of multistage
cocurrent (top) and countercurrent (bottom) continuous diafiltration

permeate is withdrawn from and recycled to References

(Morison and She 2003, Yee et al. 2007; Mohanty
and Ghosh 2008). The selection of optimal
diafiltration strategy in continuous processing is
very case specific. In general, a reduced con-
sumption of fresh diluant but a larger membrane
area is required for the countercurrent approach
(i.e., reintroduction of permeate as diluant in the
process train) as compared to cocurrent process if
the same degree of purification is to be attained
(Lipnizki et al. 2002).
Dutré B, Trägárdh G (1994) Macrosolute-microsolute sep-
aration by ultrafiltration: a review of diafiltration pro-
cesses and applications. Desalination 95:227–267
Lipnizki F, Boelsmand J, Madsen RF (2002) Concepts of
industrial-scale diafiltration systems. Desalination
144:179–184
Madsen RF (2001) Design of sanitary and sterile UF- and
diafiltration plants. Sep Purif Technol 22–23:79–87
Mohanty K, Ghosh R (2008) Novel tangential-flow coun-
tercurrent cascade ultrafiltration configuration for con-
tinuous purification of humanized monoclonal
Continuous Diafiltration: Cocurrent and Countercurrent Modes 3

antibody. J Membr Sci 307:117–125. doi:10.1016/j. Yee KWK, Wiley DE, Bao J (2007) Whey protein
memsci.2007.09.010 concentrate production by continuous ultrafiltration:
Morison KR, She X (2003) Optimisation and graphical operability under constant operating conditions. J
representation of multi-stage membrane plants. Membr Sci 290:125–137. doi:10.1016/j.
J Membr Sci 211:59–70. doi:10.1016/S0376- memsci.2006.12.026
7388(02)00375-7
E
Evapomeation (EV)
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Presently, pervaporation (PV) is applied as the
chosen membrane separation technique for the
separation of water/organic, organic/water, and
organic/organic mixtures. However, it seems
that conventional PV is not the most efficient
membrane separation process for the treatment
of some liquid mixtures as follows. Because the
polymer membranes used in PV are directly in
contact with the liquid feed solutions as shown in
Fig. 1, however, specifically designed chemical
and physical properties of the membrane are
often impaired by swelling or shrinking of the
membrane due to sorption of the feed compo-
nents. Swelling or shrinking of the polymer
membranes is disadvantageous for the mem-
brane performance with respect to the separation
of mixtures. A novel membrane separation tech-
nique known as “evapomeation (EV)” (Uragami
et al. 1988; Uragami and Saito 1989; Uragami
1991, 1992, 1993a, b; Uragam 1994; Uragami
1998, 2005, 2006a, b, 2008) makes use of the
advantages of PV but reduces the negative
effects of swelling on membrane performance.
In this technique, the feed solution is fed to the
membrane without directly contacting the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_639-1
polymer membrane. This is accomplished by
vaporizing the liquid feed so that only vapor is
supplied to the polymer membrane as shown in
Fig. 2. Therefore, swelling or shrinking of the
polymer membranes due to contact with the feed
solutions is minimized.
The advantages of EV compared to PV are as
follows:
1. In the EV process, membranes are not in direct
contact with liquid feed mixtures as only
vapors are supplied to the membranes.
Accordingly, any swelling or shrinking of the
membrane due to the feed mixtures is mini-
mized, and consequently an improvement in
membrane performance may be expected.
2. Because the organic liquid mixtures are vapor-
ized, interactions between component mole-
cules are significantly weakened, and
consequently the separation performance is
remarkably improved.
3. In EV, contaminants in a liquid feed mixture,
such as macromolecular solutes, can lead to
fouling of the membrane; this problem is
avoided in EV.
4. During EV, both temperature of the feed solu-
tion and the membrane surroundings can be
controlled; hence, an improvement in the per-
meation and separation characteristics of the
membrane can be achieved.
2 Evapomeation (EV)
Evapomeation (EV),
Fig. 1 Principle of Feed liquid
pervaporation (PV)
Membrane
vacuum
References
Uragam T (1994) Separation method of mixed solutions.
Japanese Patent 1,883,353
Uragami T (1991) Method of separating a particular com-
ponent from its liquid solution. US Patent 4,983,303,
European Patent 0,273,267
Uragami T (1992) Separation of organic liquid mixtures
through chitosan and chitosan derivative membranes
by pervaporation and evapomeation methods. In:
Brine CJ, Sandford PA, Zikakis JP (eds) Advance in
chitin and chitosan. Elsevier Applied Science, Oxford,
pp 594–603
Uragami T (1993a) Method of separating a particular
component from its liquid solution. European Patent
0,273,267
Uragami T (1993b) Method of separating a particular
component from its liquid solution. Brazilian Patent
P-8707041-3
Uragami T (1998) Structures and properties of membranes
from polysaccharide derivatives. In: Dumitriu S
(ed) Polysaccharide – structural diversity and func-
tional versatility. Marcer Dekker, New York/Basel/
Hong Kong, pp 887–924
Uragami T (2005) Structures and functionalites of mem-
branes from polysaccharides derivatives. In: Dumitriu
Evapomeation (EV), vacuum
Fig. 2 Principle of
evapomeation (EV)
Membrane
Feed liquid
S (ed) Polysaccharides structural diversity and func-
tional versatility, 2nd edn. Marcer Dekker, New York/
Basel/Hong Kong, pp 1087–1122
Uragami T (2006a) Polymer membranes for separation of
organic liquid mixtures. In: Yampolskii Y, Pinnau I,
Freeman BD (eds) Materials science of membranes for
gas and vapor separation. John Wiley & Sons, Chich-
ester, pp 355–372
Uragami T (2006b) Separation materials derived from chi-
tin and chitosan. In: Uragami T, Tokura S (eds) Mate-
rial science of chitin and chitosan,
KODANSHA. Springer, Tokyo/Berlin/Heidelberg/
New York, pp 113–163
Uragami T (2008) Structural design of polymer mem-
branes for concentration of bio-ethanol. Polym
J 40:485
Uragami T, Saito M (1989) Analysis of permeation and
separation characteristics: a new technique for separa-
tion of aqueous alcoholic solution through alginic acid
membranes. Sep Sci Technol 24:54
Uragami T, Saito M, Takigawa K (1988) Comparison of
permeation and separation characteristics for aqueous
alcoholic solutions by pervaporation and new
evapomeation methods through chitosan membranes.
Makromol Chem Rapid Commun 9:361
T
Temperature-Difference-Controlled
Evapomeation (TDEV)
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
As mentioned in the heading of “Evapomeation
(EV),” a new EV method for membrane separa-
tion that improves upon the shortcomings of
pervaporation while keeping the advantages of
this technique was developed (Uragami
et al. 1988; Uragami and Saito 1989; Uragami
1991, 1993a, b, 1998, 2005, 2006a, b; Uragami
1994). In EV, the temperatures of the feed liquid
(I) and the membrane surroundings (II) are con-
trolled, and consequently a differential between
these temperatures can be established, as shown
in Fig. 1. Such an EV method, in which this
temperature difference is controlled, is called
“temperature-difference controlled
evapomeation” (TDEV) (Uragami 1998, 2005,
2006a, b, 2008, 2011; Uragami and Morikawa
1987, 1992; Uragami and Tanaka 1991, 1993,
1994; Uragami and Shinomiya 1991, 1992;
Uragami et al. 2002).
In TDEV, when the temperature of the feed
liquid was kept constant at 40  C and the temper-
ature of the membrane surroundings was changed
for an aqueous dilute ethanol solution through a
dense poly(dimethylsiloxane) (PDMS), the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_640-1
permeation rate decreased but the ethanol to a
temperature less than the temperature of the
feed liquid concentration in the permeate
increased with lowering of the temperature in
the membrane surroundings. The decrease in the
permeation rate can be attributed to lowering the
motion of both the permeating molecules and
polymer chains consisting the PDMS membrane.
On the other hand, the increase in the ethanol/
water selectivity is explained as follows. At first,
ethanol and water molecules are vaporized from
the feed mixture at higher temperature. When
those vaporized molecules come close to the
membrane surroundings kept at a lower temper-
ature, the water molecules are more aggregated
than the ethanol molecules (because the freezing
points of water and ethanol are 0 and 114.4  C,
respectively) It is very difficult for these aggre-
gated water molecules to be incorporated into the
dense PDMS membrane and diffuse through the
dense PDMS membrane. However, the ethanol
molecules are not aggregated in the range of the
temperature in the membrane surroundings under
these permeation conditions. The increase in the
ethanol/water selectivity is due to the aggregation
of water molecules and is significantly governed
by the degree of aggregation of the water
molecules.
In Table 1, the effect of the freezing point of
the permeant in aqueous organic liquid mixtures
on the selectivity through some polymer mem-
branes in TDEV in which the feed liquid was kept
constant and the temperature of membrane
2 Temperature-Difference-Controlled Evapomeation (TDEV)
Vacuum
Membrane ( II )
Feed liquid (I)
Temperature-Difference-Controlled Evapomeation
(TDEV), Fig. 1 Principle of temperature-difference-
controlled evapomeation (TDEV)
surroundings was changed is summarized. As can
be seen from Table 1, the permeant having a
lower freezing point in the feed mixture is selec-
tively permeated. In addition, when the mem-
brane has a stronger affinity to the preferentially
permeating mixture component, an increase in
selectivity can result in TDEV.
Figure 2 shows the effect of the temperature of
the membrane surroundings on the permeation
rate and the ethanol concentration in the permeate
for an aqueous solution of 10 wt% ethanol
through a dense PDMS membrane (a) and a
porous PDMS membrane (b) in TDEV. In
Fig. 2, the temperature of the feed solution is
kept constant at 40  C, and the temperature of
the membrane surroundings was changed. As
shown in Fig. 2a, b, the tendency of the decrease
in the permeation rate decreased, and the increase
in the ethanol/water selectivity with lowering
temperature of the membrane surroundings
through these two PDMS membranes was very
similar. In spite of the fact that the ethanol/water
selectivity in these PDMS membranes was
almost equal, the permeation rates through these
PDMS membranes were remarkably different,
a 10 100
Permeation rate 103 [kg/(m2h)]
EtOH in permeate (wt%)
75
5 50
25
0 0
b 20 100
EtOH in premeate (wt%)
Permeation rate [kg/(m2h)]
15 75
10 50
5 25
0 0
–20 10 20 40
Temperature of membrane soroudings (⬚C)
Temperature-Difference-Controlled Evapomeation
(TDEV), Fig. 2 Comparison of the permeation and sepa-
ration characteristics for an aqueous solution of 10 wt%
ethanol of a dense PDMS membrane (a) and a porous
PDMS membrane (b) in TDEV. Feed liquid is aqueous
solution of 10 wt.% ethanol (40  C)
i.e., the permeation rates in a porous PDMS mem-
brane were higher by three orders of magnitude
than those of a dense PDMS membrane.
A remarkable difference in the permeation
rate between dense and porous PDMS mem-
branes can be attributed to the fact that the per-
meation through a dense PDMS membrane is due
to the solution-diffusion model (Binding
et al. 1961; Aptel et al. 1974) and that through a
porous PDMS membrane is pore flow based on,
as shown in Fig. 3.
Temperature-Difference-Controlled Evapomeation (TDEV) 3

Temperature-Difference-Controlled Evapomeation (TDEV), Table 1 Effect of the freezing point on the selectiv-
ity of the permeant in the organic liquid mixtures through polymer membranes in TDEV
Membrane Chitosan PVC PDMS
Freezing point of (CH3)2SO/H2O 18.5  C CH3COOH/H2O 16.7  C C2H5OH/H2O 114.4  C
permeant > 0 C > 0 C < 0 C
Selectivity H2O H2O C2H5OH

Uragami T (1998) Structures and properties of membranes

Membrane
Lower
temperature
Higher
Feed liquid temperature
:H2O : EtOH
Temperature-Difference-Controlled Evapomeation
(TDEV), Fig. 3 Tentative mechanism of the concentra-
tion of aqueous ethanol solutions through porous PDMS
membrane in TDEV
References
Aptel P, Cuny J, Jozenfonvice J, Morel G, Neel J (1974)
Liquid transport through membranes prepared by
grafting of polar monomer onto poly(tetrafluor-
oethylene) films. II. Some factors determining
pervaporation rate and selectivity. J Appl Polym Sci
18:365
Binding RC, Lee RJ, Jennings JF, Mertic EC (1961) Sep-
aration of liquid mixtures by pervaporation. Ind Eng
Chem 53:47
Uragami T (1991) Method of separating a particular com-
ponent from its liquid solution. US Patent 4,983,303,
European Patent 0273267
Uragami T (1993a) Method of separating a particular
component from its liquid solution. European Patent
0273267
Uragami T (1993b) Method of separating a particular
component from its liquid solution. Brazilian Patent
P-8707041-3
Uragami T (1994) Separation method of mixed solutions.
Japanese Patent 1,883,353
from polysaccharide derivatives. In: Dumitriu S -
(ed) Polysaccharide – structural diversity and func-
tional versatility. Marcer Dekker, New York,
pp 887–924
Uragami T (2005) Structures and functionalities of mem-
branes from polysaccharides derivatives. In: Dumitriu
S (ed) Polysaccharides structural diversity and func-
tional versatility, 2nd edn. Marcer Dekker, New York,
pp 1087–1122
Uragami T (2006a) Polymer membranes for separation of
organic liquid mixtures. In: Yampolskii Y, Pinnau I,
Freeman BD (eds) Materials science of membranes for
gas and vapor separation. Wiley, Chichester,
pp 355–372
Uragami T (2006b) Separation materials derived from
chitin and chitosan. In: Uragami T, Tokura S (eds)
Material science of chitin and chitosan. KODANSHA,
Springer, Tokyo/Berlin/Heidelberg/New York,
pp 113–163
Uragami T (2008) Structural design of polymer mem-
branes for concentration of bio-ethanol. Polym
J 40:485
Uragami T (2011) Concentration of bio-ethanol through
cellulose ester membranes during temperature-
difference controlled evapomeation. Mater Sci Appl
2:1499
Uragami T, Morikawa T (1987) Permeation of ethanol
through polydimethyl siloxane membranes using
temperature-difference in membrane process of the
evapomeation method. Makromol Chem Rapid
Commun 10:287
Uragami T, Morikawa T (1992) Permeation and separa-
tion characteristics of alcohol-water mixtures through
dimethylsiloxane membrane by pervaporation and
evapomeation. J Appl Polym Sci 44:2009
Uragami T, Saito M (1989) Analysis of permeation and
separation characteristics: a new technique for separa-
tion of aqueous alcoholic solution through alginic acid
membranes. Sep Sci Technol 24:54
Uragami T, Shinomiya H (1991) Concentration of aque-
ous alcoholic solutions through a modified silicone
rubber membrane by pervaporation and evapomeation.
Makromol Chem 192:2293
Uragami T, Shinomiya H (1992) Concentration of aque-
ous dimethyl sulfoxide solutions through a chitosan
membrane by permeation with a temperature differ-
ence. J Membr Sci J Membr Sci 7:183
4 Temperature-Difference-Controlled Evapomeation (TDEV)
Uragami T, Tanaka Y (1991) Method of separating liquid
component from a solution containing two or more
liquid component. European Patent 0346739
Uragami T, Tanaka Y (1993) Method of separating liquid
component from a solution containing two or more
liquid component. US Patent 5,271,846
Uragami T, Tanaka Y (1994) Separation method for
mixed solutions. Japanese Patent 1,906,854
Uragami T, Saito M, Takigawa K (1988) Comparison of
permeation and separation characteristics for aqueous
alcoholic solutions by pervaporation and new
evapomeation methods through chitosan membranes.
Makromol Chem Rapid Commun 9:361
Uragami T, Tanaka Y, Nishida S (2002) Permeation and
separation under high temperature and high pressure
for ethanol/water vapors through cross-linked
quaternized chitosan composite membranes. Desalina-
tion 147:449
C
Central Nervous System in Relation
to Membranes
Loredana De Bartolo and Antonietta Messina
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
The central nervous system (CNS) is the most
complex organ in the human body. It consists of
two components, the brain and the spinal cord.
The spinal cord attends the communication path-
way between the brain and the periphery, and like
the brain, it is made of a gray matter, constituted
by the bodies of the neurons, and a white matter,
constituted by their myelinated axons, serving the
impulse transmission. Moreover, a special blood-
spinal cord barrier made of endothelial cells and
astrocytes protects the spinal cord from the bio-
logical and chemical changes coming from the
periphery. It was long believed that regenerative
processes in the CNS were completely absent,
then after an injury, the recovering of the axonal
function was impossible (Kandel et al. 2000). In
the early 1980s, therefore, it was discovered that
CNS retinal neurons were able to regenerate in
bioengineered devices of peripheral nerves,
highlighting that the nearly absent ability to
regenerate the central neurons does not lies in
the cells themselves but in their surrounding envi-
ronment. After physical trauma, hypoxic events,
and degenerative pathologies, a rapid severing of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_642-1
the axons occurs, and in the spinal cord, cell death
is recorded in high extent due to the lost electro-
lytic homeostasis and the accumulation of free
radicals and toxic factors that stimulate apoptotic
events. While the peripheral nervous system
(PNS) consists of a particular glial cell population
able to proliferate and produce specific factors
(BDNF, CNTF, GDNF) involved in the axonal
regeneration across the area of injury, the oligo-
dendrocytes constituting the main part of the
central glia are not able to provide similar support
after damage. In the injury site of the central
nervous system, they secrete numerous inhibitor
factors for the axonal regeneration, including
NOGO proteins, NI-35, chondroitin sulfate pro-
teoglycans (NG2), and keratan sulfate proteogly-
cans. The produced signaling factors that play
neuroprotective and regenerative roles appear,
then, to be not enough to oppose this inhibition
and the inflammatory events occurring after the
damage. Furthermore, astrocytes, another com-
ponent of the central glia, became proliferative.
In order to protect the severed site from external
molecules and the spreading of apoptotic events,
they form a tight network called a glial scar,
which obstruct the axonal regeneration, creating
a wall that axons and neurogenerative factors
cannot overtake (Horner and Gage 2002). Thus,
manipulation of the chemical and biological
environment around the injured site represents
the key of the treatment of the CNS damages.
Specifically, in order to promote the axonal
regeneration of the central neurons, the
2 Central Nervous System in Relation to Membranes
neurogenerative and neuroprotective factor
levels should increase (Recknor and
Mallapragada 2006). Nowadays, it is well
known how neural cells respond to their micro-
environment, enhancing adhesion, proliferation,
and migration along the regenerating site.
Smooth surfaces, patterned supports, and struc-
tures with high mass transport properties are the
main characteristics allowing the neural regener-
ation both in vivo and in vitro systems (Morelli
et al. 2012). Since decades ago, the gold standard
of the nervous system injury treatment is the
transplantation of nerve grafts able to substitute
the malfunctioning or lost areas of the system.
Despite the implantation of nerve grafts allowed
to reach important results in the recovery of
movement and sensibility of the PNS, the central
nervous system is hard to be treated, particularly
when inner regions of the brain are severed, then
new approaches appeared to be necessary for the
treatment of the CNS injury. Due to the develop-
ment of biomaterials and new processing
methods for the scaffold design, tissue engineer-
ing and chemotherapeutic strategies are the main
approaches for the development of regenerative
strategies able to guide axonal outgrowth. A wide
range of natural and synthetic biomaterials is
available to prepare neural scaffolds and releas-
ing devices (Tysseling and Kessler 2011). Differ-
ent classes of biodegradable polymers are
available, including polycaprolactone, polyure-
thanes, polylactic derived, polyglicolic acid,
chitosan, agarose, polysaccharides, collagen and
various ECM proteins derived. Due to their con-
trolled bioerosion, these materials allow the
design of different bioengineered devices, with
different shapes and configuration purposely
made for bridging the nerve growth or the factors’
release. Any biomaterial used to prepare neural
scaffolds possess, in addition to biocompatibility,
an appropriate range of permeability, porosity,
and biomechanical properties serving to avoid
the compression of the regenerating nerves or
the sudden collapse of the device in the treated
site. Actually, three different strategies are avail-
able for the treatment of the CNS injury: the
entubulation models, the drug delivery systems,
and the cell therapy. All of them are categorized
as membrane system devices due to their mass
transport properties they allow the diffusion,
release, and removal of the different factors
involved after an injury.
The entubulation strategy consists in the trans-
plantation of tubular scaffolds purposely made to
mimic the peripheral nerve tissue. Considering
that the PNS is characterized by a regenerative
ability due to proliferation of glial cells and the
secretion of neuroprotective and
neuroregenerative factors, many devices have
been developed with the aim of entrapping the
central axons in a protect environment, where
inhibitor factors are not allowed to pass through
and neuroregenerative signals are enhanced.
These bioartificial tubular nerve grafts are
meant to ensure a correct diffusion of nutrients
and oxygen and purposely designed with specific
thickness, mechanical strength, dimension, and
porosity degree. Tubular nerve grafts made of
PLLA, PCL and PGA, and collagen and chitosan
already extensively used for peripheral nerve
regeneration are nowadays applied for the treat-
ment of CNS injury models, alone or in conjunc-
tion with brain-derived neurotrophic factor
(BDNF) to promote the axonal regeneration
(Recknor and Mallapragada 2006; Morelli
et al. 2012). Cell-adhesive proteins such as colla-
gen, laminin, and fibronectin, which bind
strongly the integrin receptors on the cell sur-
faces, assist the nerve regeneration. They are
often used to coat the lumen of the bioartificial
channels or to modify the biomaterial used for the
device preparation in order to enhance the cell
response and the regenerative process. The pat-
terning of polymeric tubular membranes with
short oligopeptides derived from ECM proteins
is another way to increase the neurite outgrowth
and the cytoskeleton organization in the
regenerating neural tissue. Along similar lines,
the incorporation of hydrogels into the nerve
tubes have been evaluated with encouraging
results for CNS applications. Collagen,
hyaluronic acid, agarose, alginate, chitosan,
methyl cellulose, xyloglucan, matrigel, fibrin,
polysia-based hydrogels, peptide hydrogels, as
Central Nervous System in Relation to Membranes
well as synthetic hydrogels, such as polyacryl-
amide and polyethylene glycol hydrogels,
revealed to be the best alternative to the classical
polymeric nerve guidance grafts. Bioengineered
tubular scaffolds have been combined also with
cells providing a promising new approach for the
CNS injury treatment. Since 1998, it is well
known that remyelination of central axons can
be promoted by using Schwann and olfactory
glial cells entubulated in bioartificial scaffolds,
and moreover, Schwann cells, when seeded in
combination with neurotrophic factors or hor-
mones, facilitated the axon regeneration. There-
fore, the strategy is to entubulate neural stem cells
(NSC), which possess the ability to differentiate
into neurons, astrocytes, or oligodendrocytes in
presence of specific growth factors and appropri-
ate chemical environment. Despite the risk of
uncontrolled proliferation and some problems in
the maintenance of cell viability, the use of the
neural stem cells in membrane systems is still the
most promising approach. Drug delivery strat-
egy. When a nerve guide or other bioartificial
implants are not appropriate due to the impossi-
bility to reach the severed central nervous area,
the delivery system of neurogenerative and
neuroprotective factors represent the alternative
strategy. A few molecules of natural and syn-
thetic origin showed to promote the neural regen-
eration. Steroids, minocycline, interleukin
10, erythropoietin, and neurotrophins, like NGF,
BDNF, and CNTF, are just some of the
neuroprotective agents implied in the inhibition
of the inflammatory response, microglial activa-
tion, and apoptotic event after a central injury
(Kandel et al. 2000). Induction of the
regeneration-associated genes expression
(RAGs) or the Rho-Rock pathway inhibition is
some of the neurogenerative properties of the
neurotrophins. Moreover, they promote their
remyelination, the sprouting and growth of new
neurons with functional recovery. Whether the
factors possess neuroprotective or
neurogenerative ability, the delivery strategies
are the same. Growth factors, proteins, and
drugs are encapsulated into the devices made of
polymer, hydrogels, or proteins and injected in
the spinal cord through epidural and intrathecal
3
routes for the spinal cord regeneration.
Hydrogels, liposomes, fibrin, collagen-based,
and other polymeric delivery devices obtained
from natural and synthetic biomaterials have
been implanted subcutaneously near the spinal
cord’s injured site, allowing the continuous
release of the neuroprotective and
neurogenerative agents and the partial recovery
of the axonal functionality (Zhong and
Bellamkonda 2008). Cell therapy. The drug/bio-
logical delivery strategies are easy with respect to
the entubulation methods, but in truth, they have
one disadvantage: the constant drug dose is
achievable only with reinjection of new delivery
devices. The cell therapy, instead, relies on a
longer production of the therapeutic factors
through the cell stimulation in the injured site or
the transplantation of autologous, allogenic, or
xenogenic cells. Generally, the cell therapy is
used for the treatment of the neurodegenerative
pathologies and of the chronic pain. In order to
implant the cells in the interested site, specific
polymeric carriers are available. A few trial
models suggested that this kind of approach
could enhance the chances of the patient to
recover partially the neuronal functionality,
opposing the symptoms and the cognitional prob-
lems. Polymeric membranes ensure a consistent
advantage for that kind of application, which
consists in the chance to control cell viability
and the diffusion of nutrients and at the same
time, the protection of the cellular population
from the immunological reaction of the body.
Genetically engineered cells encapsulated into
hollow fiber membranes are able to produce and
release ciliary neurotrophic factor (CNTF) in
patients affected by amyotrophic lateral sclerosis.
Parkinson’s disease is another degenerative
pathology treatable with the cell transplantation.
In this case, dopamine-producing cells, dispersed
also in different hollow fiber membranes of algi-
nate, showed an increase of the recovery and an
analgesic effect in the patient (Cho and Borgens
2012; Morelli et al. 2012). Therefore, the low
percentage of cells surviving after implantation
and the host rejection and the inflammatory
response represent the main disadvantages of
the cell therapy strategies. For this reason, despite
4 Central Nervous System in Relation to Membranes
the encouraging results available, the complexity
of the central nervous system made the regener-
ative strategies always promising and not conclu-
sive at the same time, and further investigation
must be done in order to ensure a safe and func-
tional approach for the recovery after an injury.
References
Cho Y, Borgens RB (2012) Polymer and nano-technology
applications for repair and reconstruction of the central
nervous system. Exp Neurol 233:126–144
Horner PJ, Gage FH (2002) Regeneration in the adult and
aging brain. Arch Neurol 59:1717–1720
Kandel E, Schwartz J, Jessell T (2000) Formation and
regeneration of synapsis. In: Principles of neuronal
science, 4th edn. McGraw-Hill Medical, New York,
pp 1087–1114
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C,
Tasselli F, di Vito A, Giusi G, Canonaco M, Drioli E,
De Bartolo L (2012) Flat and tubular membrane sys-
tems for the reconstruction of hippocampal neuronal
network. J Tissue Eng Regen Med 6:299–313
Recknor JB, Mallapragada SK (2006) Nerve regeneration:
tissue engineering strategies. In: Bronzino JD, Peter-
son DR (eds) The biomedical engineering handbook:
tissue engineering and artificial organs. Taylor &
Francis, New York
Tysseling VM, Kessler JA (2011) Biomaterials for central
nervous system regeneration. Tissue Eng Neurolog
Neurosurg 533:455–466
Zhong Y, Bellamkonda RV (2008) Biomaterials for the
central nervous system. J R Soc Interface 5: 957–975
M
Molecular Dynamics in Membranes
Elena Tocci
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rende (CS), Italy
Over the last 30 years, detailed atomistic molec-
ular modeling techniques, namely, the molecular
dynamics (MD) and the Monte Carlo (MC), have
become a widely used method for the investiga-
tion of the molecular structure of membrane
materials and transport properties in various
membrane operations (Binder 1995; Gubbins
and Moore 2010; Hofmann and Tocci 2009;
Maginn and Elliot 2010; Theodorou 2006, 2010;
Razmus and Hall 1991; Harmandaris and
Mavrantzas 2004).
Molecular dynamics simulations have been
used to build or modify membranes and to inves-
tigate the physical and surface properties of
membranes used in gas separation and water
treatment processes. The molecular modeling of
polymer-based membrane materials generally
starts with the construction of typically rectangu-
lar packing models (Hofmann and Tocci 2009).
There, the related chain segments of the respec-
tive polymer are arranged in a realistic, that is,
statistically possible, way. The limited lateral
dimensions of packing models of just several
nanometers make it impossible to simulate com-
plete membranes or other polymer-based sam-
ples. Therefore, on the one hand, bulk models
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_643-1
are considered that are typically cubic volume
elements of a few nanometers side length that
represent a part cut out of the interior of a poly-
mer membrane. On the other hand, interface
models are utilized, for example, for the interface
between a liquid feed mixture and a membrane
surface or between a membrane surface and an
inorganic filler. The quality of atomistic packing
models is typically validated via comparisons
between measured and simulated properties like
wide-angle X-ray scattering (WAXS) curves,
densities, etc.
Example: Free-Volume Distribution
The free-volume distribution in amorphous poly-
mers is of paramount importance for their trans-
port behavior toward small- and medium-sized
penetrant molecules. Atomistic molecular
modeling utilizing bulk models on the other
hand can provide additional even more detailed
information on the magnitude, the spatial distri-
bution, and the connectivity of accessible volume
within an amorphous polymer matrix (Theodorou
2010).
The accessible volume for a given penetrant
molecule is the volume of the volume domain
composed of points that can be occupied by the
center of mass of the penetrant without any over-
lap between the van der Waals spheres of the
penetrant and those of the polymer atoms. For
most polymer–penetrant pairs of practical
2 Molecular Dynamics in Membranes
interest, the accessible volume in any configura-
tion is partitioned into disjoint clusters.
Generally, for polymeric membranes with low
permeability of small molecules, such as
diisopropyldimethyl PEEK WC (DIDMPEEK),
the accessible free volume is organized in rela-
tively small isolated holes and a size distribution
that is monomodal and extending only to hole
radii of about 5 Å (Hofmann and Tocci 2009).
Polymers with ultrahigh permeability, such as
PTMSP and Teflon AF2400 of DuPont
(PO2 = 1,140 Barrer), show ultrahigh free vol-
ume. In this case, simulation data support the
existence of a bimodal distribution of accessible
volume clusters. One mode of the distribution,
with a maximum at around 3–4 Å, is comparable
to the distributions encountered in dense glassy,
low permeability polymers. The other, in parallel,
is a partly continuous phase of much larger holes
that in this case are visible as a peak between
15 and 20 Å (Hofmann and Tocci 2009; Jansen
et al. 2009).
Examples in Gas Separation: Dense
Polymeric Membranes
The permeation of small molecules in amorphous
polymers is typically following the solution dif-
fusion model, that is, the permeability Pi of a feed
component i can be envisioned as the product of
the respective solubility Si and constant of diffu-
sion Di. Both parameters can be obtained exper-
imentally and in principle also by atomistic
simulations (Theodorou 2006).
The most common approach to obtain diffu-
sion coefficients for gases and vapors is equilib-
rium molecular dynamics. The diffusion
coefficient that is obtained is a self-diffusion
coefficient by using the Einstein (Eq. 1) or by
means of the Green-Kubo (Eq. 2) formulations:
D E
½r ð0Þ  r ðtÞ2
D ¼ lim (1)
t!1 6t
ð
1
1
D¼ hvð0Þ  vðtÞi (2)
3
0
As temperature is reduced toward and below Tg,
penetrant diffusion in an amorphous polymer
matrix becomes too slow to be predictable by
MD simulations. Direct MD would require long
simulation times for the prediction of diffusivity
in low-temperature rubbery polymers and poly-
mer glasses, which are most relevant from the
point of view of membrane and barrier material
applications (Theodorou 2006; Fried 2006). In
such cases diffusion is considered as a sequence
of infrequent penetrant jumps, and the transition
state theory (TST) of Gusev et al. (1995) and the
multidimensional TST approach developed by
(Greenfield 2004) can be utilized. Transport-
related diffusion coefficients are less frequently
studied by simulation but several approaches
using non-equilibrium MD (NEMD) simulation
have also been used (Theodorou 2006).
The solubility of gases and vapors can be
obtained by means of several computational
approaches, principally the Widom particle inser-
tion (Widom 1963) and the Grand Canonical
Monte Carlo (GCMC) (Binder 1995; Theodorou
2006; Razmus and Hall 1991) methods. The
interaction energy of a gas particle inserted
within the accessible free volume of the polymer
matrix is calculated, and the excess thermody-
namic potential mexcess can be estimated from
(Eq. 3)
mexcess ¼ RTlnhexpðEint =kT Þi (3)
The solubility S is then obtained from relation
(Eq. 4)
S ¼ expðmexcess =RT Þ (4)
Also in this case, another approach is the transi-
tion state theory (TST) of Gusev et al. (1995).
The simulations of the sorption and diffusion
of low molecular weight penetrants on amor-
phous polymers have covered a range of different
polymers with varieties of chemical complexities
ranging from flexible polymers with simple
Molecular Dynamics in Membranes
chemical structure, like poly(dimethylsiloxane)
(PDMS) (Hofmann et al. 2000), poly(isobutyl-
ene) (PIB) (Hofmann et al. 2000), polyethylene
(PE) (Hofmann et al. 2000), and polypropylene
(PP) (Hofmann et al. 2000), to stiff polymers with
detailed chemical structure, like polyamides
(Heuchel et al. 2004), PIMs (Larsen et al. 2011),
Tr-PBO (Park et al. 2014) membranes, and on
polyelectrolytes (Dobrynin 2004).
The predicted self-diffusion coefficients
depend principally on the quality of the force
fields used to model the interactions not only
between the penetrant and polymer matrix but
also by intramolecular interactions between poly-
mer chains. MD simulation of gas diffusion in
polymer membranes generates a wealth of infor-
mation on the mechanism of gas transport but its
use is limited to high free-volume rubber matri-
ces and small gas molecules due to prohibitive
CPU times for diffusion coefficients smaller than
108 cm2 s1. For this reason, today, the tech-
nique is not adequate for systematic screening of
a large number of polymer candidates and gener-
ating data to be used in a materials design
approach.
The slowness of MD is an obstacle to the study
of polymer properties, but not a barrier. This is
especially true when the properties of interest are
localized, as in the case of glass transition or
diffusivity of small molecules through a polymer
matrix. At the far end of what can be achieved,
MD can also be applied to study polymer dynam-
ics on the time and length scales of polymer
entanglement. For current applications, we
focus on methods that have been illustrated with
several polymers and are on the verge of being
competitive with existing empirical methods.
References
Binder K (ed) (1995) Monte Carlo and molecular dynam-
ics simulations in polymer science. Oxford University
Press, New York
Dobrynin AV (2004) Chapter 8. Molecular simulations of
charged polymers. In: Kotelyanskii M, Theodorou DN
(eds) Simulation methods for polymers. Marcel Dek-
ker, New York, pp 259–312
3
Fried JR (2006) Molecular simulation of gas and vapor in
highly permeable polymers and references therein. In:
Yampolskii Y, Pinnau I, Freeman B (eds) Materials
science of membranes for gas and vapor separation.
Wiley, Chichester, pp 95–127
Greenfield ML (2004) Sorption and diffusion of small
molecules using Transition State theory and references
therein. In: Kotelyanskii M, Theodorou DN (eds) Sim-
ulation methods for polymers. Marcel Dekker, New
York, pp 425–490
Gubbins KE, Moore JD (2010) Molecular modeling of
matter: impact and prospects in engineering. Ind Eng
Chem Res 49:3026–3046
Gusev AA, Suter UW, Moll DJ (1995) Relationship
between helium transport and molecular motions in
glassy polycarbonate. Macromolecules 28:2582–2584
Harmandaris VA, Mavrantzas VG (2004) Chapter 6.
Molecular dynamics simulations of polymers. In:
Kotelyanskii M, Theodorou DN (eds) Simulation
methods for polymers. Marcel Dekker, New York,
pp 177–222
Heuchel M, Hofmann D, Pullumbi P (2004) Molecular
modeling of small-molecule permeation in polyimides
and its correlation to free-volume distributions. Mac-
romolecules 37(1):201–214
Hofmann D, Tocci E (2009) Chapter 1. Molecular model-
ing. A tool for the knowledge-based design of
polymer-based membrane materials. In: Drioli E,
Giorno L (eds) Membrane operations: innovative sep-
arations and transformations. Wiley-VCH Verlag
GmbH %26 Co. KGaA, Weinheim, pp 253–255, and
references therein
Hofmann D, Fritz L, Ulbrich J, Schepers C, Bӧhning
M (2000) Detailed-atomistic molecular modeling of
small molecule diffusion and solution processes in
polymeric membrane materials. Macromol Theory
Simul 9:293–327, and references therein
Jansen JC, Macchione M, Tocci E, De Lorenzo L,
Yampolskii YP, Sanfirova O, Shantarovich VP,
Heuchel M, Hofmann D, Drioli E (2009) Comparative
study of different probing techniques for the analysis
of the free volume distribution in amorphous glassy
perfluoropolymers. Macromolecules 42:7589–7604
Larsen GS, Lin P, Siperstein FR, Colina CM (2011) Meth-
ane adsorption in PIM-1. Adsorption 17(1):21–26, and
references therein
Maginn EJ, Elliot JR (2010) Historical perspective and
current outlook for molecular dynamics as a chemical
engineering tool. Ind Eng Chem Res 49:3059–3078
Park CH, Tocci E, Kim S, Kumar A, Lee YM, Drioli
E (2014) A simulation study on OH-containing
polyimide (HPI) and thermally rearranged
polybenzoxazoles (TR-PBO): relationship between
gas transport properties and free volume morphology.
J Phys Chem B 118:2746–275
Razmus DM, Hall CK (1991) Prediction of gas adsorption
in 5 Å zeolites using Monte Carlo simulation. AIChE
J 37:769–779
4 Molecular Dynamics in Membranes

Theodorou DN (2006) Chapter 2. Principles of molecular
simulation of gas transport in polymers. In:
Yampolskii Y, Pinnau I, Freeman B (eds) Materials
science of membranes for gas and vapor separation.
Wiley, Chichester, pp 49–89
Theodorou DN (2010) Progress and outlook in Monte
Carlo simulations. Ind Eng Chem Res 49:3047–3058
Widom B (1963) Some topics in the theory of fluids.
J Chem Phys 39:2808–2812
B
Bilberry Aroma Recovery by
Pervaporation
Immaculada Ortiz and Nazely Diban
Chemical and Biomolecular Engineering
Department, University of Cantabria, Santander,
Cantanbria, Spain
Introduction
Pervaporation (PV) is a membrane-based tech-
nology largely studied for aroma compound
recovery and concentration in the food industry
(Pereira et al. 2006). At least two PV pilot plants
for aroma compound recovery have been built at
Membrane Technology and Research (MTR)
Inc., California (EEUU), and Agrotechnology &
Food Innovations (A&F) in the Netherlands
(Willemsen et al. 2004), and theoretical studies
assessing the recovery and concentration of
aroma compounds by means of PV have demon-
strated the viability of this technology at indus-
trial scale (Karlsson et al. 1998; Lipnizki
et al. 2002a, b; Trifunovic et al. 2006). During
the PV, the aroma compounds contained in a
liquid or feed phase permeate selectively through
a dense hydrophobic membrane due to the chem-
ical potential gradient caused by a reduction of
the component partial pressure in the permeate
side. The aroma compounds are preferentially
transported through the membrane according to
their affinity to the membrane material and their
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_645-5
mobility in the membrane matrix, which is the
hypothesis of the most accepted mass transport
mechanism in PV known as solution-diffusion.
Bilberry (Vaccinium myrtillus L.) is a species
of shrub and is native from Europe, northwest
regions of North America, and Northern Asia
(Morton and Macleod 1990). The international
markets’ demand of bilberry’s extract has been
steadily growing in the recent years (Foster and
Blumenthal 2012). The major aroma compounds
present in crushed bilberry were identified by gas
chromatography-mass spectroscopy (GC-MS).
The results are shown in Fig. 1. Trans-Hex-2-
en-1-ol was characterized as one of the impact
flavor of the bilberry (von Sydow and Anjou
1969).
Membrane Material and Module
Configurations
The most typical organophilic membrane mate-
rials employed in PV of aroma compounds in the
literature are polydimethylsiloxane (PDMS) and
polyoctylmethylsiloxane (POMS). POMs mem-
branes present higher enrichment factors for
aroma compounds than PDMS albeit not signifi-
cantly different. Nonetheless, PDMS membranes
are largely more studied due to their stability
during operation and good properties of
processing (Karlsson and Trägardh 1993;
Lipnizki et al. 1999; Urtiaga et al. 1999).
With regard to the membrane module config-
urations, plate-and-frame is the most employed in
literature for laboratory scale studies for their
2 Bilberry Aroma Recovery by Pervaporation
kCounts
500
1 4
400
300
200
2
100 3
25
1540
Bilberry Aroma Recovery by Pervaporation,
Fig. 1 GC-MS chromatogram of the crushed bilberry:
(1) trans-hexenal, (2) 2-butyl-1-octanol, (3) 1-hexanol,
simplicity and versatility for the evaluation of
different membrane materials. However, the hol-
low fibers membrane (HFM) module configura-
tion presents important advantages, such as
higher contact area per unit volume of membrane
module and thus higher compactness of the
equipment and easier operation at industrial
scale (Urtiaga et al. 1999, 2002; Tasselli
et al. 2007).
Influence of Process Variables
Using a model ternary solution (water/ethanol/
trans-Hex-2-en-1-ol), the process variables that
exerted an important influence on the PV perfor-
mance of the impact aroma compound (trans-
Hex-2-en-1-ol) when using a PDMS HFM mod-
ule with the characteristics presented at (Garcia
et al. 2008) were:
(i) The feed composition (ethanol and aroma
compound). The results are presented in
5
50 75 100 minutes
3148 4747 6338 Scans
(4) trans-Hex-2-en-1-ol, and (5) 1-hexadecanol (Adapted
from (Garcia et al. 2008))
Fig. 2. As expected, ethanol flux, JEtOH,
increased linearly with higher ethanol con-
tent in the feed, while in contrast, aroma
compound partial flux, JHex, remained inde-
pendent on ethanol concentration but
presented a linear dependency with its own
concentration in the feed solution. The major
component flux, water, was independent on
both ethanol and aroma compound composi-
tion. The enrichment factors found for the
aroma compound, bHex, varied from 98 to
201.
(ii) The feed temperature, studied in the range
35  C < T < 50  C. The components’ par-
tial fluxes (water, ethanol, and trans-Hex-2-
en-1-ol) were found to follow an Arrhenius
dependency with temperature as plotted in
Fig. 3.
In the present application and working under
laminar flow rate conditions, 203<Re<772, the
Bilberry Aroma Recovery by Pervaporation 3

[Hex] (kg.m–3)
a b 0 0.1 0.2 0.3
20 2.00 1.8
18 1.80 1.6
16 1.60 1.4
JEtOH (g.m–2.h–1)

JHex (g.m–2.h–1)

JHex (g.m–2.h–1)
14 1.40
1.2
12 1.20
1.0
10 1.00
8 0.80 0.8
6 0.60 0.6
4 0.40 0.4
2 0.20 0.2
0 0.00 0.0
0 2 4 6 0 5 10
[EtOH] (%v/v)
XHex g Hex P0 Hex (Pa)

Bilberry Aroma Recovery by Pervaporation,
Fig. 2 (a) Effect of ethanol concentration in the feed on
the permeation flux of the ethanol in (■) binary water/
ethanol and (◊) ternary water/ethanol/Hex mixtures, and
(~) flux of trans-hex-2-en-1-ol in ternary mixtures
[Hex] = 0.1 kg.m 3, T = 50  C and Re = 772. (b) Effect
of trans-hex-2-en-1-ol partial pressure in the feed on its
permeation flux at 50  C, Re = 772, and [EtOH] = 1%v/v
(Adapted from (Garcia et al. 2008))

Bilberry Aroma Recovery 4.0

by Pervaporation,
3.5
Fig. 3 Effect of the feed
temperature on the partial 3.0
fluxes of the components Hex
2.5
when Re = 772,
[Hex] = 0.1 kg.m 3, and 2.0 EtOH
[EtOH] = 1%vv (Adapted
In Ji

1.5 Water
from (García et al. 2008))
1.0
0.5
0.0
–0.5
–1.0
3.05 3.10 3.15 3.20 3.25 3.30
1000/T(K–1)

aroma compound transfer flux was independent PV of Multicomponent Systems

on the feed flow rate. This indicated that the
concentration polarization phenomena in the
feed boundary layer was negligible in compari-
son with the aroma compound mass transfer
resistance in the membrane which normally
occurs with high membrane thickness, i.e.,
127 and 160 mm (Peng and Liu 2003; Kanani
et al. 2003), similar to the membrane thickness
herein studied, 196 mm.
PV of multicomponent systems of the bilberry
characteristic aroma flavor was performed theo-
retically by means of simulation considering the
composition in Table 1 and commercial PDMS
HFM modules. The membrane area considered
was Am = 0.0056 m2 and the membrane thick-
ness, d, was 1.96  10 4 m. Further details of the
simulation conditions can be found in (Diban
et al. 2008). The results of the simulation are
4 Bilberry Aroma Recovery by Pervaporation

Bilberry Aroma Recovery by Pervaporation, Table 1 Feed composition (found in Hirvi and Honkanen 1983), and
simulation results of the permeate composition, enrichment factors, and partial fluxes in the bilberry multicomponent
system after PV with a PDMS HFM module at 30  C and a membrane area Am = 0.0056 m2 (Diban et al. 2008)
Feed composition, CFi Permeate composition, CPi
Component (mg.kg 1) (mg.kg 1) bi Ji (g.m 2
h 1)
Trans-Hex-2-en-1-ol 0.01 1.21 120.6 3.78  10 5
n-Hexanol 0.02 4.74 236.9 14.9  10 5
Trans-Hex-2-en-1-al 0.06 2.78 46.3 8.70  10 5
Linalool 0.004 0.20 49.3 0.62  10 5
Phenyl acetaldehyde 0.003 0.02 5.5 0.05  10 5
Benzyl alcohol 0.08 0.33 4.2 1.05  10 5
Cis-Hex-3-en-1-ol 0.06 1.64 27.4 5.15  10 5
Ethanol 7800 106,934 13.7 2.51
Water 992,200 893,057 0.9 20.9

7.00E-05 180
160
6.00E-05
140
JHex(g m–2 h–1)

5.00E-05
120
4.00E-05 100
bHex

3.00E-05 80
2.00E-05 60
40
1.00E-05
20
0.00E-00 0
0 5 10 15 20 0 5 10 15 20
δ ¥ 104 (m) δ¥ 104 (m)

Bilberry Aroma Recovery by Pervaporation, thickness, d. T = 30  C, [Hex] = 10 5 kg.m 3,

Fig. 4 Change of the partial flux of trans-Hex-2-en-1- [EtOH] = 1%v/v, Re ~6  105, Am = 0.0056 m2
ol, JHex, and enrichment factor, bHex, with the membrane (Adapted from Diban et al. 2008)

collected in Table 1. There is a clear change in the Future Directions

component profile from the feed solution to the
permeate aroma compound concentrate.
Moreover, the theoretical evaluation of the
influence of the membrane thickness, d, on the
performance of the PV of trans-Hex-2-en-1-ol
was performed. The results are plotted in Fig. 4.
From these results, it is extracted that a commer-
cially available membrane with a thickness of
1.48  10 4 m led to a compromise situation
with important impact aroma compound enrich-
ment factors bHex ~90 and adequate fluxes JHex
~3  10 5 g.m 2.h 1.
1. Experimental assessment of the behavior of
real solutions to evaluate (i) the interaction
between different molecules during PV and
(ii) the aroma profiles in the permeate.
2. Integration of a sensory evaluation of the qual-
ity of the aroma compound concentrate that,
independently of the aroma profile, is mainly
affected by the presence of the impact aroma
compounds in the permeate.
3. Evaluation of other membrane materials that
reduce water mass transfer and enhance the
Bilberry Aroma Recovery by Pervaporation
aroma compound enrichment factors with the
minimum flux reduction, such as POMS.
References
Diban N, Urtiaga A, Ortiz I (2008) Recovery of key
components of bilberry aroma using a commercial
pervaporation membrane. Desalination 224:34–39
Foster S, Blumenthal M (2012) The adulteration of com-
mercial bilberry extracts. J Am Bot Counc 96:64–73
García V, Diban N, Gorri D, Keiski R, Urtiaga A, Ortiz
I (2008) Separation and concentration of bilberry
impact aroma compound from dilute model solution
by pervaporation. J Chem Technol Biotechnol
83:973–982
Hirvi T, Honkanen E (1983) The aroma of blueberries.
J Sci Food Agric 34:992–998
Kanani DM, Mikhade BP, Balakrishnan P, Singh G,
Pangarkar VG (2003) Recovery of valuable tea
aroma components by pervaporation. Ind Eng Chem
Res 42:6924–6932
Karlsson HOE, Trägårdh G (1993) Pervaporation of dilute
organic-waters mixtures. A literature review on
modeling studies and applications to aroma compound
recovery. J Membr Sci 76:121–146
Karlsson HOE, Trägårdh G, Olsson J (1998) The perfor-
mance of pervaporative units: process simulations. Sep
Sci Technol 33:1629–1652
Lipnizki F, Hausmanns S, Ten PK, Field RW, Laufenberg
G (1999) Organophilic pervaporation: prospects and
performance. Chem Eng J 73:113–129
Lipnizki F, Olsson J, Trägårdh G (2002a) Scale-up of
pervaporation for the recovery of natural aroma
5
compounds in the food industry. Part I: simulation
and performance. J Food Eng 54:183–195
Lipnizki F, Olsson J, Trägårdh G (2002b) Scale-up of
pervaporation for the recovery of natural aroma com-
pounds in the food industry. Part II: optimization and
integration. J Food Eng 54:197–205
Morton ID, Macleod AJ (1990) Food flavours part C. The
flavor of fruits. Elsevier, Amsterdam
Peng M, Liu SX (2003) Recovery of aroma compounds
from dilute model blueberry solution by
pervaporation. Food Eng Phys Prop 68:2706–2710
Pereira CC, Ribeiro CP, Nobrega R, Borges CP
(2006) Pervaporation of volatile aroma compounds
from fruit juices. J Membr Sci 274:1–23
Tasselli F, Cassano A, Drioli E (2007) Ultrafiltration of
kiwifruit juice using modified poly(ether ether ketone)
hollow fibre membranes. Sep Purif Technol 57:94–102
Trifunović O, Lipnizki F, Trägårdh G (2006) The influ-
ence of process parameters on aroma recovery by
hydrophobic pervaporation. Desalination 189:1–12
Urtiaga A, Gorri ED, Beasley JK, Ortiz I (1999) Mass
transfer analysis of the pervaporation separation of
chloroform from aqueous solutions in hollow fiber
devices. J Membr Sci 156:275–291
Urtiaga A, Gorri ED, Ortiz I (2002) Mass-transfer model-
ing in the pervaporation of VOCs from diluted solu-
tions. AIChE J 48:572–580
von Sydow E, Anjou K (1969) The aroma of bilberries
(Vaccinium myrtillus L.) I. Identification of volatile
compounds. Lebensm Wiss Technol 2:78–81
Willemsen JHA, Dijkink BH, Togtema A (2004)
Organophilic pervaporation for aroma isolation-
industrial and commercial prospects. Membr Technol
2:5–10
C

Chromium Transport Through Ion
Exchange Membranes
Eugenio Bringas and Immaculada Ortiz
Department of Chemical and Biomolecular
Engineering, University of Cantabria, Santander,
Cantabria, Spain
based on the use of selective liquid membranes,
especially emulsion liquid membranes (ELMs)
(Salazar et al. 1992) supported liquid membranes
(SLMs) (Kentish and Stevens 2001),
non-dispersive solvent extraction (NDSX)
(Bringas et al. 2012), and the emulsion
pertraction technology (EPT) (Bringas
et al. 2006a).

Occurrence and Removal of Hexavalent

Chromium from Polluted Waters
Formulation of Selective Liquid
Membranes for Hexavalent Chromium
The widespread use of chromium in industrial
Removal
applications such as leather tanning, metallurgy,
electroplating processes, and so forth has caused
The main characteristics of the compounds to be
chromium contamination of surface and ground-
employed as selective carriers in the formulation
waters (Pagilla and Canter 1999; Lin 2002;
of selective liquid membranes in industrial appli-
Rengeraj et al. 2001). Public concerns arise as a
cations are as follows: (i) high selectivity toward
result of the sufficient evidence of chromium
the target species, (ii) minimum extraction capac-
(VI) carcinogenicity in humans and the
ity of competing compounds, (iii) ease of regen-
bioaccumulation into flora and fauna (IARC
eration, (iv) high solubility in low-cost solvents,
1990; Kimbrough 1999).
(v) long-term stability, (vi) low cost, and (vii) not
Conventional processes reduce Cr6+ to Cr3+,
exhibiting toxic and carcinogenic properties.
which is less toxic, less soluble, and less mobile
Figure 1 shows the distribution of hexavalent
than Cr6+. Trivalent chromium is then converted
chromium species in aqueous solution as a func-
to the hydroxide form and removed after precip-
tion of pH and the total chromium concentration
itation (Hashim et al. 2011). Other technologies
(Bringas et al. 2006a). It is noticed that at basic
have been reported in literature as feasible alter-
pH values, the major species is chromate
natives to achieve the removal and recovery of
(CrO42
), while in the acid range (1< pH <7),
hexavalent chromium from wastewaters: adsorp-
the coexistence of hydrogen chromate (HCrO4
)
tion and ion exchange (Mohan and Pittman 2006;
and dichromate (Cr2O72
) is expected. There-
Rivero et al. 2004), membrane processes
fore, the extraction of Cr6+ takes place through
(Bohdziewicz 2000) and separation processes
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_646-1
2 Chromium Transport Through Ion Exchange Membranes

Chromium Transport −2 −1 0 1 2 3 4 5 6 7 8 9 10
Through Ion Exchange 2
Membranes,
Fig. 1 Speciation diagram 1 Cr2O72-
of Cr6+ in aqueous solution

Log [Cr] total

0
(Bringas et al. 2006a)
H2CrO4 HCrO4- CrO42-
−1

−2

−3

−4
−2 −1 0 1 2 3 4 5 6 7 8 9 10
pH

an anion- exchange mechanism, and thus, solvat-

ing and basic extractants are required.
The extraction of chromium by solvating
extractants is based on the formation of an
organic intermediate by the interactions between
an electron donor (usually a phosphinic or a
phosphoric moiety) and an electron acceptor
(usually a proton) as shown by the following
reaction which occurs in acid media:
S þ Hþ þ X
$ SHX
where S is the solvating carrier and X represents
the target species.
The commercial solvating extractants that
employed the most on the removal of hexavalent
chromium are TBP (tributyl phosphate marketed
by Lanxess) (Venkateswaran and Palanivelu
2005), Cyanex 921 (trioctylphosphine oxide,
TOPO, marketed by Cytec Industries) (Alguacil
et al. 2004), and Cyanex 923 (a mixture of four
trialkylphosphine oxides marketed by Cytec
Industries) (Alguacil et al. 2004).
Tertiary amines and salts of quaternary amines
represent the most important groups of basic
extractants employed in the extraction of
hexavalent chromium being the extraction mech-
anism described by the following ion-exchange
reactions:
Salts of quaternary amines (chloride form)
QCl þ X
$ QX þ Cl

Tertiary amines
T þ HY $ ðTH Þþ Y
 Protonation (3)
ðTHÞþ Y
þ X
$ ðTHÞþ X
þ Y

 Ion exchange (4)
where QCl is the chloride salt of a quaternary
amine, T is a tertiary amine, and HY is a
mineral acid.
(1)
Aliquat 336 (N-methyl-N,N-dioctyloctan-1-
- ammonium chloride marketed by BASF)
(Bhowal et al. 2012) and Alamine 336 (mixture
of tertiary amines with C8 and C10 groups
marketed by BASF) (Bringas et al. 2006b) are
the most reported commercial quaternary and
tertiary amines employed in the removal of
hexavalent chromium species.
Removal of Hexavalent Chromium from
Polluted Groundwaters by the EPT
Technology
Bringas et al. (2006a, b, 2007) reported the meth-
odology for the optimal design of selective liquid
membrane processes as efficient alternatives for
the separation and selective recovery of
hexavalent chromium from polluted groundwater
generated by effluent leaking from surface depo-
sition of industrial wastes. Furthermore, other
(2) competitive anionic species (mainly sulfate and
chloride anions) were also present in the ground-
water due to the specific location being close to
Chromium Transport Through Ion Exchange Membranes 3

1.FUNDAMENTALS

Problem Statement Selection of Extraction (EX) and Back-Extraction (BEX) MBSX Technology Selection
Agents
- Effluent characterisation - Proposal of EX and BEX reactions - Process configuration
- Objectives - Kinetic or equilibrium Patten - Operational conditions
- Obtention of the equilibrium/kinetic parameters

2. TECHNICAL EVALUATION

Kinetic Analysis of the Separation - Concentration Process Mathematical Modeling of the Separation - Concentration Process

- Process Viability - Mass transfer hypothesis

- Analysis of the influence of the operation variables on the EX - Solute mass balances in the different fluid phases
and BEX kinetics - Mass transfer coefficients
- Model validation

3. PROCESS DESIGN 4. ECONOMICAL EVALUATION

- Removal and recovery requirements (Constrains) Detailed cost evaluation of the selected alternative
- Preliminary capital cost definition (Objective Function) - Capital cost evaluation
- Proposal of design alternatives (Network Superestructures) - Operation cost evaluation
- Mathematical modeling of the network superestructures - Analysis of the investment recovery
(Opimization Model)
- Application of the mathematical optimization techniques to select
the alternative with minimum total cost

Chromium Transport Through Ion Exchange Membranes, Fig. 2 Design methodology of selective liquid
membrane processes

the shore. The process should be designed to
(i) reduce the chromium concentration in the
polluted water below the disposal limit (0.5 mg
L
1) and (ii) obtain a concentrated chromium
solution (>20 g L
1) with negligible concentra-
tions of sulfate and chloride anions. The design
methodology is briefly illustrated in Fig. 2.
Synthetic solutions that simulate the anionic
composition of the real groundwater
6+
[Cr ] = 500–1,300 mg L
1,
[SO42
] = 900–3,000 mg L
1 and
[Cl
] = 300–1,000 mg L
1, were employed as
feed solutions. The pH of the feed solution was
adjusted to 1.5 using H2SO4. The organic solution
was formulated as follows: 10 % (v/v) of Alamine
336 as the anionic extractant, 3 % (v/v) of
Pluronic PE 3100 as surfactant, and Isopar
L fluid as solvent. The emulsion was prepared
by dispersing the stripping solution (NaOH
3–6 mol L
1) in the organic phase at a volume
ratio organic/stripping = 4/1.
After defining the separation system, the
experimental and theoretical description of the
extraction equilibria was performed following
the guidelines reported in Fig. 2. In general,
extraction systems involving ionic species are
generally thought to reach chemical equilibrium
at the interface, and thus equilibrium models of
the chemical reactions are proposed. Table 1
reported the extraction mechanism and the equi-
librium parameters for the multicomponent sys-
tem, Alamine 336/chromium/sulfate/chloride.
The emulsion pertraction technology (EPT)
which combines the advantages of ELM, i.e.,
high efficiency due to large surface area for
mass transfer, and SLM, i.e., extraction and strip-
ping are performed in one step without dispersion
of the organic phase into the aqueous feed phase,
was selected as the most suitable configuration of
the selective liquid membrane technology. More
details about the technology can be found else-
where (Bringas et al. 2006a; Bringas and Ortiz
2014). Kinetic experiments were performed in a
laboratory experimental setup containing a mem-
brane contactor Liqui-Cel ® Extra–Flow 2.5  8
with fiber X-30 that provides an effective mem-
brane area of 1.4 m2. Figure 3 shows the evolu-
tion with time of the chromium concentration in
4 Chromium Transport Through Ion Exchange Membranes

Chromium Transport Through Ion Exchange Membranes, Table 1 Extraction mechanism and equilibrium
parameters
Extraction reaction Equilibrium parameter
HCrO
þ
4 þ H þ R3 N , ðR3 NH ÞHCrO4
K1 = 4.83 mol
2 m6
þ
7 þ 2H þ 2R3 N , ðR3 NH Þ2 Cr 2 O7
Cr 2 O2
K2 = 0.741 mol
4 m12
HSO
þ
4 þ H þ R3 N , ðR3 NH ÞHSO4
K3 = 1.37 10
3 mol
2 m6
ðR3 NH ÞHSO4 þ Cl
, ðR3 NH ÞCl þ HSO

4
K4 = 1.52

2 100
Aqueous
[Cr+6](mol/m3) stripping
80 Phase
1,5 Aqueous
[Cr+6](mol/m3)

Inlet Phase Stripping

60
1 Outlet
40
0,5
20

0 0
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6
t (h)
Feed Organic Stripping

Chromium Transport Through Ion Exchange Membranes, Fig. 3 Qualitative and quantitative evolution of the
chromium concentration in the fluid phases (Feed solution: flows in continuous mode; Emulsion: recirculated)

the different fluid phases (feed, organic, and strip- reason the selectivity had to be controlled in the
ping) and a photograph of the fluid phases at the extraction step.
end of the experiment. Similar extraction and The kinetic analysis was completed with the
back-extraction results were reported for sulfate proposal of the multicomponent separation math-
and chloride anions (Bringas et al. 2006a). ematical model of the EPT process with the
The kinetic results confirmed the high selec- corresponding design parameters: (i) mass trans-
tivity of the carrier Alamine336 toward chro- port coefficients in the aqueous feed phase
mium species. The total chromium boundary layer (kL), in the membrane (km), and
concentration decreased from 500 mg L
1 at the in the organic phase stagnant layer (koAv) for the
module inlet to 0.8 mg L
1 at the module outlet in different species involved in the separation-
one pass when the residence time in the module is concentration process (see Fig. 4) and (ii) the
0.014 h. The chromium concentration in the strip- equilibrium parameters of the extraction reac-
ping phase reached an average value of 14.6 g tions reported in Table 1. The model described
L
1 after 1.3 h, and thus, a concentration factor of satisfactorily the kinetics and selectivity of the
18,733 was reached before depletion of the strip- separation-concentration EPT process under a
ping reagent. From the analysis of the results wide range of operational conditions and served
obtained for the competitive species, it was con- as a tool to perform the optimal design of the
cluded that the back-extraction process was not separation process (Bringas et al. 2006a).
selective because all the species were totally Finally, a novel design methodology based on
back-extracted from the organic phase. For this the application of mathematical optimization was
developed in order to determine the optimal EPT
Chromium Transport Through Ion Exchange Membranes 5

Chromium Transport Parameter Value Obtaining

Through Ion Exchange
Membranes, KL,Cr 0.217 . (Q1/3
2
)(m/h)
Fig. 4 Values of the mass
transport coefficients in the KL,Sulphate 0.234 . (Q1/3)(m/h)

Mass Transport Coefficients

EPT mathematical model Aqueous Phase Stagnant Layer
2

(kLi)
KL,Chloride 0.317 . (Q1/3
2
)(m/h) Calculated

KL,H+ 0.256 . (Q1/3

2
)(m/h)

Km,Cr 1.2 10−3 m/h

Membrane (kmi)
Km,Sulphate/ Chloride 1.5 10−3 m/h
Parametric
Organic Phase Stagnant Layer Estimation
.A
(ko)
Ko v 2.94 104h−1

1,41 m3/h 1,41 m3/h

7,7 mol/m3 2 0,041 mol/m3
A1=248 m

2,5 m3/h 3
2,5 m /h
2,5 m3/h 0,041 mol/m3 0,01 mol/m3
2
7,7mol/m3
A total = 591 m m3a A3=150 m2
S4a

3 3
1,09 m /h 1,09 m /h
3
7,7 mol/m3 2 0,041 mol/m
A2=193 m

a 3 a 3
Q = 2,5 m /h Q = 2,5 m /h
3 3
[Chromium(VI)] in = 7,7 mol/m [Chromium(VI)] out ≤ 0,01 mol/m

Chromium Transport Through Ion Exchange Membranes, Fig. 5 Optimal process configuration for the aqueous
feed solution

process configuration able to achieve, at mini- known flow rate of 2.5 m3 h
1 and a chromium
mum cost, the separation and concentration concentration of 400 mg L
1 (7.7 mol m
3).
objectives, (i) the contaminant removal up to the Comparison of the results obtained from the anal-
required concentration level ([Cr6+] <0.5 mg ysis of the different design alternatives concluded
L
1) and, (ii) the selective contaminant recovery that a network configuration with three treatment
to obtain a concentrated solution that can be modules combined in series and parallel and with
reused elsewhere ([Cr6+] 20 g L
1). The different a total membrane area of 591 m2 was the most
design alternatives were represented by means of suitable process configuration to comply, at min-
network superstructures that were modeled imum cost, with the concentration specifications
through the developed EPT mathematical in the outlet streams. Figures 5 and 6 show the
model, generating optimization problems that optimal networks for the aqueous feed solution
were solved following global optimization tech- and the emulsion phase, respectively.
niques (Bringas et al. 2007).
The procedure was illustrated for the treat-
ment of an incoming groundwater stream with a
6 Chromium Transport Through Ion Exchange Membranes

3
0,13 m /h
Co =0,002 mol/m3
3
Cg = 0,1 mol/m
2
A1 = 248 m
3 3
0,24 m /h 0,13 m /h
Co = 0,002 mol/m3 Co = 0,42 mol/m
3
3
Cg = 0,1 mol/m Cg = 400 mol/m
3
e
S4
0,11m3/h 0,24 m3/h
3
Co = 0,002 mol/m Co = 0,002 mol/m3
3
Cg = 0,1 mol/m Cg = 400 mol/m
3

m2e A2=193 m2 A3 = 150 m2

3 0,24 m3/h
0,24m /h 3
3 Co = 0,42 mol/m
Co = 0,24 mol/m
Cg = 396,9 mol/m3
Cg = 223,2 mol/m3
Atotal = 591m2 0,048 m3/h
Cg = 0,1 mol/m3

0,048 m3/h
Cg = 400 mol/m3

[Chromium(VI)]back-extration ≥ 380 mol/m3

Chromium Transport Through Ion Exchange Membranes, Fig. 6 Optimal process configuration for the emulsion
phase

Future Directions emulsion liquid membrane in a modified spray col-

Future development will require research and
development activities in the following areas:
1. Evaluation of the operation cost (energy and
material costs) to be considered in the formu-
lation of the objective function employed to
determine the optimal process network
2. Analysis of the long-term performance of the
separation process to evaluate the stability of
the selective carrier which guarantees the pro-
cess economic viability
3. Rigorous evaluation cost of the optimal pro-
cess network
References
Alguacil FJ, López-Delgado A, Alonso M, Sastre AM
(2004) The phosphine oxides Cyanex 921 and Cyanex
923 as carriers for facilitated transport of chromium
(VI)-chloride aqueous solutions. Chemosphere 57:813
Bhowal A, Bhattacharyya G, Inturu B, Datta S (2012)
Continuous removal of hexavalent chromium by
umn. Sep Purif Technol 99:69
Bohdziewicz J (2000) Removal of chromium ions (VI) from
underground water in the hybrid complexation-
ultrafiltration process. Desalination 129:227
Bringas E, Ortiz I (2014) Emulsion pertraction technology
for zinc recovery. In: Drioli E, Giorno L (eds) Ency-
clopedia of membranes. Springer-Verlag Berlin Hei-
delberg 2014. doi:10.1007/978-3-642-40872-4_646-1
Bringas E, San Román MF, Ortiz I (2006a) Separation and
recovery of Anionic pollutants by the emulsion
pertraction technology. Remediation of polluted
groundwaters with Cr(VI). Ind Eng Chem Res 45:4295
Bringas E, San Román MF, Ortiz I (2006b) Removal of
anionic pollutants from groundwaters using Alamine
336: chemical equilibrium modeling. J Chem Technol
Biotechnol 81:1829
Bringas E, Karuppiah R, San Román MF, Ortiz I,
Grossmann IE (2007) Optimal groundwater remedia-
tion network design using selective membranes. Ind
Eng Chem Res 46:5555
Bringas E, San Román MF, Urtiaga AM, Ortiz I (2012)
Membrane contactors (NDSX and EPT): an innovative
alternative for the treatment of effluents containing
metallic pollutants. Int J Environ Waste Manag 9:201
Hashim MA, Mukhopadhyaya S, Sahu JN, Sengupta
B (2011) Remediation technologies for heavy metal
contaminated groundwater. J Environ Manage 92:2355
IARC (1990) IARC monographs on the evaluation of the
carcinogenic risk of chemical in humans, Chromium,
Chromium Transport Through Ion Exchange Membranes
Nickel and Welding, Environmental and Experimental
Data. IARC, Lyon
Kentish SE, Stevens GW (2001) Innovations in separa-
tions technology for the recycling and re-use of liquid
waste streams. Chem Eng J 84:149
Kimbrough DE, Cohen Y, Winer AM, Creelman L,
Mabuni C (1999) A critical assessment of chromium
in the environment. Crit Rev Environ Sci Technol 29:1
Lin C (2002) The chemical transformations of chromium
in natural waters-A model study. Water Air Soil Pollut
139:137
Mohan D, Pittman CU (2006) Activated carbons and low
cost adsorbents for remediation of tri- and hexavalent
chromium from water. J Hazard Mater 137:762
7
Pagilla KR, Canter LW (1999) Laboratory studies on
remediation of chromium contaminated soils.
J Environ Eng 125:243
Rengeraj S, Yeon KH, Moon SH (2001) Removal of
chromium from water and wastewater by
ion-exchange resins. J Hazard Mater B87:273
Rivero MJ, Primo O, Ortiz MI (2004) Modellins of Cr
(VI) removal from polluted groundwaters by ion
exchange. J Chem Technol Biotechnol 79:822
Salazar E, Ortiz MI, Urtiaga AM (1992) Kinetics of the
separation of chromium(VI) with emulsion liquid
membranes. Ind Eng Chem Res 31:1523
Venkateswaran P, Palanivelu K (2005) Studies on recov-
ery of hexavalent chromium from plating wastewater
by supported liquid membrane using tri-n butyl phos-
phate as carrier. Hydrometallurgy 78:107
E
Emulsion Pertraction Technology
for Zinc Recovery
Immaculada Ortiz and Eugenio Bringas
Department of Chemical and Biomolecular
Engineering, University of Cantabria, Santander,
Cantabria, Spain
The emulsion pertraction technology (EPT) is a
separation process that combines the ability of
liquid membranes to promote the uphill transport
of target species by the coupling between mass
transfer and chemical reaction and the benefits of
using membrane contactors, namely, large inter-
facial area, nondispersive contact, and indepen-
dent flow of the fluid phases. Figure 1 shows the
flow diagram of the EPT process that comprises
two essential process units: a microporous hollow
fiber membrane contactor (see Fig. 2) and the
emulsion vessel that contains a pseudo-emulsion
consisting of the organic phase formulated with a
selective organic carrier and the dispersed strip-
ping solution. The target solute is chemically
transferred from the aqueous feed to the organic
phase that is embedded in the pores of the hollow
fibers due to their hydrophobic character. Next,
the solute-carrier complex diffuses to the inter-
face between the organic and the droplet of strip-
ping phase where the back-extraction reaction
occurs. The solute is recovered from the internal
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_648-5
aqueous phase after emulsion settling (San
Román et al. 2010; Urtiaga et al. 2010; Carrera
et al. 2009; Bringas et al. 2006; Urtiaga
et al. 2005; Klaassen and Jansen 2001). In the
forthcoming section, the potential of the EPT
technology to develop separation processes with
zinc recovery is evaluated.
Recovery of Zinc from Liquid Wastes by
EPT
Zinc’s electropositive nature makes it well-suited
for use as a coating for protecting iron and steel
products from corrosion. For this reason, the sur-
face treatment industry accounts for almost half
zinc modern-day demand. The processes
involved in the surface treatment of components
are predominantly water-based, and thus the gen-
eration and management of complex liquid
wastes is an issue of concern (Bringas
et al. 2012). EPT has been proven to be an effi-
cient technology to perform both the selective
removal and recovery of zinc from different
wastes produced in the context of surface treat-
ment industry: (i) spent pickling acids (SPA)
generated in the hot-dip galvanizing process
(see composition in Table 1) and (ii) spent
chromium-based passivation baths (SPB)
employed in zinc electroplating operations (see
composition in Table 1).
2 Emulsion Pertraction Technology for Zinc Recovery

Hollow Fiber Contactor — —

Feed Solution Rafinate AC ↔ A + C
Mass —
AC
transfer —
A C

Back-extraction

Extraction
— —
A + C ↔ AC
— Emulsion
Concentrate AC
Pore —
C
Emulsion Tank
Feed A
Solution Hollowfiber

Stripping Emulsion
droplet

Emulsion Pertraction Technology for Zinc Recovery, Fig. 1 Performance of the EPT process

Figures 3 and 4 depict the separation and
recovery objectives to be achieved by the appli-
cation of EPT to the treatment of SPA and SPB.
Under the usual composition of SPA, zinc
forms anionic chlorocomplexes (ZnCl42 and
ZnCl3 ) while iron is present in the form of
neutral or cationic compounds (Regel
et al. 2001). Tributyl phosphate (TBP) and
water are reported as the most suitable extraction
and back extraction reagents enabling the selec-
tive separation and concentration of zinc with
minimum iron extraction (Cierpezewski
et al. 2002). On the other hand, the information
provided by the equilibrium isotherms depicted
in Fig. 5 confirms the commercial selective car-
rier bis(2,4,4- trimethylpenthyl) phosphinic acid
(Cyanex272) as a suitable reagent to formulate
the liquid membrane due to its capacity to selec-
tively separate Fe3+ and Zn2+ (tramp ions) from
chromium under the typical pH conditions
(1.8–2.5) of the passivation baths. Sulphuric
acid is selected as stripping agent (Urtiaga
et al. 2010).
Figure 6 shows the kinetic results obtained
with the SPA-TBP-water and the EPT process.
It is concluded that the extraction (EX) and back-
extraction (BEX) percentages of zinc and iron,
when steady state conditions (regarding zinc
kinetics) are reached, are respectively, 79 %
(EX Zn), 98 % (BEX Zn), 23 % (EX Fe), and
38 % (BEX Fe). Under these operation condi-
tions, the maximum value of selectivity of zinc
over iron in the stripping solution is 15 kg of
Zn/kg of iron (Ortiz et al. 2004; Samaniego
et al. 2006; Samaniego et al. 2007; Carrera
et al. 2009; Bringas et al. 2012). On the other
hand, the efficiency of the EPT process to carry
out the regeneration of real passivation baths is
demonstrated in Fig. 7 which shows reductions in
the zinc and iron contents higher than 80 % after
3 h of experimental running with an almost neg-
ligible variation of the chromium concentration.
Furthermore, zinc is selectively recovered in the
stripping solution (concentration >35 kg/m3)
being the concentrations of iron (<0.45 kg/m3)
and chromium (<0.003 kg/m3) almost negligible
(Urtiaga et al. 2010; Bringas et al. 2011; Diban
et al. 2011; Bringas et al. 2012).
Therefore, these results confirm the EPT pro-
cess as a suitable alternative to perform the treat-
ment of spent pickling acids and spent
passivation baths allowing at the same time the
Emulsion Pertraction Technology for Zinc Recovery 3

Emulsion Pertraction
Technology for Zinc
Recovery,
Fig. 2 Characteristics of
hollow fiber contactors for
a bench scale EPT process

Parameter/Characteristic Value/Description

Fiber material Polypropylene

Shell material Polypropylene

Type of fiber X-50

Internal diameter of the

fiber 240 μm

Thickness 30 μm

Average pore diameter 0.04 μm

Porosity 40%

Effective lenght 0.15

Interfacial area 1.4 m2

Number of fibers 10200

Emulsion Pertraction Technology for Zinc Recovery, Table 1 Physical-chemical properties of spent pickling acids
(SPA) and spent chromium-based passivation baths (SPB)
SPA SPB
Parameter Value Parameter Value
pH 0 pH 1.8–2.5
Zn2+ (mg/L) 122,000 Zn2+ (mg/L) 2500–11,780
Fe2+ (mg/L) 100,000 Fe3+ (mg/L) 20–90
Cl (mg/l) 300,000 Cr3+ (mg/L) 4500–9350
Free acidity, H+ (mol/L) 1 NO3 (mg/L) 67,520

zinc recovery for further reuse as was illustrated Future Directions

by Figs. 3 and 4.
Future development will require research and
development activities in the following areas:
4 Emulsion Pertraction Technology for Zinc Recovery

FEED SOLUTION SEPARATION PROCESS SEPARATION AND RECOVERY OBJECTIVES

TBP Raffinate Coagulant (FeCl3)
(FeCl2, HCl)

Spent Pickling Acids Emulsion Pertraction

(Zn2+, HCL, Fe2+) Technology

Electrolytic
recovery of zinc
Stripping solution
Service (ZnCl2, HCl)
water Galvanizing
process

Emulsion Pertraction Technology for Zinc Recovery, Fig. 3 Treatment of spent pickling acids by EPT with zinc
recovery

FEED SOLUTION SEPARATION PROCESS/OBJECTIVES RECOVERY OBJECTIVES

Metallic pleces from zinc Regenerated passivation bath

electroplating: Incoming of (Cr3+)
Zn2+ and Fe3+

Spent Passivation Emulsion Pertraction

Bath Technology

Electrolytic
recovery of zinc
Stripping solution
(ZnSO4)
H2SO4 Cyanex272 Electroplating
process

Emulsion Pertraction Technology for Zinc Recovery, Fig. 4 Regeneration of chromium-based passivation baths by
EPT with zinc recovery

1. Determination of the optimal operational con- 2. Analysis of the long-term performance of the
ditions to: (i) maximize the extraction and separation process to evaluate the stability of
back-extraction kinetics and (ii) achieve max- the selective carrier which guarantees the pro-
imum values of selectivity which permit the cess’ economic viability.
exploitation of the different process streams
generated after the application of the EPT
process.
Emulsion Pertraction Technology for Zinc Recovery 5

Emulsion Pertraction
Technology for Zinc Selective separation
Recovery,
Fig. 5 Extraction 100
iron
isotherms of iron, zinc, and
chromium with Cyanex272
75

% Extraction
50

25
chromium

zinc
0
0 1 2 3 4 5 6 7
Equilibrium pH

Emulsion Pertraction Zn in SPA

Technology for Zinc 120
Recovery, Zn in stripping
Fig. 6 Evolution with time 100 Fe in SPA
of iron (discontinuous line) Fe in stripping
and zinc (continuous line)
CZn - CFe (g L-1)

concentration in the SPA 80

and stripping solution (0.5 L
of SPA with the 60
composition indicated in
Table 1; 1 L of organic
solution containing 50 % v/v 40
TBP in Shellsol D70; 1 L of
water) 20

0
0 30 60 90 120 150 180
t (min)
6 Emulsion Pertraction Technology for Zinc Recovery
Emulsion Pertraction
Technology for Zinc
Recovery,
Concentration (kg m−3)
Fig. 7 Extraction
percentages and
% Extraction
concentrations in the
stripping solution after 3 h
of EPT regeneration of SPB
using Cyanex272 as
selective extractant
References
Bringas E, San Román MF, Ortiz I (2006) Separation and
recovery of anionic pollutants by the emulsion
pertraction technology. Remediation of polluted
groundwaters with Cr(VI). Ind Eng Chem Res
45:4295–4303
Bringas E, Mediavilla R, Urtiaga A, Ortiz I (2011) Devel-
opment and validation of a dynamic model for regen-
eration of passivating baths using membrane
contactors. Comp Chem Eng 35:918–927
Bringas E, San Román MF, Urtiaga AM, Ortiz I (2012)
Integrated use of liquid membranes and membrane
contactors: enhancing the efficiency of L-L reactive
separations. Chem Eng Process. doi:10.1016/j.
cep.2012.11.005
Carrera JA, Bringas E, San Román MF, Ortiz I (2009)
Selective membrane alternative to the recovery of zinc
from hot-dip galvanizing effluents. J Membr Sci
326:672–680
Cierpezewski R, Miesiac I, Regel-Rosocka M, Sastre AM,
Szymanowski J (2002) Removal of zinc(II) from spent
hydrochloric acid solutions from zinc hot galvanizing
plants. Ind Eng Chem Res 41:598–603
Diban N, Mediavilla R, Urtiaga A, Ortiz I (2011) Zinc
recovery and waste sludge minimization from chro-
mium passivation baths. J Hazard Mater 192:801–807
100
% Extraction
80
Stripping composition
60
40
0.43 kg m−3
20 0.003 kg m−3
0
[Zn] [Fe] [Cr]
Klaassen R, Jansen AE (2001) The membrane contactor:
environmental applications and possibilities. Environ
Prog 20:37–43
Ortiz I, Bringas E, San Román MF, Urtiaga AM
(2004) Selective separation of zinc and iron from
spent pickling solutions by membrane-based solvent
extraction. Sep Sci Technol 39:2441–2455
Regel M, Sastre AM, Szymanowski J (2001) Recovery of
zinc(II) from HCl spent pickling solutions by solvent
extraction. Environ Sci Technol 35:630–635
Samaniego H, San Román MF, Ortiz I (2006) Modelling
of the extraction and back-extraction equilibria of zinc
from spent pickling solutions. Sep Sci Technol
41:757–769
Samaniego H, San Román MF, Ortiz I (2007) Kinetics of
zinc recovery from spent pickling effluents. Ind Eng
Chem Res 46:907–912
San Román MF, Bringas E, Ibáñez R, Ortiz I (2010)
Liquid membrane technology: fundamentals and
review of its applications. J Chem Technol Biotechnol
85:2–10
Urtiaga A, Abellán MJ, Irabien JA, Ortiz I (2005) Mem-
brane contactors for the recovery of metallic com-
pounds. Modelling of copper recovery from WPO
processes. J Membr Sci 257:161–170
Urtiaga A, Bringas E, Mediavilla R, Ortiz I (2010) The
role of liquid membranes in the selective separation
and recovery of zinc for the regeneration of Cr(III)
passivation baths. J Membr Sci 356:88–95
H
Heavy Metal Recovery by Membrane cheaper. At the same time, a clean permeate that
Operations meets the applicable effluent guidelines is
Jose Sabate
Department d’Enginyeria Agroalimentaria i
Biotecnologia, Universitat Politecnica de
Catalunya, Castelldefels, Spain
Several industries such as metal plating facilities,
mining operations, fertilizer industries, tanneries,
batteries, paper industries, pesticides, etc., pro-
duce heavy metal (Cd, Cr, Cu, Hg, Ni, Pb, Zn)
wastewaters. Heavy metals are not biodegradable
and persist in the environment: waters, soils, sed-
iments, etc. Further, their recovery could be
attractive from the economical perspective, and
several technologies have been studied and pro-
posed to carry it out: chemical precipitation, ion
exchange, adsorption, membrane filtration,
coagulation-flocculation, flotation, and electro-
chemical methods (Coman et al. 2013; Fu and
Wang 2011; Kurniawan et al. 2006). Membrane
separation technologies yield a high efficiency
and allow continuous operation. However, to pre-
vent membrane clog, a pretreatment of the pol-
luted effluent to achieve a clean feed is required.
Further, they need careful operation and periodic
washing to prevent membrane damages and
fouling.
Membrane separations can reduce the volume
of contaminated water, making the next pro-
cesses necessary to full recovery easier and
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_649-1
obtained. That can be achieved with high effi-
ciency using various membrane technologies:
ultrafiltration (UF), nanofiltration (NF), reverse
osmosis (RO), and electrodialysis (ED)
(Coman et al. 2013; Fu and Wang 2011;
Kurniawan et al. 2006).
UF membranes reject macromolecules, but
their pores are not small enough to retain heavy
metal ions such as Cd2+, Cu2+, Hg2+, Ni2+, Ni3+,
etc. Nevertheless, they can be concentrated with
the addition of a soluble polymer or surfactant
that binds the metal ions. Those processes are
named polymer-enhanced ultrafiltration (PEUF)
and surfactant-enhanced ultrafiltration (SEUF)
(Coman et al. 2013; Fu and Wang 2011;
Kurniawan et al. 2006). At low pH, metal ions
are released from the polymer and a new ultrafil-
tration operation allows one to separate them.
The polymer can be regenerated by alkali addi-
tion and reused.
RO is used to remove almost everything from
the water which includes small molecules and
ions. It can produce drinking water from brackish
water or seawater. Therefore, it has been shown
to concentrate heavy metal ions such Cd2+, Cu2+,
and Ni2+. However, compared to other membrane
technologies, RO requires the highest pressure
and energy cost.
Nanofiltration (NF) is the intermediate process
between UF and RO (Soldenhoff et al. 2005). NF
membranes usually have an electrical charge,
2 Heavy Metal Recovery by Membrane Operations
positive for pH values lower than the membrane
isoelectric point (IEP) and negative for higher pH
values. NF yields high rejections of heavy metal
ions, although NF membrane pores are larger than
heavy metal ions in solution. That is due to the
contribution to the separation process of several
mechanisms: steric (sieving), electric (Donan),
and dielectric (born and image forces). Dielectric
and Donan effects strongly favor the rejection of
polyvalent ions. That makes NF very suitable for
heavy metal concentration, which can be done in
one step and at lower pressure and energy cost
than RO.
Electrodialysis (ED) is another membrane
process for the separation of ions that uses an
electric field as the driving force. It is an alterna-
tive to RO for the production of drinking water. It
has been demonstrated to be able to concentrate
hexavalent and trivalent chromium and Cd2+, Cu2+,
Co2+, Ni2+, and Fe3+.
Membrane technologies can contribute to the
heavy metal recovery from contaminated under-
ground water, soils, sediments, sludge,
etc. However, a previous extraction of metals is
needed, which can be achieved with acids, che-
lating agents, dendrimers, or surfactants.
Cross-References
▶ Electrodialysis
▶ Heavy Metals Recovery by Chelating Agents
and Membranes
▶ Heavy Metals Recovery by Polymer Enhanced
Ultrafiltration
▶ Nanofiltration
▶ Reverse Osmosis
▶ Ultrafiltration
References
Coman V, Robotin B, Ilea P (2013) Nickel recovery/
removal from industrial wastes: a review. Resour
Conserv Recycl 73:229–238
Fu F, Wang Q (2011) Removal of heavy metal ions from
wastewaters: a review. J Environ Manage 92:
407–418
Kurniawan TA, Chan GYS, Lo WH, Babel S (2006) Phys-
ico–chemical treatment techniques for wastewater
laden with heavy metals. Chem Eng J 118:83–98
Soldenhoff K, McCulloch J, Manis A, Macintosh P (2005)
Nanofiltration in metal and acid recovery. In: Fane
AG, Schafer AI, Waite TD (eds) Nanofiltration: prin-
ciples and applications. Elsevier, Amsterdam,
pp 459–477
H
Heavy Metal Recovery by Polymer-
Enhanced UF
Jose Sabate
Department d’Enginyeria Agroalimentaria i
Biotecnologia, Universitat Politecnica de
Catalunya, Castelldefels, Spain
Polymer-enhanced ultrafiltration (PEUF) is one
of the membrane operations that can be used to
separate or concentrate heavy metal from liquid
streams. It is also called polymer-assisted ultra-
filtration (PAF), complexation-ultrafiltration pro-
cess (CUFP), or polymer-supported ultrafiltration
(PSU) (Rivas et al. 2009).
Ultrafiltration membranes reject macromole-
cules, but their pores are not small enough to
retain heavy metal ions such as Cd2+, Cu2+, Ni2+,
Ni3+, Hg2+, etc. Nevertheless, if a soluble polymer
able of binding polyvalent cations is added to a
solution containing heavy metal ions (F), the
resulting metal-polymer complex will be retained
by UF membranes. Then, a clean permeate
(P) can be obtained and the heavy metals will
be concentrated in the retentate stream (R).
See figure 1.
The polymers contain functional groups such
as amine, carboxylated, phosphonic, or sulfonate
which link to metals either through ionic or che-
lating bonds. The most used synthetic polymers
are polyacrylic acid (PAA) and polyethy-
leneimine (PEI) (Rivas et al. 2009). The use of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_650-1
natural polymers (chitosan, humic acids, etc.) and
polymers anchored on the membrane represents
growing alternatives.
A suitable polymer should have a high affinity
for target ions and should be able to be recycled in
order to make the process economically feasible.
It should be biodegradable to prevent new envi-
ronmental problems, but it cannot have a very
short half-life in working conditions. As commer-
cial or natural polymers have a molecular weight
distribution, they must previously undergo a
diafiltration process to remove short chains,
which would bind heavy metals but would leak
through the UF membrane. Further, its interac-
tions with membrane materials should be consid-
ered to minimize fouling.
Modeling PEUF has usually been carried out
through the classic complexation (or exchange
ions) equilibrium reactions. For instance, the
union between a heavy metal ion, Mm+, and a
neutral ligand group of the polymer, L, can be
represented by the following chemical equilibri-
ums and their respective constants:
Mmþ þ nL ⇆ MLn mþ bn (1)
For n=1, 2, 3. . .
The protonation of the L group is described
by:
2 Heavy Metal Recovery by Polymer-Enhanced UF

Heavy Metal Recovery

by Polymer-Enhanced
UF, Fig. 1 Scheme of
PEUF. (F: feed, R: polymer
retentate, P: permeate).
F R

polluted P
water

Mm+

LHþ ⇆ L þ Hþ Ka (2) Micellar-enhanced ultrafiltration (MEUF) is a

High values of bn indicate a strong affinity
between polymer and target ion. Generally, the
basic forms of ligands (R-COO, R-NH2, etc.)
bind the metal ions, but the acid forms (R-COOH,
R-NH3+, etc.) do not do it. This fact can be used
for polymer recycling. When an acid is added to
the metal-polymer complex solution, metal ions
are shifted by protons from the ligand sites.
A second ultrafiltration operation yields to a per-
meate containing free heavy metal ions and a
retentate with polymer. The polymer can be
regenerated by the alkali addition and therefore
reused. The global process requires the consump-
tion of an acid and an alkali, and it is a concen-
tration operation as the permeate in acid medium
contains most of the heavy metal from the initial
contaminated water, but in a smaller volume.
Nanofiltration and reverse osmosis mem-
branes are able to retain and therefore concentrate
heavy metal ions without the need of chemical
addition. Nevertheless, they require higher pres-
sures and energy consumption than
UF. Selectivity is an additional advantage of
PEUF as bn values are particular for any metal-
polymer pair.
similar process to PEUF. Instead of a polymer, a
surfactant solution over the critical micellar con-
centration is used. Micelles bound to metal ions
and are large enough to be rejected by UF mem-
branes (Mungray et al. 2012).
Cross-References
▶ Heavy Metal Recovery by Membrane
Operations
▶ Heavy Metals Recovery by Chelating Agents
and Membranes
▶ Nanofiltration
▶ Reverse Osmosis
▶ Ultrafiltration
References
Mungray AA, Kulkarni SV, Mungray AK (2012) Removal
of heavy metals from wastewater using micellar
enhanced ultrafiltration technique: a review. Cent Eur
J Chem 10:27–46
Rivas BL, Pereira E, Maureira A (2009) Functional water-
soluble polymers: polymer–metal ion removal and
biocide properties. Polym Int 58:1093–1114
Z

Zinc Recovery by Supported Liquid Recovery of zinc by supported liquid mem-

Membrane branes has been done at a laboratory scale. It may
be carried out by using organic extractants com-
Carlos Moreno mercially available, mostly phosphoric acid
Department of Analytical Chemistry, Faculty of derivatives such as bis(2,4,4-trimethylpentyl)
Marine and Environmental Sciences, University monothiophosphinic acid Fig. 1, bis
of Cádiz, Puerto Real, Spain (2-ethylhexyl) hydrogen phosphate, or bis(2,4,4-
trimethylpentyl) phosphinic acid.

Zinc is an essential element for life, being indis-

pensable for humans, animals, and plants. It is Cross-References
also extensively used by humankind in many
industrial applications (electrical or automotive ▶ Cobalt Removal and Recovery by Supported
industries, surface treatments, etc.), both directly Liquid Membranes
and as oxides, sulfides, or in alloys such as brass.

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_651-1
2 Zinc Recovery by Supported Liquid Membrane

H3C CH3 CH3 S CH3 H C

3 CH3

P
H3C CH3
OH

Zinc Recovery by Supported Liquid Membrane,

Fig. 1 Chemical structure of bis(2,4,4-trimehylpentyl)
monothiophosphonic acid
D
Deionization by Membrane
Operations
Maarten Biesheuvel
Wetsus, European Centre of Excellence for
Sustainable Water Technology, Leeuwarden,
Netherlands
Deionization, or desalination, is the process in
which salt ions are removed from a polar liquid,
which is virtually always water. Water deioniza-
tion and water desalination are generally consid-
ered as synonyms, though deionization can be
applied in a more restricted sense to denote
those processes where during water treatment
cations move in the one direction and anions in
the other direction.
Of course, during deionization, the total
removal rate of anions (times their charge num-
ber) must equal the total removal rate of cations
(time charge), to keep the produced effluent water
electroneutral (conserve electroneutrality). The
condition of electroneutrality will hold both for
the produced freshwater and for the produced
concentrate, the brine.
To make ions go in different directions, deion-
ization processes in the limited sense as defined
above make use of electrical field effects, i.e., by
applying an external current to a water flow cell
or system, ions in the water are induced to move
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_654-3
in the electric field, with cations moving to posi-
tions of lower electrical potential (i.e., in the
direction of the field strength), while anions
move in the opposite direction.
The most well-known membrane process for
deionization is electrodialysis and the various
modifications thereof, including electrodeio-
nization, a process in which ion-exchange resin
particles fill the water flow channels in between
the ion-exchange membranes and electrodialysis
reversal, a modification of electrodialysis in
which the applied electrical current is temporar-
ily reversed during short periods of time to abate
biofouling and scaling on the membranes (Sonin
and Probstein 1968; Strathmann 2010;
Nikonenko et al. 2010; Andersen et al. 2012).
A novel deionization technology making use of
membranes is membrane capacitive deionization in
which ion-exchange membranes are placed in front
of porous electrodes (either in the form of freestand-
ing membranes or as a coating on the electrode) to
capacitively remove salt from water in a cyclic pro-
cess, i.e., ions are temporarily stored in the electrodes
in one phase of the cycle and are released again
during the phase where a brine is produced (Lee
et al. 2006; Li and Zou 2011; Biesheuvel
et al. 2011; Nie et al. 2011; Zhao et al. 2012).
2 Deionization by Membrane Operations
Cross-References
▶ Membrane Capacitive Deionization
References
Andersen MB et al (2012) Current-induced membrane
discharge. Phys Rev Lett 109:108301
Biesheuvel PM, Zhao R, Porada S, van der Wal A (2011)
Theory of membrane capacitive deionization includ-
ing the effect of the electrode pore space. J Colloid
Interface Sci 360:239–248
Lee J-B, Park K-K, Eum H-M, Lee C-W (2006) Desalina-
tion of a thermal power plant wastewater by membrane
capacitive deionization. Desalination 196:125–134
Li HB, Zou L (2011) Ion-exchange membrane capacitive
deionization: a new strategy for brackish water desali-
nation. Desalination 275:62–66
Nie CY, Zhan YK, Pan LK, Li HB, Sun Z (2011)
Electrosorption of different cations and anions with
membrane capacitive deionization based on carbon
nanotube/nanofiber electrodes and ion-exchange
membranes. Desalination Water Treat 30:266–271
Nikonenko VV et al (2010) Intensive current transfer in
membrane systems: modelling, mechanisms and appli-
cation in electrodialysis. Adv Colloid Interface Sci
160:101–123
Sonin AA, Probstein RF (1968) A hydrodynamic theory of
desalination by electrodialysis. Desalination
5:293–329
Strathmann H (2010) Electrodialysis, a mature technology
with a multitude of new applications. Desalination
264:268–288
Zhao R, Biesheuvel PM, Van der Wal A (2012) Energy
consumption and constant current operation in mem-
brane capacitive deionization. Energy Environ Sci
5:9520–9527
D
Diffusion in Membranes
Boguslaw Kruczek
Department of Chemical & Biological
Engineering, University of Ottawa, Ottawa, ON,
Canada
Introduction
Diffusion is the net movement of a substance
(atom, ion, or molecule) from a region of high
concentration to a region of low concentration. In
the case of membranes, diffusion along with pore
flow is the main transport mechanism. Diffusion
dominates in dense and microporous membranes
whereas pore flow in meso- and macroporous
membranes. Consequently, membrane processes
such as gas separation (GS), pervaporation (PV),
and reverse osmosis (RO) are governed by diffu-
sion, or more precisely the solution-diffusion
mechanism, whereas ultrafiltration (UF) and
microfiltration (MF) by the pore flow mechanism.
Diffusion in Dense Membranes
Polymeric membranes have generally a dense
structure with no visible pores (they are also
referred to as nonporous membranes). Molecules
permeate through transient free volume elements
between polymer chains. A molecule entrapped
in a cavity between the polymer chains bounces
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_657-1
around the cavity walls and eventually jumps to
an adjacent cavity once transient opening for the
molecule passage appears. Molecular dynamic
simulations, which allow calculations of the fluc-
tuations in the volume between polymer chains
due to thermal motion, have been used to visual-
ize diffusion of gases in polymers (Baker 2012).
Figure 1 shows motion of a carbon dioxide mol-
ecule in a 6FDA-4PDA polymer matrix. The
molecule bounces around the cavity in the first
100 ps and it does not move more than 5 Å, which
is indicative of the cavity size. Then, thermal
motion moves a segment of the polymer chain
allowing the molecule to jump to an adjacent
cavity, where it remains until another movement
of the polymer chain allows it to jump to another
cavity (Baker 2012). The diffusion coefficient
(D) in polymer membranes is therefore defined
(Koros and Fleming 1993):
f l2d
D¼ (1)
6
where f is the average jump frequency and ld is
the average jump length. The smaller the mole-
cule the more frequent jumps between the cavi-
ties. However, in addition to the size, the shape of
the molecule is also very important. For example,
carbon dioxide is known to be much more diffu-
sive in polymer membranes than methane even
though carbon dioxide has a slightly greater
molar volume than methane. On the other hand,
methane is a spherical molecule with a kinetic
2 Diffusion in Membranes

Diffusion in Membranes,
Fig. 1 Motion of a carbon
dioxide molecule in a
6FDA-4PDA polymer
Cavity
matrix (Reprinted from size
Smit et al. (1992).
Copyright Elsevier
(permission pending))

Jump length λ
25
From Smit et al. (1992)
Jump
20

Movement in cavity
Position (Å)

15 Movement in cavity

10
Jump length

5 Cavity size

0
0 20 40 60 80 100 120 140 160 180 200
Simulation time (picoseconds)

diameter of 3.72 Å, while the molecule of carbon
dioxide is an oblate ellipsoid 5.25 Å long, but
with the diameter of only 3.03 Å. Consequently,
as carbon dioxide molecule bounces around in a
cavity it occasionally becomes oriented in such a
way that it can jump through a gap between the
polymer chains as small as 3.03 Å. Such a small
gap would not permit jumping of the methane
molecule (Baker 2012).
As temperature increases, the thermal motions
of polymer chains allowing the molecule to jump
from one cavity to the other become more fre-
quent, and also the molecule bounces faster with
a cavity, which means that once a transient open-
ing of appropriate size becomes available, it will
more likely jump into the adjacent cavity. Exper-
imentally observed dependence of D in poly-
meric membranes on temperature follows the
Arrhenius relationship (Burggraaf 1996):
 
DEa
D ¼ D exp
RT
where DEa is the activation energy for diffusion,
D* is a preexponential factor often related to as
the entropy of activation and the average jump
length, and R and T are the universal gas constant
and the absolute temperature, respectively. Dif-
fusion process in which D follows Eq. 2 is
referred to as an activated diffusion. The activa-
tion energy for diffusion in polymeric mem-
branes is positive; thus, the greater the DEa the
smaller the D; also it indicates that D increases
with T, which is consistent with molecular
dynamics simulations. In turn, DEa is directly
proportional to a cohesive energy density
(CED), which is indicative of strength of attrac-
tive forces between adjacent polymer chains. The
CED increases when polar and hydrogen bond
groups are present in polymer chains (Koros and
Fleming 1993).
(2) Diffusion in Microporous Membranes
Microporous membranes have permanent path-
ways (pores) for transport of molecules. They are
Diffusion in Membranes 3

Diffusion in Membranes, Activated diffusion constriction energy barrier

Fig. 2 Diffusion
mechanisms in ΔEa
microporous membranes
(Reprinted from Thornton
et al. 2010. Copyright John
Wiley & Sons. (permission adsorption-site energy barrier
Surface diffusion
pending))
ΔEs

Kundsen diffusion Direction and velocity

generally made from inorganic materials such as
zeolites, carbonized polymers, and amorphous
silica; however, organic membranes made from
polymers with intrinsic microporosity (PIM),
such as polytrimethylsilylpropyne (PTMSP), are
also considered as microporous (Baker 2012).
The three most common diffusion mecha-
nisms in microporous membranes, shown in
Fig. 2, include activated diffusion (small pores),
surface diffusion (intermediate pores), and Knud-
sen diffusion (large pores). The exact pore size
ranges for a given diffusion mechanism are deter-
mined based on the difference (W) between the
potential energy outside the pore (Eout) and the
potential energy within the pore (Ein) (Thornton
et al. 2010).
As a molecule approaches a pore opening,
each atom in the gas molecule interacts with
every atom from the pore wall through van der
Waals forces. The potential difference is also
referred to as a suction energy; because a positive
W translates to a force sucking the molecule from
outside to inside of the pore (adsorption), while a
negative W results in a force repulsing the mole-
cule from the pore. The activated transport takes
place when W < 0, and the activation energy for
diffusion in Eq. 2 corresponds to DEa ¼ jW j
(Thornton et al. 2010).
Figure 3 presents an example of the potential
energy difference as function of pore size (d) for a
single oxygen molecule entering a cylindrical
carbon pore from outside environment, in which
Eout = 0. The pore diameter corresponding to
W = 0 is referred to as a minimum pore size
(dmin), while the pore diameter corresponding to
W = RT represents Knudsen diameter (dK). Acti-
vated diffusion occurs when d < dmin, surface
diffusion dominates when dmin < d < dK, while
Knudsen diffusion dominates when d > dK.
Table 1 summarizes dmin and dK for different
gases in carbon and silica pores with two different
pore geometries.
Activated Diffusion Versus Surface
Diffusion
When transport is dominated by activated diffu-
sion, there is no adsorption and membrane per-
meability (P) is solely governed by the diffusion
coefficient, i.e.:
   
 DEa  jW j
P ¼ P exp ¼ P exp (3)
RT RT
where DEa is the activation energy for diffusion,
which is identical to DEa in Eq. 2, which is equal
to the absolute value of the potential difference.
On the other hand, when transport is dominated
by surface diffusion, membrane permeability (Ps)
is governed by both the diffusion coefficient (Ds)
and the solubility coefficient (Ss). The latter is a
4 Diffusion in Membranes

Diffusion in Membranes, 0.6

Fig. 3 Potential energy Activated Surface Knudsen
difference for a single 0.5 diffusion diffusion diffusion
oxygen molecule at the
entrance of a carbon 0.4
cylindrical pore (Reprinted
from Thornton et al. 2010. 0.3
Copyright John Wiley &

W (eV)
Sons. (permission 0.2
pending))
0.1

0
dmin dK
−0.1

−0.2
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Pore size(Å)

Diffusion in Membranes, Table 1 Minimum pore size for the activated transport (dmin) and minimum pore size for
Knudsen diffusion (dK) at room temperature (298 K). All pore sizes are given as the PAS pore sizea (Adapted from
Thornton et al. 2010)
Pore geometry
Cylindrical pore Slit-shaped pore
Carbon Silica Carbon Silica
Gas dmin (Å) dK (Å) dmin (Å) dK (Å) dmin (Å) dK (Å) dmin (Å) dK (Å)
He 2.30 5.69 2.53 6.37 1.86 2.19 2.06 4.35
H2 2.57 8.82 2.79 9.79 2.10 6.52 2.31 7.22
CO2 2.95 12.30 3.17 13.35 2.46 9.27 2.65 10.12
O2 3.10 11.68 3.31 12.68 2.59 8.76 2.79 9.58
N2 3.27 11.49 3.48 14.46 2.75 8.60 2.94 9.39
CH4 3.49 13.74 3.69 14.84 2.95 10.43 3.13 11.32
CO 3.32 12.14 3.52 13.16 2.79 9.14 2.98 10.00
Ar 3.18 11.68 3.39 12.67 2.66 8.76 2.86 9.56
n-C5H12 5.27 23.51 5.45 25.04 4.59 18.33 4.75 19.57
C2H6 4.02 16.69 4.21 17.93 3.44 12.82 3.62 13.86
SF6 4.66 19.46 4.85 20.81 4.03 15.05 4.20 16.15
a
Positron annihilation spectroscopy (PAS) diameter d0 = d – dd, where dd is the electron cloud thickness surrounding
the surface atoms (dd = 3.32 Å)

q
thermodynamic factor that correlates the concen- Ss ¼ K o exp (4)
tration of molecules in the adsorbed phase to the RT
external pressure, which typically follow a Lang-
muir isotherm. At the same time, Ss follows where q (>0) is a heat of adsorption, which implies
Arrhenius relation: that Ss decreases with temperature. Surface diffu-
sion is an activated process, which depends on q:
Diffusion in Membranes
aq
Ds ¼ Ds exp (5)
RT
where a is a proportionality constant (0 < a <1).
The product aq is the activation energy for sur-
face diffusion, which represents the energy bar-
rier separating two adjacent sorption sites
(Thornton et al. 2010). Since Ps = DsSs, combin-
ing Eqs. 4 and 5 leads to:
 
ð1  aÞq
Ps ¼ Ps exp (6)
RT
The term, (1 – a)q is positive; therefore, Ps,
unlike P, decreases with temperature. In the
case of dense polymeric membranes, the perme-
ability coefficient is also a product of the diffu-
sivity and the solubility coefficients, and the
latter, similarly to the surface diffusion solubility
coefficient, decreases with temperature. On the
other hand, the corresponding increase in diffu-
sivity overcompensates a decrease in solubility.
Thus, the permeability coefficient in dense poly-
meric membranes follows Arrhenius-type rela-
tionship similar to the permeability coefficient
5
for activated diffusion in microporous
membranes.
The third diffusion mechanism, Knudsen dif-
fusion, is not an activated process. Although
Knudsen diffusion coefficient increases with
temperature, it does not follow Arrhenius-type
relationship (Thornton et al. 2010).
References
Baker RW (2012) Membrane technology and applica-
tions. Wiley, West Sussex
Burggraaf AJ (1996) Transport and separation properties
of membranes with gases and vapours. In: Burggraaf
AJ, Cot L (eds) Fundamentals of inorganic membrane
science and technology. Elsevier Science, Amsterdam,
pp 331–433
Koros WJ, Fleming GK (1993) Membrane-based gas sep-
aration. J Membr Sci 83:1–80
Smit E, Mulder MHV, Smolders CA, Karrenbeld H, van
Eerden J, Feil D (1992) Modeling of the diffusion of
carbon dioxide in polyimide matrices by computer
simulation. J Membr Sci 73:247–257
Thornton AW, Hill JM, Hill AJ (2010) Modelling gas
separation in porous membranes. In: Yuri
Yampolskii Y, Freeman B (eds) Membrane gas sepa-
ration. Wiley, Hoboken, pp 85–109
D
Dual Mode Sorption Model
Donald R. Paul
Department of Chemical Engineering, Texas
Materials Institute, Austin, TX, USA
The dual mode sorption model is a convenient
and commonly used equation for describing gas
sorption in polymers at temperatures below the
glass transition temperature, Tg, of the polymer.
Gas sorption in glassy polymers generally
(a) exhibits nonlinear isotherms that are concave
to the pressure axis, unlike the linear ones seen
above Tg, (b) shows greater levels than for rub-
bery polymers with the extent being larger the
higher is the Tg, and (c) depends on the prior
history of the sample and the details of the mea-
surement protocol (Horn and Paul 2012). The first
two aspects are well illustrated in Fig. 1 that
shows the concentration of carbon dioxide, C,
dissolved in five different polymers as a function
of the pressure, p, in the external carbon dioxide
gas phase. Butyl rubber shows a linear isotherm,
while all four of the glassy polymers show fea-
tures (a) and (b) mentioned above at this mea-
surement temperature, i.e., T = 35
C. The
extent of carbon dioxide sorbed into these glassy
materials increases the higher is the Tg; i.e.,
their glass transition temperatures descend in
the following order: 310
C for the polyimide
Matrimid 210
C for poly(phenylene oxide)
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_662-3
(PPO) 186
C for polysulfone (PSF) 100
C for
polystyrene.
The dual mode sorption model consists of the
sum of Henry’s law term and a Langmuir term,
i.e.,
C0H bp
C ¼ kD p þ (1)
1 þ bp
where kD is Henry’s law coefficient, CH0 is the
Langmuir capacity term, and b is an affinity
parameter. It appears that Barrer et al. (1958)
were the first to propose this now well-known
equation. Equation 1 provides a very good fit of
data like that in Fig. 1 where the CH0 obtained by
the fitting would increase as the polymer Tg
increases relative to the measurement
temperature T, i.e., C0H  Tg  T, and is thought
to be related to the unrelaxed volume of the glass;
see Paul (2010) for a recent summary of the
extensive literature in this area. The CH0 term
would be zero for butyl rubber, i.e., Eq. 1 reduces
to Henry’s law, since it is not in the glassy state.
Petropoulos (1970) proposed that the Lang-
muir population may have a finite, but different,
mobility than Henry’s law population. Paul and
Koros (1976) extended this analysis to give
expressions for the time lag and the following
expression for the permeability coefficient, P,
for gases in glassy polymers:
2 Dual Mode Sorption Model

70 diffusion coefficient for the Langmuir population

CO2 at 35°C, Bulk Polymers and p2 is the upstream pressure of the permeating
60 gas. This has become known as the dual mobility
model. It predicts that the permeability decreases
50 slightly as the upstream pressure increases and
Matrimid
C [cm3(STP)/cm3]

PPO this is what is commonly observed experimen-

40
tally in simple cases where the polymer is not
PSF
plasticized significantly by the permeating gas.
30

20 Polystyrene
References
10
Butyl Rubber Barrer RM, Barrie JA, Slater J (1958) Sorption and diffu-
0 sion in ethyl cellulose. III. Comparison between ethyl
0 5 10 15 20 25 cellulose and rubber. J Polym Sci 27:177–197
CO2 Pressure (atm) Horn NR, Paul DR (2012) Carbon dioxide sorption and
plasticization of thin glassy polymer films tracked by
optical methods. Macromolecules 45:2820–2834
Dual Mode Sorption Model, Fig. 1 Sorption isotherms
Paul DR (2010) Fundamentals of transport phenomena in
for CO2 in various polymers at 35
C (Reprinted with
polymer membranes. In: Drioli E, Giorno L (eds)
permission from Horn and Paul 2012. Copyright 2012
Comprehensive membrane science and engineering,
American Chemical Society)
vol 1. Academic, Oxford, pp 75–90
Paul DR, Koros WJ (1976) Effect of partially
C0H bDH immobilizing sorption on permeability and the diffu-
P ¼ kD DD þ (2) sion time lag. J Polym Sci Polym Phys Ed 14:675–685
1 þ bp2 Petropoulos JH (1970) Quantitative analysis of gaseous
diffusion in glassy polymers. J Polym Sci Part
where DD is the diffusion coefficient associated A-2(8):1797–1801
with Henry’s law population and DH is the
D
Dynamic Optimization of Membrane set of differential Eq. (2) represents dynamical
Operation system. This is usually the model of the process
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Dynamic optimization is usually referred to
open-loop optimal control. It encompasses sev-
eral methods whose purpose is to determine tra-
jectories of dynamic (time-dependent) variables
in optimal manner. These methods may be used
to find optimal control of processes or to design
optimal experiments for parameter estimation.
The generalized representation of dynamic opti-
mization problem (DOP) is as follows
ð tf


 
min G x tf , tf þ F ðxðtÞ, u ðtÞ, tÞdt
u ðtÞ t0
:
s:t: x ðtÞ ¼ fðxðtÞ, u ðtÞ, tÞ


h xðt0 Þ, t0 , xðt0 Þ, tf ¼ 0
g ðxðtÞ, u ðtÞ, tÞ  0
where t is time, u(t) denotes vector of control
variables, u(t) is vector of state variables, and G
(∙) and F(∙) stand, respectively, for nonintegral
and integral part of optimization objective. The
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_664-5
whose optimal control one searches for. Sets of
functions h(∙) and g(∙) may express various types
of equality/inequality constraints which are
imposed by the physical reality.
In order to find solution to DOP, one can
exploit various techniques, stochastic (such as
genetic algorithms, simulated annealing, etc.) or
deterministic ones. Deterministic methods are
based on the following three principles: varia-
tional calculus (developed by Euler and
Lagrange), dynamic programming (Bellman
1957), and Pontryagin’s maximum/minimum
principle (Pontryagin et al. 1962). The latest one
gave rise to most popular numerical techniques
such as control vector parameterization, control
vector iteration, boundary condition iteration,
orthogonal collocation, and multiple shooting
techniques.
(1)
Various dynamic optimization problems were
solved already in literature on membrane pro-
(2) cesses. These applications include optimization
of membrane reactors performance (Parvasi
et al. 2009; Rahimpour and Elekaei Behjati
(3)
2009), other membrane-assisted processes
(4) (Kuhn et al. 2009; Bui et al. 2010), membrane
separation (Fikar et al. 2010; Paulen et al. 2011)
as well as membrane fouling and cleaning (Van
Boxtel and Otten 1993; Blankert et al. 2006;
Zondervan and Roffel 2008).
2 Dynamic Optimization of Membrane Operation
References
Bellman R (1957) Dynamic programming. Princeton
University Press, Princeton, United States
Blankert B, Betlem BHL, Roffel B (2006) Dynamic
optimization of a dead-end filtration trajectory:
blocking filtration laws. J Membr Sci
285(1–2):90–95. doi:10.1016/j.memsci.2006.07.044,
ISSN 0376-7388
Bui VA, Vu LTT, Nguyen MH (2010) Simulation and
optimisation of direct contact membrane distillation
for energy efficiency. Desalination 259(1–3):29–37.
doi:10.1016/j.desal.2010.04.041, ISSN 0011-9164
Fikar M, Kovács Z, Czermak P (2010) Dynamic optimiza-
tion of batch diafiltration processes. J Membr Sci
355(1–2):168–174. doi:10.1016/j.memsci.2010.03.019
Kuhn J, Lakerveld R, Kramer HJM, Grievink J, Jansens PJ
(2009) Characterization and dynamic optimization of
membrane-assisted crystallization of adipic acid. Ind
Eng Chem Res 48(11):5360–5369. doi:10.1021/
ie802010z
Parvasi P, Khosravanipour Mostafazadeh A, Rahimpour
MR (2009) Dynamic modeling and optimization of a
novel methanol synthesis loop with hydrogen-
permselective membrane reactor. Int J Hydrog Energy
34(9):3717–3733. doi:10.1016/j.
ijhydene.2009.02.062, ISSN 0360-3199
Paulen R, Foley G, Fikar M, Kovács, Czermak P (2011)
Minimizing the process time for ultrafiltration/
diafiltration under gel polarization conditions.
J Membr Sci 380(1–2):148–154. doi:10.1016/j.
memsci.2011.06.044, ISSN 0376-7388
Pontryagin LS, Boltyanskii VG, Gamkrelidze RV,
Mishchenko EF (1962) The mathematical theory of
optimal processes. Wiley, New York
Rahimpour MR, Elekaei Behjati H (2009) Dynamic opti-
mization of membrane dual-type methanol reactor in
the presence of catalyst deactivation using genetic
algorithm. Fuel Proc Technol 90(2):279–291.
doi:10.1016/j.fuproc.2008.09.008, ISSN 0378-3820
Van Boxtel AJB, Otten ZEH (1993) New strategies for
economic optimal membrane fouling control based on
dynamic optimization. Desalination 90(1–3):363–377.
doi:10.1016/0011-9164(93)80187-R, ISSN 0011-
9164
Zondervan E, Roffel B (2008) Dynamic optimization
of chemical cleaning in dead-end ultra filtration.
J Membr Sci 307(2):309–313. doi:10.1016/j.
memsci.2007.09.067, ISSN 0376-7388
D

Dynamic-Volume Diafiltration The process of dynamic-volume diafiltration

poses a dynamic optimization problem (Fikar
Zoltán Kovács et al. 2010). The goal of optimization is to find
Department of Food Engineering, Institue of the optimal time-dependent function of a that
Bioengineering and Process Engineering, Szent drives the process from its initial state to a pre-
Istvan University, Budapest, Hungary scribed terminal state. Optimality is defined as the
minimization of the objective function J without
violating given constraints. The mathematical
Dynamic-volume diafiltration is a type of batch problem can be formulated as follows:
diafiltration process that is designed to achieve the
twin aims of simultaneous macrosolute concen- min J s:t:
tration and microsolute removal by employing aðtÞ
: c1 q
optimal time-varying control of diluant feeding. c1 ¼ ðR1  aÞ, c1 ð0Þ ¼ c1, 0,
The technological goal in a general batch pro- V
: c2 q
cess is to increase the macrosolute concentration c1 ðtf Þ ¼ c1, f , c2 ¼ ðR2  aÞ,
V
from c1,0 to c1,f and to reduce the microsolute
c2 ð0Þ ¼ c2, 0, c2 ðtf Þ ¼ c2, f ,
concentration from c2,0 to c2,f. The fractionation :
is accomplished by introducing a diluant into the V ¼ ða  1Þq, V ð 0Þ ¼ V 0 ,
feed reservoir. Choosing the right strategy of a  ½0, amax 
scheduling the addition of diluant is a critical
aspect to consider in batch processing (Lutz where c1, c2, and V represent the actual
1997). Processes can be characterized upon their macrosolute concentration, microsolute concen-
a-strategies (a is the ratio of diluant flow rate to tration, and volume in the feed tank, respectively.
permeate flow rate). Frequently used batch It is assumed that the system is well mixed and the
diafiltration techniques, such as traditional diluant is solute-free. R1 and R2 denote the rejec-
diafiltration, variable-volume diafiltration, tion of macrosolute and microsolute, respectively.
pre-concentration followed by variable-volume It should be mentioned that, in a general case, the
diafiltration, intermittent feed diafiltration, and actual value of both q and R depends on the
sequential dilution diafiltration, employ arbitrarily concentrations of macrosolute as well as on
predefined schemes of diluant addition. In con- microsolute. Moreover, process parameters (e.g.,
trast, dynamic-volume diafiltration is designed by pressure, temperature, hydrodynamic conditions,
the evaluation of the optimal time-varying profile etc.) also affect q and R.
of diluant flow for the entire course of operation.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_665-3
2 Dynamic-Volume Diafiltration

In practice, several objective functions can be nanofiltration, and microfiltration systems

considered for optimization, for instance,time (Paulen et al. 2012). In general, optimal a control
minimization: need not to be any of the conventional diafiltration
concepts, and thus, it might need advanced con-
J A ¼ tf trol systems. In many cases, however, it might be
attractive to implement the optimal trajectory
diluant minimization: since it can lead to reduced operation time, diluant
consumption, and product losses. The computed
ð tf
optimal profile may vary case by case depending
JB ¼ aðtÞqðtÞ dt on the complexity of the membrane response
0
model, the initial and final values, and the con-
or minimization of complex economic index: straints involved in the model.

ð tf
JC ¼ k1 tf þ k2 c1 ½1  R1 ðtÞ qðtÞ dt
ð tf 0
þ k3 aðtÞqðtÞ dt
0 Fikar M, Kovács Z, Czermak P (2010) Dynamic optimiza-
where total cost is a sum of three terms that are the
operational cost of the pump, cost of the valuable
component loss, and the cost of the utilized dilu-
tion water. k1, k2, and k3, are the respective cost
factors.
This technique can be useful to evaluate opti-
mal operation of membrane filtration plants
including reverse osmosis, ultrafiltration,
References
tion of batch diafiltration processes. J Membr Sci
355(1–2):168–174. doi:10.1016/j.
memsci.2010.03.019
Lutz H (1997) Membrane filtration with optimized addi-
tion of second liquid to maximize flux, United States
Patent 5,597,486. Assignee: Millipore Investment
Holdings Limited, Wilmington
Paulen R, Fikar M, Foley G, Kovács Z, Czermak P (2012)
Optimal feeding strategy of diafiltration buffer in batch
membrane processes. J Membr Sci 411–412:160–172
E
Ease of Expansion in Gas Separation
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende (CS), Italy
Quite often during the operation of a system for
the treatment of gases, it is necessary to expand it
for treating greater streams. In some cases, future
expansion is contemplated even during the initial
phase of a project. In other cases, it could be a
necessity not foreseen during system design
phase (Miller and Stöcker 1989; Brunetti
et al. 2010).
Membrane system expansion is very easy,
since this only requires the addition of identical
modules. This is the advantage offered by the
modularity of membrane units and the reduced
equipment and control systems required for oper-
ating it. In comparison, considering the other
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_666-1
reference technologies for gas separation, PSA
and absorption systems can also be expanded,
but it requires additional design considerations
and adds cost in the initial phase of the project.
The cryogenic units cannot be expanded if it is
not foreseen during the design phase. Generally
they can be over-dimensioned, and a capacity
increase is often obtained without modification
to the cold box itself through addition of a tail gas
compressor.
References
Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
brane engineering progresses and potentialities in gas
separations. In: Yampolskii Y, Freeman B (eds) Mem-
brane gas separation. Wiley, New York, pp 281–312
Miller GQ, Stöcker J (1989) Selection of a hydrogen
separation process NPRA annual meeting, 19–21
Mar, San Francisco
E
Electrical Double Layer
Karel Bouzek and Tomas Bystron
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technicka 5,
Prague 6, Czech Republic
An electrical double layer is usually considered
to form at the phase interface between two elec-
trically conducting media. In such a case, on one
side of the interface, an excess of positive charge
exists, which is counterbalanced by an identical
excess of negative charge localized on the oppo-
site side of the interface. The overall system
charge is thus equal to zero. In membrane sci-
ence, this definition has, to a certain degree, been
modified, the reason being that membranes can
be produced from a broad spectrum of materials,
including (i) electronic conductors (e.g., metals),
(ii) ionic conductors (e.g., O2 -conducting
ceramics), (iii) functionalized polymers provi-
ding ionic conductivity through the liquid filling
the void volume of the material (ion-selective
membranes), and (iv) nonfunctionalized poly-
meric or ceramic membranes.
Whereas, in the first two cases, the traditional
definition is valid, in the last two, the situation is
different. This is due to the fact that the bulk
membrane material is neither an electronic nor
an ionic conductor. Hence the double layer only
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_669-1
forms on one side of the phase interface. The
Fig. 1 provides a schematic sketch of the two
mentioned cases. In the case of functionalized
materials, the charge-carrying groups covalently
bound to the polymeric backbone are oriented
towards the void volume of the membrane inte-
rior, thus forming an electrically charged film
covering the phase interface on the side of the
solution. The charge of this film is compensated
by that of the mobile ions present in the solution
and located close to the film (see Fig. 1a).
In the case of the non-functionalized mate-
rials, the surface charge fixed to the surface of
the solid phase is formed by specific adsorption of
ions of one sign. Both the sign of the adsorbed
ions and the extent of the adsorption are deter-
mined by the properties of the membrane mate-
rial. In this case, too, the fixed charge is
compensated by the charge of ions moving in
the system and located close to the absorbed
surface film (see Fig. 1b).
An electrical double layer significantly influ-
ences the properties of the membrane, mainly
with respect to its transport properties and behav-
ior under current load. In selected cases the sur-
face of the membrane materials is modified to
achieve the preferred adsorption and thus the
required transport and properties, including
selectivity.
2 Electrical Double Layer

Electrical Double Layer, Fig. 1 Schematic sketch of

structure of the Electrical Double Layer for (a)
functionalized and (b) nonfunctionaalized membrane
materials
E
Electrical Interactions in Membranes and inorganic nature. These carriers interact with
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology, Prague, Technická 5,
Prague 6, Czech Republic
In general electrical (electrostatic) interactions
arise as a result of the interaction of electrically
charged particles (charge carriers) with sur-
rounding matter (electrically charged and neu-
tral) (Stuart 1989). In the case of membranes,
probably the most important interactions to con-
sider are those between electrically charged
bodies, such as ions dissolved in solution and
ion-conducting, functionalized, or even inert
membranes. In living systems the electrostatic
interactions between the charged/polar and neu-
tral/nonpolar side of a solute molecules with
each other and with a solvent are responsible
for the formation/assembly of monolayer and
bilayer biological membranes and their
functioning.
On the fluid side the charge carriers are typi-
cally mobile ions or colloidal particles of organic
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_670-1
the charge carriers fixed in the material of the
membrane (see also the electrical double layer).
The charge fixed in the membrane material is, in
principle, of dual origin: (i) it comes from the
component introduced and incorporated during
its synthesis, and (ii) it is the result of the specific
adsorption of ions on the surface of the solid
phase. Electrostatic interactions between fixed
and freely moving charge carriers are responsible
not only for several phenomena characteristic of
membrane separation processes, such as the exis-
tence of Donnan potential, the selectivity of mass
transport, or mass transport enhancement under
current load by electroosmotic flux, but also for
the existence of life itself. These facts document
the importance of electrical interactions in mem-
brane materials with respect to their transport
properties.
References
Stuart McLaughlin (1989) The Electrostatic Properties of
Membranes. Annu. Rev. Biophys. Biophys. Chem.
18:113–136
E
Electrical Potential
Karel Bouzek and Tomas Bystron
Faculty of Chemical Technology, University of
Chemistry and Technology, Prague, Technická 5,
Prague 6, Czech Republic
Electric potential is a scalar physical quantity
determined by the electric energy (or work in
general) necessary to transfer a unit positive elec-
tric charge from infinity to the point of interest in
a studied system. The point in infinity is formally
chosen as a reference state characterized by zero
electric potential. From this more or less abstract
and intuitive definition of the reference state, it is
apparent that the absolute value of electric poten-
tial is not available experimentally. However, it is
possible to measure electric potential difference,
known as voltage.
We can distinguish between outer (external)
and inner (internal) electric potential. In the case
of outer electric potential, the charge is
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_671-1
transferred to the closest proximity of the exter-
nal surface of the phase P. However, the distance
from this surface has to be large enough to avoid
the appearance of molecular and image forces. At
the same time it should not cause any weakening
of the electric interaction with the charge located
on the internal side of the phase interface. The
inner electric potential is determined by the
strength of the electric field in the interior of the
phase P. It thus represents the work necessary to
transport the charge from infinity to the phase P.
The difference between the inner electric poten-
tial and the outer electric potential corresponds to
the surface potential of phase P (Arthur and Alice
1997).
References
Arthur W. Adamson, Alice P. Gast (1997) Elecrical
Aspects of Surface Chemistry, in Physical Chemistry
of Surfaces, 6th edn. John Wiley & Sons, Inc.
ISBN:0-471-14873-3)
E
Electrical Work in Membranes
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technická 5,
Prague 6, Czech Republic
An electrical work is defined as the work
connected with the charge carrier transport
between two points in an electric field, i.e., from
point of potential ’1 to point of potential ’2.
Thus, electrical work in membranes is the pro-
duct of the transported electrical charge and the
difference in electric potentials between which it
has passed (Arthur and Alice 1997). Since the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_673-1
resistivity of the membrane can be approximated
by ohmic resistivity, the electrical work dissi-
pated in the membrane is equal to the ohmic
potential loss in the membrane multiplied by the
current load. Expressed alternatively, it is equal
to the square of the current load multiplied by the
ohmic resistivity.
References
Arthur W. Adamson, Alice P. Gast (1997) Elecrical
Aspects of Surface Chemistry, in Physical Chemistry
of Surfaces, 6th edn. John Wiley & Sons, Inc. ISBN:
0-471-14873-3
E
Electrically Enhanced Processes by
Membrane Operations
Karel Bouzek
University of Chemistry and Technology Prague,
Prague 6, Czech Republic
Electrically membrane operations are typically
limited to systems involving electrically charged
particles. In such a case, the application of an
electric field can often significantly enhance the
ongoing process. In selected cases, it is the appli-
cation of an external electric field that makes the
desired processes possible at all. By applying an
electric field, electrically charged particles are
dragged in the direction determined by the polar-
ity of their charge and the vector of the electric
field. This movement is responsible for electric
current flow through the system. Part of the
electric charge carried by one type of particles
corresponds to what is known as the transference
number of the given particle. It is proportional to
the particle mobility in the system and the electric
charge it carries [1].
In the case of membrane operations enhanced
by an electric field, generally functionalized
ion-selective membranes are considered. Electro-
dialysis and dialysis are typical representatives of
an electrically enhanced and a nonenhanced pro-
cess, respectively. Electrodialysis is used to desa-
linate a treated stream containing dissolved ions
by transporting them, due to the action of the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_674-1
electric field, against the concentration gradient
to the concentrate stream [2]. In the case of dial-
ysis the situation is the reverse, since the
dissolved species move in the direction of the
concentration gradient away from the treated
stream to the solution free of the removed com-
ponents flowing along the opposite side of the
membrane. It is thus clear that electrodialysis is
typically a significantly more intensive process in
terms of the desalination rate. At the same time, it
produces a significantly lower volume of the
stream carrying the removed components. The
electric field thus enhances the intensity of the
mass flux during membrane processes involving
charged species and makes it possible to transport
the charged species against the concentration
gradient. On the other hand, dialysis is not limited
to charged particles.
Electrically enhanced membrane operations
can also be carried out with nonfunctionalized
membrane materials or with membrane materials
carrying no fixed electric charge, electrofiltration
being an example. Here, the applied electric field
influences the membrane operation indirectly by
preventing blockage of the membrane surface.
This is ensured by the electrophoretic transport
of the charged colloidal particles concentrated in
the solution away from the surface of the filtering
membrane, see also Electrofiltration.
It is, therefore, evident that the application of
an external electrical field can significantly
enhance or modify processes, including mem-
brane operations.
2 Electrically Enhanced Processes by Membrane Operations

References Applications, Desalination, Trends and Technologies,

Colin A (1976) Vincent: The Motion of Ions in Solution
under the Influence of an Electric Field. J. Chem.
Educ, vol. 53, pg. 490
Fernando Valero, Angel Barceló and Ramońn Arboás
(2011). Electrodialysis Technology - Theory and
Michael Schorr (Ed.), ISBN: 978-953-307-311-8,
InTech, DOI: 10.5772/14297. Available from: http://
www.intechopen.com/books/desalination-trends-and-
technologies/electrodialysis-technology-theory-and-
applications
E
Electrodialysis
Heiner Strathmann
Institute for Chemical Technology, Stuttgart
University, Stuttgart, Germany
The principle of electrodialysis is illustrated in
Fig. 1 which shows a series of alternating anion-
and cation-exchange membranes arranged
between two electrodes. The membranes are sep-
arated by a spacer gasket and form individual
cells, through which an electrolyte solution is
pumped. When an electrical potential difference
between the electrodes is established, the cations
migrate toward the cathode. They pass through
the cation-exchange membrane, but they are
retained by the anion-exchange membrane. Like-
wise the anions migrate toward the anode and
pass through the anion-exchange membrane but
are retained by the cation-exchange membrane.
The overall result is that an electrolyte is concen-
trated in alternate compartments, while its ion
content is depleted in the other compartments.
In an industrial size electrodialysis stack,
100–400 cell pairs are arranged between the elec-
trodes. Various spacer and stack constructions
such as the so-called sheet flow are used in prac-
tical applications (Schaffer and Mintz 1966).
The concept of a sheet flow stack is illustrated
in Fig. 2 which shows the arrangement of the
spacers and membranes in a stack. The spacers
not only separate the membranes and provide the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_677-1
proper mixing of the solutions in the cells, but in
their frames, they also contain the manifolds for
the two different flow streams in the stack.
Practical problems which affect the efficiency
of electrodialysis are concentration polarization
and membrane fouling. Concentration polariza-
tion which determines the so-called limiting cur-
rent density is controlled by hydrodynamic
parameters of the feed flow in the stack. Mem-
brane fouling is controlled by a technique which
is referred to as “clean in place” or electrodialysis
reversal (Katz 1979).
The total costs in electrodialysis are the sum of
the plant capital and the plant operating costs.
The capital related costs are proportional to the
required membrane area for a given capacity
plant and a for a given feed and product concen-
tration. The operating costs are proportional to
the required desalination energy which is the
function of the transferred ions, i.e., the concen-
tration difference between the feed and product
ion concentration. The energy EV required to
desalinate 1 m3 of water by electrodialysis is
given by
Fr A
CP i


EV ¼ Cf  Cp
x
Here rACP is the area resistance of the cell pair,
which can be estimated from measurements of
membrane resistance and conductivities of solu-
tions, F is the Faraday constant, i is the current
2 Electrodialysis

Electrodialysis, Concentrate
Fig. 1 Schematic diagram
illustrating the principle of Diluate
electrodialysis A C A C C
+ – + – + – +
– + – +
– + – –
+ – + – –
Anode + + Cathode
+ + – – + + – – – –
– – –
+ +
+ –
+
+ – – –
+ – + – –
+ + – + – – + + – + – – + – –
+ – + – –
Electrode + – + – – Electrode
rinse + – + – – rinse
Feed

Repeating unit

Ion-exchange
Electrode membrane
cell

Concentrate
Diluate

Electrode
rinse solution

Feed solution

Feed solution

Electrode Diluate cell

Spacer Concentrate cell

Electrodialysis, Fig. 2 Schematic drawing illustrating the construction of a sheet flow stack design

density, Cf and Cp are the feed and product water
concentrations, and x is an efficient term which is
generally close to 1.
Electrodialysis has advantages and limitations
compared to other deionization processes such as
reverse osmosis. A main advantage of electrodi-
alysis compared to reverse osmosis is that very
little feed pretreatment is required and higher
brine concentrations can be achieved.
A major disadvantage especially for the pro-
duction of potable water is the fact that only ions
are removed, while uncharged components such
as microorganisms or organic contaminants will
not be eliminated. Another disadvantage of
electrodialysis is the relatively high energy con-
sumption when solutions with high salt concen-
trations have to be processed. Thus,
electrodialysis can only be cost-effectively
applied in water desalination in a certain range
of feed water salt concentration and required
product water (Strathmann 2010).
References
Katz WE (1979) The electrodialysis reversal process.
Desalination 28:31–40
Electrodialysis 3

Schaffer LH, Mintz MS (1966) Electrodialysis. In: Strathmann H (2010) Electrodialysis, a mature technology
Spiegler KS (ed) Principles of desalination. Academic, with a multitude of new applications. Desalination
New York, pp 3–20 264:268–288
E
Electromembrane Processes
Gérald Pourcelly
Institut Européen des Membranes, CC 047,
Université Montpellier II, Montpellier, France
Electromembrane processes involve
ion-exchange membranes. They can be divided
into three types: (i) Separation of components
such as salts or acids and bases from electrolyte
solutions. In this case, the driving force for the
ion transport across the membrane is an electrical
potential as in electrodialysis or a concentration
gradient as in both diffusion dialysis and Donnan
dialysis. (ii) The second type of processes
involves an electrochemical reaction producing
chemicals such as chlorine, acids and bases, or
organic and inorganic compounds. The most
known process of this type is the chlorine-alkali
production where the ion-exchange membrane is
the key component. (iii) The third type of
ion-exchange membrane processes involves the
conversion of chemical into electrical energy and
vice versa. The solid polymer electrolyte fuel cell
is the most significant application (Strathmann
2004).
(i): In dialysis, the driving force for the com-
ponent transport is a difference of concentration
between the two solutions separated by a mem-
brane. In diffusion dialysis and Donnan dialysis
the driving force is also a concentration gradient
but the membrane is carrying anions or cations
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_679-1
according to its permselectivity. Diffusion dialy-
sis with anion exchange membranes is used on a
large scale to recover acids from pickling solu-
tions (Kobuchi et al. 1987). Donnan dialysis is
used for water softening or for recovering organic
acids from their salts (Kliber and Wisnieskwi
2011).
Electrodialysis (ED) is used to transport salt
ions from one solution through ion-exchange
membranes to another solution under the influ-
ence of an applied electric potential difference.
The elementary cell consists of a feed (diluate)
compartment and a concentrate (brine) compart-
ment formed by an anion exchange membrane
and a cation exchange membrane placed between
two electrodes. In almost all practical ED pro-
cesses, multiple ED cells (few hundreds) are
arranged into a configuration called an ED stack
Fig. 1.
Conventional ED is used mainly for desalina-
tion of saline solutions (chemicals) or milk whey
(food industry). It can be combined with bipolar
membranes (bipolar membrane electrodialysis)
and used to produce acids and bases from their
corresponding salts, Fig. 2. This process is eco-
nomically very attractive and has several inter-
esting potential applications mainly in food
industry, fine chemicals, or biotechnologies
(Pourcelly et al. 2009).
(ii): The most known membrane electrolysis
processes are for the production of chlorine and
caustic soda (Pletcher and Walsh 1990) or special
organic compounds (Sata 1991). In the chlorine-
2 Electromembrane Processes

CONCENTRATE (OUTLET)

DILUATE (OUTLET)

ELECTROLYTE

Na+ Na
+
Na
+
Na
+ +
Na Na
+

+ + + + +
Na Na Na Na Na
ANODE CATHODE

Cr Cr Cr Cr Cr

Cr Cr Cr Cr Cr Cr
D C D C D C D C D C D

DILUATE (INLET)

CONCENTRATE (INLET)

Electromembrane Processes, Fig. 1 Scheme of a conventional two-compartment electrodialysis stack (C): concen-
trate, (D): diluate compartments

Electromembrane Processes, Fig. 2 Electrodialysis with bipolar membrane. Scheme of a three-compartmentcell

alkali process, the cells are arranged in a similar
way as in an electrodialysis stack but in two
different configurations using monopolar or bipo-
lar electrodes. Due to the severe operating condi-
tions (80  C, 35 wt% NaOH, wet chlorine), the
membrane is a composite structure of sulfonated
and carboxylated perfluorinated reinforced
polymers.
(iii): Ion-exchange membranes are used today
also as key components in energy storage and
Electromembrane Processes
conversion systems such as batteries and fuel
cells. A fuel cell is an electrochemical reactor in
which energy is converted into electrical energy.
Generally fuel cells are fed with hydrogen which
is transformed into protons at a catalytic anode
with electrons. Protons then migrate across a
proton conducting membrane and combine with
oxygen to produce water at the catalytic cathode
(Lucia 2014).
References
Kliber S, Wisnieskwi JA (2011) Removal of bromate and
associated anions from water by Donnan dialysis with
3
anion exchange membranes. Desalin Water Treat
35:158–163
Kobuchi Y, Motomura H, Noma Y, Hanada F (1987)
Application of ion exchange membranes to recover
acids by diffusion dialysis. J Membr Sci 27:173–179
Lucia U (2014) Overview on fuel cells. Renew Sustain
Energy Rev 30:164–169
Pletcher D, Walsh FC (1990) Industrial electrochemistry.
Chapman & Hall, London
Pourcelly G, Bazinet L (2009) Developments of BPM
technology in food and bio-industries. In: Pabby AK,
Rizvi SSH, Sastre AM (eds) Handbook of membrane
separations. CRC Press, Boca Raton, pp 581–634
Sata T (1991) Ion exchange membranes and separation
processes with chemical reactions. J Appl Electrochem
21:283–294
Strathmann H (2004) In: Ion exchange membrane separa-
tion processes. Membrane technologies series.
Elsevier, Amsterdam
E
Electroosmosis
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technicka 5,
Czech Republic
Electroosmosis is the term used for the convec-
tive flow of a solution containing charge carriers,
e.g., in the form of dissociated salts, through the
pores or structure of a material with an electri-
cally charged internal surface. In the field of
membrane processes, this phenomenon is typi-
cally discussed in connection with the utilization
of ion-selective membranes under current load.
However, it can potentially occur in any mem-
brane material. The schematic sketch of the prin-
ciple of electroosmotic flux initiation in an
ion-selective membrane pore (void space) is
shown in Figure 1.
The driving force of electroosmotic flux is the
electric field. Flux velocity is directly propor-
tional to the hydraulic permeability of a mem-
brane and indirectly proportional to the viscosity
of the pore fluid. The latter parameter represents
an excess of free charge carriers of one sign in the
bulk of the pore fluid. An excess of one-sign
charge carriers is possible on account of an intrin-
sic property of an ion-selective membrane, i.e.,
the presence of charge-carrying functional
groups in the membrane structure. These ion
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_681-1
groups are bonded by a covalent bond to the
backbone of the membrane material. They are
thus fixed and immobilized in the structure. In
the case of conventional membrane materials, the
role of fixed charge can be carried out by ions
specifically adsorbed on the pore walls or along
the backbone of membrane materials. The charge
carried by functional groups and/or adsorbed in
the internal structure of the membrane has to be
compensated by an excess charge of opposite
sign present in the pore fluid. The electroosmotic
convective flow of the pore fluid is induced by
friction force between the solvated mobile charge
carriers (ions) moving under the action of the
electric field and the surrounding liquid phase
molecules (Squires and Bazant 2004).
Electroosmotic flux represents one of the
mechanisms of mass transfer through an
ion-selective membrane. Its significance
increases with increasing current load and, thus,
the intensity of the electric field applied across
the membrane (Fila and Bouzek 2008).
References
Fila V, Bouzek K (2008) The effect of convection in the
external diffusion layer on the results of a mathemat-
ical model of multiple ion transport across an ion-
selective membrane. J Appl Electrochem. 38:1241
Squires TM, Bazant MZ (2004) Induced-charge electro-
osmosis. J Fluid Mech 509:217
2 Electroosmosis

Electroosmosis, Fig. 1 The schematic sketch of a prin-

ciple of electroosmotic flux initiation in the membrane
with an electric charge carriers fixed on the pore (void
fraction) wall
F

Faujasite clear solutions at low temperatures (70–300  C,

Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
FAU (faujasite) belongs to the family of alumino-
silicate
usually 100  C) and pressure (autogenous) under
alkaline conditions. Starting typically from
sodium aluminate and sodium silicate, the zeolite
is obtained in its Na+ form (Blatter and
Schumacher 1991). Replacement of the Na+ cat-
ions by protons (leading to the H-zeolite form) is
required for applications in acid catalysis. In addi-

molecular sieves defined

by the formula tion, for specific catalytic applications, incorpora-
ðCa, Mg, Na2 Þ ðH2 OÞ ½Al58 Si134 O384  FAU
29 240
(www.iza-online.org). Two types of synthetic
FAU zeolites referenced as Linde X and Linde
Y differ in Si/Al atomic ratio, which is typically
in the range from 1 to 1.5. one to two for the X and
higher for the Y zeolite. The 24-tetrahedra
cuboctahedral units (sodalite cages) in the FAU
framework type are connected via hexagonal
prisms (double six-rings) forming a three-
dimensional porous channel structure along
[110]. These are characterized by 12-oxygen ring
window openings with the aperture of 8 Å and
supercages of approximately 12 Å (McCusker and
Baerlocher 2001). The FAU-type zeolite
supercage viewed along [111] is shown in Fig. 1
(International Zeolite Association (IZA)).
The combination of large void volume and
large pore openings in a three-dimensional chan-
nel system makes FAU thermally stable molecular
sieve ideal for many catalytic, ion-exchange, and
adsorption applications. FAU zeolites are gener-
ally synthesized by hydrothermal crystallization
of reactive alkali metal aluminosilicate gels or
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_689-1
tion of various metal cations into the structure is
carried out by impregnation or ion exchange and
results in modification of the number and nature of
acid sites influencing the diffusion of reactants
and products. X-type zeolite has a wide range of
industrial applications for gas or vapor adsorption,
separation, and as catalyst (isomerization of
1-butene, alkylation of toluene with ethylene or
methanol, cycloaddition of carbon dioxide to
ethylene oxide (Ribeiro et al. 1984)). However,
in many large-scale industrial applications, its
chemical analogue with Si/Al ratio higher than
1.5 (zeolite Y) has superseded zeolite X because
of its higher chemical and thermal stability. USY
(ultra-stable Y zeolite prepared by dealumination
of zeolite Y) is one of the most widely employed
zeolitic materials in the petrochemical industry,
essentially as a fluid cracking catalyst (FCC) of
heavy petroleum distillates, for increasing the
yield of gasoline and diesel fuel from crude oil.
Considering membrane applications, the produc-
tion of tubular FAU zeolite membranes has been
mainly considered for alcohol dehydration by
vapor permeation (Sato et al. 2008).
2 Faujasite

References

Blatter F, Schumacher E (1991) The preparation of pure

zeolite NaY and its conversion to high-silica faujasite,
an experiment for laboratory courses in inorganic
chemistry. J Chem Educ 68:519–521
International Zeolite Association (IZA). http://www.iza-
online.org. Accessed July 2013
McCusker LB, Baerlocher C (2001) Zeolite structures. In:
van Bekkum H, Flanigen EM, Jacobs PA, Jansen JC
(eds) Introduction to zeolite science and practice,
vol 137, Studies in Surface Science and Catalysis.
Elsevier, London, pp 37–67
Ribeiro FR et al (1984) Zeolites: science and technology.
Martinus Nijhoff Publishers, The Hague
Sato K, Sugimoto K, Nakane T (2008) Mass-production of
tubular NaY zeolite membranes for industrial purpose
and their application to ethanol dehydration by vapor
permeation. J Membr Sci 319:244–255

Faujasite, Fig. 1 The FAU-type zeolite supercage – view

along [111] direction (International Zeolite Association
(IZA))
A
Affinity Separation
and Crystallization of Fc Fragments
Nilay Bereli, Handan Yavuz and Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Immunoglobulins are used by the immune system
present in serum and tissue fluids to identify and
neutralize foreign targets. Immunoglobulins are
“Y”-shaped molecules comprised of two identi-
cal light chains (L) and two identical heavy
chains (H) linked via disulfide covalent forces
and via non-covalent interactions. Each chain
has constant (CL and CH) and variable (VL and
VH) domains (Holt et al. 2003). These form two
antigen-binding fragments (Fab) that specifically
recognize and bind to antigen molecule and a
constant fragment (Fc) which is responsible for
the effector function and biodistribution of the
antibody (Beale 1987). Proteolytic digestion pro-
vides important information to determine an anti-
body molecule’s structure and function.
Antibody molecules can be cleaved into frag-
ments and each of these fragments has a distinct
activity. A number of enzymes like papain, pep-
sin, ficin, bromelain, and elastase can be used for
this purpose, papain being the most frequently
used (Luo et al. 2002). Because of their smaller
size as functional components of the whole mol-
ecule, antibody fragments offer several advan-
tages over intact antibodies for use in certain
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_690-1
immunochemical techniques and experimental
applications. For this purpose, researchers have
attempted to use smaller, more stable counter-
parts of antibodies and have also been searching
for alternative ways to obtain antibody-like
receptors (Haupt et al. 1998). Thus,
bioengineered antibody fragments that are
smaller than antibodies and have the ability to
bind antigen bivalently have been promoted by
the researchers (Cortese 1995). IgG molecule can
be digested with papain for gaining Fab and Fc
fragments.
For the separation of Fab and Fc fragments,
HiTrap_r Protein A column can be used and
collected the fragments by the fraction unit of
the fast protein liquid chromatography (FPLC)
system (Ert€urk et al. 2011; Bereli et al. 2013;
Aslıy€uce et al. 2013). As shown in Fig. 1, a
successful separation was observed and Fab and
Fc fragments were separately collected. The
retention times of the fragments were achieved
at 3.06 and 11.64 min, respectively. The calcu-
lated chromatographic parameters such as tR, N,
k0 , a, and Rs values are summarized and given in
Table 1. Rs value was calculated as 4.70 for Fc
fragment. Because the Rs value should be higher
than 1.0 for a good resolution of two peaks in
such a chromatography system, the results for the
resolution of Fab fragment/Fc fragment can be
accepted as good resolution values.
2 Affinity Separation and Crystallization of Fc Fragments

Affinity Separation
and Crystallization of Fc 450
Fragments, Fig. 1 FPLC
chromatogram of IgG after Fab
digestion with papain 350

Absorbance (m/U)
(Ert€urk et al. 2011)
250

Fc
150

50

–50
0 5 10 15 20 25
Time (min)

Affinity Separation and Crystallization of Fc Fragments, Table 1 Chromatographic separation data

Fragment tR N K’ a Rs
Fab 3.06 52.39 1.19 6.14 -
Fc 11.16 1089.60 7.31 - 4.70

References
Aslıy€uce S, Uzun L, Say R, Denizli A (2013) Immuno-
globulin G recognition with Fab fragments imprinted
monolithic cryogels: evaluation of the effects of metal-
ion assisted-coordination of template molecule. React
Funct Polym 73:813–820
Beale D (1987) Molecular fragmentations. Some applica-
tions in immunology. Dev Comp Immunol
11:287–296
Bereli N, Ert€urk G, Tumer MA, Say R, Denizli A (2013)
Oriented immobilized anti-hIgG via Fc fragment-
imprinted PHEMA cryogel for IgG purification.
Biomed Chromatogr 27:599–607
Cortese R (1995) Identification of biologically active pep-
tides using random libraries displayed on phage. Curr
Opin Biotechnol 6:73–80
Ert€
urk G, Bereli N, Uzun L, Tumer MA (2011) Affinity
separation and characterization of IgG subfragments
by fast protein liquid chromatography with HiTrap_r
Protein A column. Hacet J Biol Chem 39:133–138
Haupt K, Mosbach K (1998) Plastic antibodies:
developments and applications. Tibtech November
16, 468–475.
Holt LJ, Herring C, Jespers LS, Woolven BP, Tomlinson
IA (2003) Domain antibodies: proteins for therapy.
Trends Biotechnol 21:484–490
Luo Q, Mao X, Kong L, Huang X, Zou H (2002) High-
performance affinity chromatography for characteriza-
tion of human immunoglobulin G digestion with
papain. J Chromatogr B 776:139–147
F
Flavanoids Separation
Beatriz Mello
UFSCar, Federal University of Sao Carlos, Buri,
SP, Brazil
Flavonoids are a water-soluble class of polyphe-
nols derived from plant secondary metabolites
through the condensation of cinnamic acid with
malonyl-CoA groups (Bloor 2001). This conver-
sion can lead to the formation of flavones,
isoflavones, flavonols, and anthocyanins. Flavo-
noid chemical structures are based on a C6-C3-C6
skeleton that differs among each other by the
saturation of heteroatomic ring C (Stobiecki and
Kachilicki 2006). Further reactions as
glycosilation, acylation, and alkylation cause the
formation of a huge variety of flavonoids in the
plant kingdom. The flavonoids consist of six
major subgroups: chalcone, flavone, flavonol, fla-
vanone, anthocyanins, and isoflavonoids. Exam-
ples of some of these subgroups are shown in
Fig. 1. Together with carotenes, flavanoids are
also responsible for the coloring of fruits, vegeta-
bles, and herbs. For analysis purposes, there is
basically a flavonoids division into glycosides,
aglycones, and anthocyanins. Each of these
types is quantified by different analytical
methods. The most important dietary sources are
fruits, tea, and soybean. Green and black tea con-
tains about 25 % flavonoids. Other important
sources of flavonoids are apple (quercetin) and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_692-2
citrus fruits (rutin and hesperidin). Flavonoids
are becoming very popular because they have
many health-promoting effects. Some of the activ-
ities attributed to flavonoids include antiallergic,
anticancer, antioxidant, anti-inflammatory, and
antiviral activities.
Essential to the study of flavonoids is having
the means available for their separation (analytical
and preparative) and isolation. Thin-layer chro-
matography is a rapid, simple, and versatile
method for fractionation flavonoids. However,
this method has been substituted to qualitative
and quantitative applications of high-performance
liquid chromatography (HPLC). In HPLC analy-
sis, flavonoids can be separated, quantified, and
identified in only one operation by coupling
HPLC to ultraviolet (UV), mass, or nuclear mag-
netic resonance (NMR) detectors. Another tech-
nique that has been gaining attention is capillary
electrophoresis (CE). All the methods use the
effects of the presence of the flavonoid phenyl
ring which is an excellent chromophore and is
responsible for the easy detection of flavonoids.
Their UV spectra provide enough information to
distinguish the type of phenol (Marston and
Hostettmann 2006)
Flavonoids can be also separated from each
other by the use of a polymeric membrane.
A relatively high concentration of polyphenolics
and flavonoids present in the juices were fraction-
ated by various methods including ultrafiltration
to get a retentate that showed very high oxygen
radical absorbance capacity (ORAC) even at 50 %
2 Flavanoids Separation

Flavanoids Separation,
Fig. 1 Examples of some
flavonoids. (a)
quercetin – flavonol, (b)
cyanidin – anthocyanin, (c)
hesperidin – flavanone

recovery of thin juice (Kumar 2006). Membrane- References

based processes are usually more energy efficient
than distillation, adsorption, and chromatography.
Furthermore, membranes have the advantage of
compatibility with a wide range of solvents and
chemical products, ability to process thermally
sensitive compounds, easy amenability to auto-
mation, smaller footprint, and seamless scale-up.
These advantages open up several possibilities of
membrane application in the production of bioac-
tive compounds through preconcentration of
dilute solutions, fractionation of a complex mix-
ture, recovery of intermediates, and recycling of
solvents. However, it is also important to be aware
of the membrane-based separation drawbacks,
such as limited selectivity, fouling leading to per-
formance decline, cleaning, and higher capital
costs in certain installations.
Bloor SJ (2001) Overview of methods for analysis and
identification of flavonoids. In: Packer L (ed) Methods
in enzymology – flavonoids and other polyphenols.
Academic, San Diego, pp 3–14
Kumar A (2006) Membrane separation technology in
processing bioactive components. In: Functional food
ingredients and nutraceuticals. CRC Press, Boca Raton,
pp 193–208
Marston A, Hostettmann K (2006) Separation and quanti-
fication of flavonoids. In: Andersen OM, Markham KR
(eds) Flavonoids: chemistry, biochemistry and applica-
tions. CRC Press, Boca Raton, pp 1–32
Stobiecki M, Kachilicki P (2006) Isolation and identifica-
tion of flavonoids. In: Grotewold E (ed) The science of
flavonoids. Springer, New York, pp 47–70
F
Flexibility in Gas Separation
Adele Brunetti
National Research Coucil, Institute on
Membrane Technology, Rende, CS, Italy
The flexibility (also called easy of expansion) is
the ability to operate under variable feed quality
conditions, either on a short-term or long-term
basis (Miller and Stöcker 1989; Brunetti
et al. 2010). The changes in feed composition
occur very often in refinery applications, partic-
ularly when the source of the feed is a catalytic
process or when the feedstock to the upstream
unit changes as well as in flue gas streams.
In membrane processes, the increase in feed
impurity concentrations tend to cause a decrease
in product purity, which, however, can be
maintained for small feed composition changes
by adjusting the feed-to-permeate pressure ratio.
In most refinery membrane applications, how-
ever, the major product impurity is methane and
this can be allowed to increase slightly in the
product without major downstream impact. The
flue gas stream contains an amount of CO2 rang-
ing from 5 % to 35 % depending on the process,
the rest being mainly nitrogen and few percent-
age of oxygen. Whether the CO2 concentration is
always higher than 20 %, the membrane systems
can be considered highly flexible. On the con-
trary, for CO2 concentration lower than 20 % the
membrane operation offers a very low flexibility.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_693-1
A further reduction in CO2 concentration, in fact,
produces a reduction of the driving force with a
consequent decrease in CO2 recovery and in
product purity.
The response time of membrane systems is
essentially instantaneous and corrective action
has immediate results. The start-up time required
by the process is extremely short.
The flexibility of the absorption process is
moderate. This system, in fact, responds quite
well to the changes in the feed composition;
however, significant differences in the fraction
of the desired specie contained in the feed imply
higher solvent flow rate that is strictly related to
the size of equipment apart from the absorber.
Furthermore, the fact that the feed stream con-
tains oxidizing compounds (oxygen or sulfur
dioxide) induces major problems of amine deac-
tivation and promotes corrosion.
The PSA process shows a great ability to
maintain purity and recovery under changing
conditions. The process is self-compensating
and even relatively large changes in feed impu-
rity concentrations have little impact on perfor-
mance. As the concentration of a feed impurity
increases, its partial pressure increases, increas-
ing also the amount of the impurity which will be
adsorbed. The purity can be maintained constant
by a simple cycle time adjustment. The response
time to variations is rapid but not abrupt, gener-
ally requiring 5–15 min for responding to a step
change in feed quality. The new steady-state
2 Flexibility in Gas Separation
upon restart following shutdown is reached in
about 1 h.
The cryogenic process has very low flexibility
because changes in the concentration of the lower
boiling components of the feed affect the product
purity directly. Recovery is not strongly affected.
Response time is not as rapid as for PSA or
membrane systems. Start-up is 8–24 h depending
on the procedure used.
References
Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
brane engineering progresses and potentialities in gas
separations. In: Yampolskii Y, Freeman B (eds) Mem-
brane gas separation. Wiley, New York, pp 281–312
Miller GQ, Stöcker J (1989) Selection of a hydrogen
separation process. In: NPRA annual meeting, 19–21
Mar, San Francisco
F
Fossil Fuels Processing by
Membrane Operations
May-Britt Hagg
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Norway
Control of anthropogenic emissions of green-
house gases (GHG) is one of the most challenging
environmental issues related to global climate
change. The larger part of emissions are coming
from fossil fuels. The Energy Information
Administration (EIA) 2010 predicted a 49 %
increase of energy demands from 2007 to 2035
following more and more countries becoming
industrialized. The International Energy Outlook
2010 reference case reported that world energy-
related carbon dioxide (CO2) emissions would
increase from 29.7 billion metric tons in 2007 to
33.8 billion metric tons in 2020 and 42.4 billion
metric tons in 2035 (IEO 2010). The emissions of
the greenhouse gas CO2 is produced in a variety
of ways as shown in Table 1 (Hay and Firman
2002). Among them, fossil fuel power plants are
responsible for roughly 40 % of total CO2 emis-
sions, and coal-fired power plants being the main
contributor. Changing from fossil energy to alter-
native renewable energy would be ideal; how-
ever, we will still be dependent on fossil fuels
for many years ahead both due to limitations of
technology development and also increased
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_694-2
growth. Hence, carbon capture and sequestration
(CCS) is seen as an efficient way to mitigate the
emission of CO2 in order to fight against global
warming. The key motivation for CCS is that we
may continue to use fossil fuels without causing
significant CO2 emissions. Clearly coal-fired
power plants need to be firstly tackled, especially
by retrofitting capture to existing plants. Differ-
ent techniques such as chemical and physical
absorption, physical adsorption, cryogenics, and
membrane separation may be used for CO2 cap-
ture. Membranes are already an alternative and
competitive technology for other selected gas
separation processes such as natural gas sweeten-
ing, biogas upgrading, and hydrogen production
during the last two or three decades. Alternative
ways of using membranes for fossil fuel
processing at power plants are illustrated in
Fig. 1. Additionally, membranes are also being
used for CO2 removal from natural gas and
upgrading of biogas.
Postcombustion: The membrane is then typi-
cally retrofitted to the plant as an end-of-pipe
solution, and the main gas components are CO2
and N2. For a coal-fired power plant the content
of CO2 will be 10–15 %, while for a natural gas
plant the CO2 content may be as low as ~5 %
unless there is an integrated solution. The flue gas
will at this point have a temperature of around
70  C and is at atmospheric pressure. These con-
ditions are in general not very favorable for mem-
brane separation as there is hardly any driving
force, and much energy must be used in order to
2 Fossil Fuels Processing by Membrane Operations

Fossil Fuels Processing by Membrane Operations, Table 1 Overview of global stationary CO2 sources larger than
0.1 million tons (Mt) of CO2/year
Process Number of sources Emissions (Mt CO2/year)
Fossil fuels Power 4,492 10,539
Iron and steel industry 269 646
Cement production 1,175 932
Refineries 638 798
Petrochemical industry 470 379
Oil and gas processing N/A 50
Other sources 90 33
Biomass Bioethanol and bioenergy 303 91
Total 7,887 13,468
(IPCC special report on CCS, working group III)

create sufficient partial pressure difference over
the membrane. The recommended membrane
solution in this case will be to use a membrane
with very high flux and selectivity which can be
achieved with a facilitated transport membrane
having a fixed or mobile carrier to enhance the
transport (Kim et al. 2004), or to use an innova-
tive two-stage process solution where air is being
used as sweep on the second stage and fed to the
burner (Merkel et al. 2010). In both cases, energy
demand is minimized by using only a fan on the
feed side and pulling vacuum on the permeate
side. The membrane material will be
polymeric. Impurities in the flue gas stream
(SO2, NOx, particles) may be a challenge for
the membrane material.
Precombustion: When used in precombustion
the membrane will be an integrated solution with
the gas turbine and CO2 may thus be removed at
higher pressure. After the shift reaction H2 and
CO2 will be in a mixture, with close to 40 mol%
CO2. The pressure will be in the range of
25–30 bar, and temperature around 300–350  C
unless there has been a sulfur removal unit up
front of the membrane. The high temperature,
pressure, and concentration are very favorable
for Palladium membranes which can achieve
extremely efficient separation of the two main
components, allowing hydrogen to permeate
(Jordal et al. 2004). An advantage is also that
CO2 is captured at high pressure, and less energy
will be needed for sequestration. The main chal-
lenge for this membrane solution is the module
construction at this high temperature and also
potential poisoning of the membrane.
Oxyfuel combustion: This solution is very ele-
gant, using a membrane to separate out pure
oxygen. The air separating membrane is, how-
ever, still not fully developed. These membranes
are suitable for advanced power generation
requiring pure oxygen for combustion or gasifi-
cation and are based on zirconia and perovskite
where oxygen is transported through the material
as O2 . The materials are stable at very high
temperatures (>500  C) but again module design
is very challenging at these high operating
temperatures.
Cross-References
▶ Oxyfuel by Jurgen Caro
▶ Oxygen Transport Ceramic Membranes:
Perovskite and Non-perovskite by Vesna
Middelkoop
Fossil Fuels Processing by Membrane Operations 3

Fossil Fuels Processing

by Membrane
Operations,
Fig. 1 Alternative
membrane processing at a
power plant

Postcombustion N2
(PC) O2
Coal
Power & Heat CO2 Separation

Air
CO2
Precombustion
(IGCC)
Steam CO2
Air/O2

CO2
Coal Shift, Gas Cleanup H2 Power Compression
Gasification and
+ CO2 Separation & Heat
Dehydration
Air
Oxyfuel Combustion

Air N2
Air Separation

O2

Coal CO2
Power & Heat

References Jordal K, Bredesen R, Kvamsdal HM, Bolland O (2004)

Energy 29:1269–1278
Hay BP, Firman TK (2002) Inorg Chem 41:5502–5512 Kim TJ, Li B, Hägg MB (2004) J Polym Sci
International Energy Outlook 2010 – highlights. http:// B 42:4326–4336
www.eia.doe.gov/oiaf/ieo/highlights.html. Accessed Merkel TC, Lin H, Wei X, Baker R (2010) J Membr Sci
28 Sept 2010 359:126–139
G
Global Optimization of Membrane
Processes
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universtät Dortmund,
Dortmund, Germany
For a number of years, researchers and engineers
in many fields have reported the problem of
obtaining multiple solutions while solving
problems of nonlinear programming (NLP).
Multiplicity of solutions is caused by the
nonconvex nature being present typically in
many engineering problems. Global optimization
(GO), sometimes called nonconvex optimization,
encompasses several techniques which can be
used to handle the problem of finding the best of
these solutions, the global optimum.
General form of GO problem is same as for
NLP problem and it may be stated as
min f ðxÞ
x
s:t: hðxÞ ¼ 0
gðxÞ  0
where x represents vector of optimization
(decision) variables, f(x) is optimization crite-
rion, h(x) and g(x) stand for vectors of equality
and inequality constraints, respectively.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_701-5
To find the global optimum, many methods
have been developed. These can be basically
classified into two branches, stochastic and deter-
ministic ones. Stochastic methods (Weise 2007)
such as simulated annealing, genetic algorithms,
and particle swarm optimization got inspired by
natural phenomena. In general, they randomly
search through the solution space (space where
constraints are satisfied) and due to that usually
do not require gradient information. It is often
reported that weakness of these algorithms is that
they cannot guarantee convergence to global
optimum in finite time.
On the other hand, deterministic methods
search through the whole solution space system-
atically and thus can provide so-called
e-convergence (e is arbitrarily small positive
number) guarantee to the global optimum. Most
popular are methods based on branch-and-bound
algorithms and interval analysis (Horst and Tuy
1990).
The latter type of methods was successfully
used in Chen et al. (2006) for globally optimal
design of membrane fuel cell. Other applications
of methods of GO involve parameter estimation
(Papamichail and Adjiman 2004), optimal con-
trol problems (Esposito and Floudas 2000), and
problems of nonlinear and mixed integer
nonlinear programming (Chachuat et al. 2006).
Other references on GO problems in chemical
engineering can be found in Rangaiah (2010).
2 Global Optimization of Membrane Processes
References
Chachuat B, Singer AB, Barton PI (2006) Global methods
for dynamic optimization and mixed-integer dynamic
optimization. Ind Eng Chem Res 45(25):8373–8392
Chen KI, Winnick J, Manousiouthakis VI (2006) Global
optimization of a simple mathematical model for a
proton exchange membrane fuel cell. Comput Chem
Eng 30(8):1226–1234. doi:10.1016/j.compch-
emeng.2006.02.009, ISSN 0098-1354
Esposito W, Floudas C (2000) Deterministic global opti-
mization in nonlinear optimal control problems. J Glob
Optim 17:97–126
Horst R, Tuy H (1990) Global optimization deterministic
approaches, 3rd edn. Springer, Berlin
Papamichail I, Adjiman CS (2004) Global optimization of
dynamic systems. Comput Chem Eng 28:403–415
Rangaiah GP (2010) Stochastic global optimization: tech-
niques and applications in chemical engineering,
Advances in process systems engineering. World Sci-
entific, Hackensack. ISBN 9789814299206
Weise T (2007) Global optimization algorithms theory
and application. http://www.it-weise.de/
H
Hybrid Processes
Marco Scholz
Aachener Verfahrenstechnik - Chemical Process
Engineering, RWTH Aachen University,
Aachen, Germany
In membrane science, hybrid processes are pro-
cesses, in which membrane technology is com-
bined with conventional separation equipment to
perform a separation more efficiently. The objec-
tive is to combine the positive characteristics of
each individual technology to obtain a process
which is better than the individual process.
Reverse osmosis, gas permeation, and in par-
ticular pervaporation are the most prominent
membrane processes which are combined with
conventional separation equipment to form
hybrid processes (Melin and Rautenbach 2007).
Conventional separation equipment is either lim-
ited by equilibrium and kinetics (e.g., amine) or
by thermodynamic equilibrium only (e.g., cryo-
genic). However, the membrane separation is
controlled by kinetics. Hence, combining both
the equilibrium and the kinetic limited separation
can have outstanding advantages. For instance,
combining a distillation column and a
pervaporation module is profitable as the
pervaporation unit breaks the azeotrope and the
bulk separation is performed by distillation.
Combining membrane technology and con-
ventional separation technology can significantly
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_707-5
reduce the equipment size. By applying hybrid
processes, thermodynamic limitations can be
overcome or more efficient processes can be
designed regarding the capital as well as the
operational costs.
There are many different process configura-
tions, in which membranes and conventional sep-
aration equipment can be combined. Depending
on the process, membranes are applied for both,
to perform the bulk separation and to polish the
respective products. Hybrid processes are partic-
ularly interesting when membrane units are
added to existing separation equipment. Hence,
debottlenecking of processes or research activi-
ties can easily be performed without shutting
down the separation process (Hömmerich and
Rautenbach 1998).
Examples of Hybrid Processes
Skiborowski et al. analyzed a hybrid process in
which seawater is desalinated (Skiborowski
et al. 2012). Reverse osmosis modules are com-
bined with forward-feed multi-effect distillation.
For low energy costs, they identified the reverse
osmosis network as the most profitable plant. For
moderate energy costs and for high energy costs,
the hybrid process and the multi-effect distilla-
tion are the optimal process configuration,
respectively.
Baker and Lokhandwala investigated natural
gas processing in detail (Baker and Lokhandwala
2 Hybrid Processes
2008). Here, typically membrane technology and
amine scrubbing compete. The carbon dioxide
content in the feed gas and the feed gas flow
rate determine which separation technology
should be applied. Interestingly, for high carbon
dioxide mole fractions and for high feed flow
rates, the combination of membrane technology
and amine absorption is the most efficient process
configuration.
The vapor recovery of gasoline vapors from
storage tanks can be done by applying rubbery
gas permeation membranes and condensation
equipment (Rautenbach et al. 1996). Here, the
bulk separation is done by condensation and the
gas is subsequently polished in a gas permeation
unit. Both, the recovery of gasoline and environ-
mental standards for the exhaust gas, have to be
considered in the design of such a plant.
In the MTBE (methyl tert-butyl ether) produc-
tion methanol, MTBE and n-C4 have to be sepa-
rated. The separation is complex due to the
formation of azeotropes (Hömmerich and
Rautenbach 1998). Two hybrid processes can be
applied: one in which the mixture is fed to a
pervaporation module to remove the methanol
while the MTBE and the n-C4 fraction are sepa-
rated in a distillation column. In the other pro-
cess, the raw mixture is fed to a distillation
column while the pervaporation module operates
at a side draw. This latter hybrid process out-
classes the conventional process, in which differ-
ent distillation columns are applied.
References
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47:2109–2121
Hömmerich U, Rautenbach R (1998) Design and optimi-
zation of combined pervaporation/distillation pro-
cesses for the production of MTBE. J Membr Sci
146:53–64
Melin T, Rautenbach R (2007) Membranverfahren-
Grundlagen der Modul-und Anlagenauslegung.
Springer, Berlin
Rautenbach R, Knauf R, Struck A, Vier J (1996) Simula-
tion and design of membrane plants with Aspen Plus.
Chem Eng Technol 19:391–397
Skiborowski M, Mhamdi A, Kraemer K, Marquardt
W (2012) Model-based structural optimization of sea-
water desalination plants. Desalination 292:30–44
H
Hydrogen Production by Membrane
Reactors
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende(CS), Italy
Hydrogen, the energetic vector of the future, is
expected to become more and more important
according to leading energy scenarios as also
reported in the EU-White Paper (http://ec.europa.
eu/research/energy/pdf/efchp_hydrogen13.pdf) on
renewable and alternative energy. Moreover, BP
and GE announced plans to develop jointly up to
15 new hydrogen power plants to generate elec-
tricity over the coming decade (http://www.bp.
com/content/dam/bp/pdf/investors/BP_Annual_
Report_and_Form_20F_2014.pdf). The hydro-
gen required is planned to be derived from fossil
fuels, including coal and natural gas, while devel-
oping, in the meantime, new plants equipped for
carbon capture technologies capable of reducing
CO2 emissions by 90 % (http://www.worldwatch.
org/node/4516). If one considers that, at present,
96 % hydrogen is directly produced from fossil
fuels and ca. 4 % indirectly by using electricity
generated through them (Kothari et al. 2008), the
need to find new efficient and competitive tech-
nologies able to maximize hydrogen production
from fossil fuels while lowering CO2emissions
and other pollutants appears evident.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_708-1
In addition, up to now, steam is utilized for
most H2 obtained industrially from natural gas or
light hydrocarbons. Conventional technologies
can also operate with alternative fuel sources
such as, for instance, bioalcohols and other bio-
masses, having attracted great attention owing to
their being renewable sources (Abanades
et al. 2013; Vizcaıno et al. 2012; Sanz
et al. 2014; Iulianelli et al. 2014). Along with
these technologies,which can be integrated with
CO2 separation units, membrane reaction and
separation units are becoming more and more
promising and significant in hydrogen production.
Membrane reactors couple conversion and sepa-
ration in the same operating unit and this leads to a
conversion higher than the thermodynamic one of
conventional reactors, a lower reaction volume, a
pure (permeate) hydrogen stream, and a concen-
trate in CO2 (retentate) stream. The permeate
hydrogen stream has a pure grade that can be
directly fed without any further treatment to a
polymeric electrolyte membrane fuel cell and no
performance loss is observed (Brunetti
et al. 2008).
Thus, the new model reactor has several advan-
tages with respect to conventional technology,
i.e., the production of a new carrier and CO2
capture, since pure hydrogen and CO2 concen-
trated streams exit this reactor.
Membrane reactors can operate in various sec-
tions of the hydrogen production plants: replacing
both steam reforming (SR) as well as high- and
low-temperature water gas shift (WGS) reactors.
2 Hydrogen Production by Membrane Reactors

1 High temperature and low pressure thermody-

namically favor the process because the reaction
is endothermic and also characterized by an

r
ba
MSR
increase in the number of moles. This reaction is

10
ar
thermodynamically limited and the selective

5b

ar
X CH (-)

hydrogen removal will increase its conversion.

1b
4

r
0.5 The development of ceramic and supported

ba
1
I =10
I = 0 (TR)
0 permeation of other species through the metallic
200 400
T (°C)
Hydrogen Production by Membrane Reactors,
Fig. 1 Equilibrium conversion of Methane as function of
the temperature for both membrane and traditional reactors
at differrent feed pressure values for H2O/CH4 initial ratio
of 3. For membrane reactor, the permeate pressure is 1 bar
and the sweep contained in the permeate chamber is the
times higher than the methane amount in the reaction
volume. (Marigliano et al. 2001, 2003)
Steam reforming is the reaction between
hydrocarbons and water vapor. The steam
reforming of methane is the best known of this
reaction class owing to its industrial importance in
hydrogen and syngas production (Scholz 1993).
A methane steam reformer is industrially operated
at 700–1100
C and 20–30 bar over Ni-based
catalyst; the main species and reactions involved
are (Xu and Froment 1989a, b)
CH4 þ H2 O ¼ CO þ 3 H2 DH298
¼ 206 kJ mol1
CO þ H2 O ¼ CO2 þ H2 DH298
¼ 41 kJ mol1
CH4 þ 2H2 O ¼ CO2 þ 4H2 DH298
1
¼ 165 kJ mol
r metallic (e.g., palladium-based) membranes has
ba
5
r promoted the investigation of the membrane
1 0b
a
reformer for a high-temperature reaction. Dense
palladium–based membranes are characterized by
infinite hydrogen selectivity which prevents the
600 structure of the palladium.
The operating conditions (temperature, pres-
sure, flow rate, composition, etc.) have to be
completely rethought since the permeation signif-
icantly affects the reforming process/reaction.
Methane steam reforming can be operated at a
significantly lower temperature (400–500
C)
since the reaction pressure favors hydrogen per-
meation. The higher the feed pressure, the higher
the hydrogen removal and as a consequence the
methane conversion (see Fig. 1).
The stream produced by reformers and/or coal
gasification plants contains around 50 % molar of
hydrogen (on a dry basis) and between 40 % and
45 % molar of CO, which is usually reduced in an
upgrading stage producing more hydrogen at the
same time, by WGS reaction. The upgrading stage
of traditional processes consists of a multistage
CO-shift process based on two catalytic reactors:
the first operates at high temperatures (about
350–400
C) to take advantage of the faster reac-
tion rates, whereas the other operates at low tem-
peratures (around 220–300
C) to refine the
carbon monoxide conversion, thus allowing a
lower final CO concentration (less than 1 %
molar) (Raggio et al. 2005).
CO þ H2 O ¼ CO2 þ H2
DH0 298 ¼ 41 kJ mol1
The H2-rich stream coming out from the last reac-
tor is fed to a pressure swing adsorption (PSA)
Hydrogen Production by Membrane Reactors
unit for H2 separation from other gases. Most
often another reaction unit is added for oxidizing
CO to CO2, to meet the purity targets for fuel cell
uses (CO concentration lower than 10–20 ppm).
Additionally, the reduction of the percentage of
CO in the system reduces coking of metal catalyst
surfaces, implying a longer lifetime. This means
an intensified process with a reduced plant size
and a higher yield. In some cases, the interesting
results achieved at laboratory level thanks to this
effect have even led to several patents (Deckman
et al. 2005; Gummalla et al. 2010; Lamm
et al. 2005; Tsay et al. 2007; Wei 2009; Willms
and Birdsell 2000).
However, most of the studies on WGS in MRs
were carried out in a low and medium temperature
range (180–250
C and 250–320
C, respectively)
by using CuO-based catalysts, owing to the thermo-
dynamics constraints on the reaction (Barbieri
et al. 2008; Dittmeyer et al. 2001; Mendes
et al. 2010, 2011; Paglieri and Way 2002; Pinacci
et al. 2010). Only few works in the literature have
explored the combination of a high-temperature
WGS catalyst with Pd-based membranes
(Augustine et al. 2011; Bi et al. 2009; Brunetti
et al. 2012, 2015; Catalano et al. 2013; Chein
et al. 2013; Iyoha et al. 2007; Pinacci et al. 2010;
Uemiya et al. 1991). An interesting review on the
recent advances of this technology for high-
temperature applications is proposed by Cornaglia
et al. (2015).
Rather than the limitations of thermodynam-
ics, fast kinetics and promoted permeation are
the main advantages offered by the high temper-
ature. However, a fundamental role is played by
the characteristics of the membrane used in the
reactor. In fact, until now one of the main hur-
dles limiting the large-scale development of
these MRs is the high cost of Pd-based mem-
branes, partly owing to the cost of palladium
that could further increase if Pd membranes are
exploited on a large industrial scale (Helmi
et al. 2014). For this reason, great efforts are
being made to obtain thin Pd layers on appro-
priate supports in order to maximize the perme-
ate flux, minimize the support influence, and
3
reduce the cost related to Pd (PachecoTanaka
et al. 2005; Zhang et al. 2009).
References
Abanades A, Rubbia C, Salmieri D (2013) Thermal crack-
ing of methane into hydrogen for a CO2-free utilization
of natural gas. Int J Hydrog Energy 38(20):8491–8496
Augustine AS, Ma YH, Kazantzis NK (2011) High pres-
sure palladium membrane reactor for the high temper-
ature water–gas shift reaction. Int J Hydrog Energy
36:5350–5360
Barbieri G, Brunetti A, Tricoli G, Drioli E (2008) An
innovative configuration of a Pd-based membrane reac-
tor for production of pure hydrogen. Experimental
analysis of water gas shift. J Power Sources
182:160–167
Bi Y, Xu H, Li W, Goldbach A (2009) Water-gas shift
reaction in a Pd membrane reactor over Pt/Ce0.6Zr0.4O2
catalyst. Int J Hydrog Energy 34:2965–2971
Brunetti A, Barbieri G, Drioli E (2008) A PEM-FC and H2
membrane purification integrated plant. Chem Eng Pro-
cess: Process Intesif 47(7):1081–1089. doi:10.1016/j.
cep.2007.03.015, special issue “Euromembrane 2006”
Brunetti A, Drioli E, Barbieri G (2012) Medium/high tem-
perature water gas shift reaction in a Pd-Ag membrane
reactor: an experimental investigation. RSC Adv
2(1):226–233
Brunetti A, Caravella A, Fernandez E, Pacheco Tanaka
DA, Gallucci F, Drioli E, Curcio E, Viviente JL,
Barbieri G (2015) Syngas upgrading in a membrane
reactor with thin Pd-alloy supported membrane. Int
J Hydrog Energy 40(34):10883–10893. doi:10.1016/j.
ijhydene.2015.07.002
Catalano J, Guazzone F, Mardilovich IP, Kazantzis NK,
Ma YH (2013) Hydrogen production in a large scale
water gas shift Pd based catalytic membrane reactor.
Ind Eng Chem Res 52:1042–1055
Chein R, Chen Y-C, Chung JN (2013) Parametric study of
membrane reactors for hydrogen production via high-
temperature water gas shift reaction. Int J Hydrog
Energy 38:2292–2305
Cornaglia L, Munera J, Lombardo E (2015) Recent
advances in catalysts, palladium alloys and high tem-
perature WGS membrane reactors. A review. Int
J Hydrog Energy 40:3423–3437
Deckman HW, Fulton JW, Grenda JM, Hershkowitz
F (2005) Electric power generation with heat
exchanged membrane reactor. EP Patent 1,294,637
Dittmeyer R, Hollein V, Daub K (2001) Membrane reac-
tors for hydrogenation and dehydrogenation processes
based on supported palladium. J Mol Catal A Chem
173:135–184
Gummalla M, Vanderspurt TH, She Y, Dardas Z,
Olsommer B (2010) Power plant with membrane
4 Hydrogen Production by Membrane Reactors
water gas shift reactor system. US Patent
20,100,104,903
Helmi A, Gallucci F, van SintAnnaland M (2014) Resource
scarcity in palladium membrane applications for carbon
capture in integrated gasification combined cycle units.
Int J Hydrog Energy 39:10498–10506
Iulianelli A, Pirola C, Comazzi A, Galli F, Manenti F,
Basile A (2014) Chapter 1: Water gas shift membrane
reactors. In: Basile A, Hai F, Di Paola L, Piemonte
V (eds) Membrane reactors for energy applications
and basic chemical production. Woodhead (in press)
Langford Lane, Kidlington, OX5 1GB, UK
Iyoha O, Enick R, Killmeyer R, Howard B, Ciocco M,
Morreale B (2007) H2 production from simulated coal
syngas containing H2S in multi-tubular Pd and 80 wt%
Pd-20 wt% Cu membrane reactors at 1173 K. J Membr
Sci 306:103–115
Kothari R, Buddhi D, Sawhney RL (2008) Comparison of
environmental and economic aspects of various hydro-
gen production methods. Ren Sust En Rev 12:553–563
Lamm A, Poschmann T, Schaefer J (2005) Apparatus for
generating virtually pure hydrogen for fuel cells. US
Patent 20,050,039,401
Marigliano G, Barbieri G, Drioli E (2001) Effect of energy
transport in a palladium based membrane reactor for
methane steam reforming process. Catal Today
67(1–3):85–99. doi:10.1016/S0920-5861(01)00268-1
Marigliano G, Barbieri G, Drioli E (2003) Equilibrium
conversion for a palladium membrane reactor. Depen-
dence of the temperature and pressure, Chem. Eng. and
Processing, 42, 231–236; DOI:10.1016/S0255-2701
(02)00092-2.
Mendes D, Chibante V, Zheng J-M, Tosti S, Borgognoni F,
Mendes A, Madeira LM (2010) Enhancing the produc-
tion of hydrogen via water–gas shift reaction using
Pd-based membrane reactors. Int J Hydrog Energy
35:12596–12608
Mendes D, Sá S, Tosti S, Sousa JM, Madeira LM, Mendes
A (2011) Experimental and modeling studies on the
low-temperature water-gas shift reaction in a dense
Pd–Ag packed-bed membrane reactor. Chem Eng Sci
66:2356–2367
PachecoTanaka DA, LlosaTanco MA, Niwa S, Wakui Y,
Mizukami F, Nambra T et al (2005) Preparation of
palladium and silver alloy membrane on a porous
a-alumina tube via simultaneous electroless plating.
J Membr Sci 247(1e2):21–27
Paglieri SN, Way JD (2002) Innovations in palladium
membrane research. Sep Purif Methods 31:1–169
Pinacci P, Broglia M, Valli C, Capannelli G, Comite
A (2010) Evaluation of the water gas shift reaction in
a palladium membrane reactor. Catal Today
156:165–172
Raggio G, Pettinau A, Orsini A, Fadda M, Cocco D,
Deiana P, Pelizza ML, Marenco M, Second interna-
tional conference on clean coal technologies for our
future, Castiadas, Sardinia, Italy, 10–12 May 2005
Sanz R, Calles JA, Alique D, Furones L (2014) H2 produc-
tion via water gas shift in a composite Pd membrane
reactor prepared by the pore-plating Method. Int
J Hydrog Energy 39:4739–4748
Scholz WH (1993) Process for industrial of hydrogen and
associated environmental effects. Gas Sep Purif
7(3):131–139
Tsay D, Weiss SE, Tsay TC, (2007) Single stage membrane
reactor for high purity hydrogen production. US Patent
20,070,157,517
Uemiya S, Sato N, Ando H, Kikuchi E (1991) The water
gas shift reaction assisted by a palladium membrane
reactor. Ind Eng Chem Res 30:589–591
Vizcaıno AJ, Lindo M, Carrero A, Calles JA (2012) Hydro-
gen production by steam reforming of ethanol using Ni
catalysts based on ternary mixed oxides prepared by
coprecipitation. Int J Hydrog Energy 37(2):1985–1992
Wei W (2009) Polygeneration systems. US Patent
20,090,084,035
Willms RS, Birdsell SA (2000) Apparatus and method for
simultaneous recovery of hydrogen from water and
from hydrocarbons. US Patent 6,165,438
Xu J, Froment GF (1989a) Methane steam reforming,
methanation and water gas shift: I. Intrinsic kinetics.
AIChE J 35:88–96
Xu J, Froment GF (1989b) Methane steam reforming:
II. Diffusional limitations and reactor simulation.
AIChE J 35:97–103
Zhang K, Gao H, Rui Z, Liu P, Li Y, Lin YS (2009) High-
temperature stability of palladium membranes on
porous metal supports with different intermediate
layers. Ind Eng Chem Res 48:1880–1886
I
Intermittent Feed Diafiltration
Zoltán Kovács
Department of Food Engineering, Institue of
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary
Intermittent feed diafiltration is characterized
as a batch diafiltration process in which the
processed liquor is first concentrated to a
predetermined volume and then diluted back to
its original volume with a diluent. This
concentration-dilution sequence may be repeated
several times to obtain the desired degree of
separation of macrosolutes from microsolutes.
As a final step, an additional post-concentration
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_712-3
may be applied to achieve the required final vol-
ume. A mathematical analysis of intermittent
feed diafiltration can be found in (Wang et al.
2007).
Note that the processing scheme of intermit-
tent feed diafiltration is basically a slight modifi-
cation of the method employed by sequential
dilution diafiltration (also called discontinuous
diafiltration by sequential dilution).
References
Wang L, Yang G, Xing W, Xu N (2007) Mathematic
model of the yield for diafiltration processes. Sep
Purif Technol 59:206–213. doi:10.1016/j.
seppur.2007.06.007
L
Langerhans Islet
Loredana De Bartolo and Antonietta Messina
Institute on Membrane Technology ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
The islets of Langerhans are endocrine cell clus-
ter well ordered in lobules, of 0.3–0.7 mm in
diameter, containing from 3,000 to 4,000 cells,
and located mainly in the tail region of the pan-
creatic gland. Discovered in 1869, though
representing only 2 % of the whole organ, they
serve to coordinate the physiological control of
the glycemic values in the blood. Five different
hormone-secreting cell types constitute the islets’
cytoarchitecture: alpha cells producing glucagon,
beta cells producing insulin and amylin, delta
cells producing somatostatin, PP cells (gamma
cells) producing the pancreatic polypeptide, and
epsilon cells producing ghrelin. In human beings,
the alpha and beta cells are in close relationship
with each other. Representing nearly 90 % of the
total islet cells, their secretive activity is modu-
lated by the blood glucose levels: when low con-
centrations of sugar are detected, the islets
respond with the glucagon secretion to induce
the glucose release from the hepatic deposits
into the bloodstream. After a meal the high con-
centration of the blood sugars causes the beta cell
activation determining the insulin-induced glu-
cose metabolism and the production of the energy
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_713-1
requested by the body. Since the interaction
between the hormone-secreting cells of the islets
and the paracrine, electric, and nervous-
regulating factors is highly complex, the tiniest
decompensation in the islet cells’ functions, mod-
ulation, and survival can result in the onset of
severe pathologies and organic disorders, which
leads patients to severe complications and a high
risk of death. Actually, 98 % of the diseases
involving the pancreas referred to the loss of the
ability in modulating the food sugars’ conversion
into energy, due to the malfunctioning or destruc-
tion of the insulin-producing beta cells by auto-
immune responses. Thus, sustaining and/or
replacing malfunctioning islets is the only thera-
peutic approach in order to induce the partial
recovery of the metabolic functions in the
patients (Patel et al. 2014). Before 1893 and the
discovery of the pancreas involved in the income
of the diabetes, starving was the only treatment
possible for people suffering for diabetes. Then,
first attempts in the development of grafts were
made using deceased donor’s islets serving as
substitutes for the malfunctioning pancreas.
Many patients showed a partial recovery; how-
ever, after transplantation, these islet grafts were
inevitably destroyed due to the immune and
inflammatory reaction in the hosts. In truth,
despite the risk/benefit trade being quite high
for the patients, the transplantation still remains
the only therapeutically approved approach to
gain the patients recovery of the pancreatic activ-
ity. Allo and autotransplantation are nowadays
2 Langerhans Islet
performed through the infusion of purified islets
into the portal vein of the liver, and 50 % of the
receivers are able to regain the pancreatic func-
tionality and recover from the systemic compli-
cations in 1 year. However, the number of
available and compatible donors is quite limited,
and the lifetime immunosuppression therapy
exposes the patient to infections, diseases, and
harmful side effects. Thus, new techniques
labeled as tissue engineering approaches have
been developed to overcome these disadvantages
and foresee the use of polymeric membrane sys-
tems to produce engineered device containing
islets of insulin-producing cells, to control the
release of the cell products from the islets, their
sustainment, and their protection from the immu-
noreactive species in the site of implantation.
Coordinated by local drug delivery systems,
consisting in boles of low-dose anti-rejection
drugs able to minimize the immune response as
well as any inflammatory effects at the site of
implantation, the encapsulation technique is the
most promising method. The islets are wrapped
in a tight coating made of biocompatible poly-
mers acting as a perm-selectivity membrane that
serves to mimic the heterogeneous and safe envi-
ronment where oxygen and nutrient perfusion is
provided continuously and appropriate space and
ECM-like physical and mechanical support,
essential for the correct insulin production and
secretion and the islets’ survival, are provided.
Different classes of encapsulating devices are
available and classified depending on their size
in macro-, micro-, and nano-devices. Classified
as extravascular diffusion devices when placed
subcutaneously or in the peritoneal cavity and
intravascular diffusion system, three
macrodevices have been approved for the clinical
trials: the TheraCyte system, made up of two
composite Teflon-based membranes in between
the islets are placed; the Islet Sheet device, con-
stituted by supported alginate sheets containing
the pancreatic islets; and the Beta O2 device able
to increase the oxygen exchange in the implanta-
tion site being made of oxygen-generating bio-
material able to deliver locally the oxygen to the
cells. Additional macrodevices consist of tubular
porous membranes filled with islets generally
placed into the vessels, where adequate kinetic
properties allowed the insulin release straight into
the blood stream. Micro devices constituted by
single cluster of beta cells incorporate into semi-
permeable polymeric membranes, and nano-
devices are nowadays under investigation in a
few animal models. They differ generally on the
processing methods used for the encapsulation of
the islets and both allow to increase the insulin
release rate and the oxygen exchange into the
islets. The micro systems are processed in a
spherical system of alginate hydrogels coated
with poly-ornithine and polylysine or by cross-
linking a thin hydrogel sheet onto an islet cluster
by the conformal coating methods, whereas the
nano-devices (1–100 mm) consist of islets encap-
sulated by alternating charged polylysine,
polyglutamic acid, and PEG-biotin polymers
over the cell aggregate surface through the
layer-by-layer method. The decreased thickness
of the capsules obtained by covering the islets
with a single sheet of molecules increases and
improves the insulin release kinetics after
implantation and resulting as well in higher dif-
fusion of nutrients in the core of the cell clusters.
Independently on the size of the device, three
different encapsulated replacement strategies
are available for the implantation: All-In/
Biodegrade-Out replacement, made of biode-
gradable components easily absorbed by the
body; All-In/All-Out replacement, designed to
not react with the host tissues as the cytother-
apeutics devices, the islet sheet medical devices,
and the beta-O2 device; and Flush/Reload
replacement used for the macrodevices designed
in order to grow into the host to provide a vascu-
lar interface (David and Marchetti 2014). New
cell sources. To overcome the shortage of donor
organs and the side effect linked to the autoim-
mune destruction of the patient islets as for dia-
betes type I, alternative sources of beta cells have
been researched. The adult stem cells or progen-
itor cells appear to be the most promising.
Through reprogramming cell strategy
(transdifferentiation), pancreatic precursor cells
are reprogrammed in insulin-producing cells.
Moreover, the own patients pancreas exocrine
cells and the skin cells that can undergo to the
Langerhans Islet
reprogrammation technique representing a prom-
ising new source for the beta cells supply, being
not needed the immunosuppression therapy after
the implant (Domı̀nguez-Bendala et al. 2013).
Therefore, another potential source of beta cells
may be the xenotransplantation with pig pancreas
cells. Interestingly, human and porcine insulin
differ only for one amino acid, and insulin
extracted from porcine pancreas has been used
for the treatment of patients with diabetes before
the development of recombinant human insulin
technology. However, several problems need to
be overcome for porcine islet transplantation to
become a viable clinical option; however, studies
in rodents and large animals have shown great
promise that justifies cautious optimism for the
near future. In the last years, another chance to
improve the tissue engineering of the pancreas
appears to be the prevention of the inflammation
at the site of the transplant, co-transplanting mes-
enchymal stem cells. The MSCs that have been
demonstrated offer natural defenses by blocking
the signals of the immune responses, limiting
inflammation, stimulating the blood vessel
growth, and promoting the long-term function
of islets due to their trophic effects.
Up until now, though the most important pro-
gress in the pancreatic islet transplantation is
3
settled in preclinical trials and only one lead
research project has been presented in the last
years on baboons, 95 % of the patients who
received the capsule implantation resulted in con-
siderable improvements of the glucose metabo-
lism with the reverse of the main diabetes side
effects at 1 year and more than 80 % at 5 years
after implants opening new hopes in the further
improvement of new strategies for the diabetes
treatment in the nearest future.
References
David SW, Marchetti P (2014) Encapsulated islets for
diabetes therapy: history, current progress, and critical
issues requiring solution. Adv Drug Deliv Rev
67–68:35–73
Domı̀nguez-Bendala J, Pileggi A, Ricordi C (2013) Islet
cell therapy and pancreatic stem cells, Chapter 70. In:
Atala A, Lanza R (eds) Handbook of stem cells,
2nd edn. Academic, New York, pp 835–853
Patel T, Salvatori M, Hemal S et al (2014) Pancreatic islets
regeneration: the bioengineering approach,
Chapter 41. In: Orlando G, Lerut JP, Soker S, Stratta
RJ (eds) Regenerative medicine applications in organ
transplantation, 1st edn. Academic, New York,
pp 599–607
L
Liquid Chromatography – Organic
Carbon Detection (LC-OCD)
Loreen O. Villacorte
FMC Technologies, Separation Innovation and
Research Center, Arnhem, The Netherlands
Liquid chromatography – organic carbon detec-
tion (LC-OCD) is an analytical technique for
identification and quantification of natural
organic matter (NOM) constituents in aquatic
environments and water-soluble synthetic
organic matter in technical waters. This tech-
nique has several specific applications including
NOM investigation in drinking water, wastewa-
ter, and marine waters and quality control moni-
toring of ultrapure water used in power plants and
the semiconductor industry (Huber and Frimmel
1994; Huber et al. 2011). It is widely applied in
membrane-based water treatment to characterize
the different NOM constituents in the source
waters (e.g., Kennedy et al. 2005; Amy
et al. 2011; Villacorte et al. 2012), to assess the
organic removal efficiency of pretreatment and
membrane filtration processes (e.g., Frimmel
et al. 2004; Villacorte et al. 2009, 2010; Huang
et al. 2011; Zheng et al. 2010), and to identify the
NOM constituents that cause fouling in MF/UF
and NF/RO systems (e.g., Huber 1998; Hender-
son et al. 2011; Kennedy et al. 2008; Jiang
et al. 2010; Batsch et al. 2005; Zheng et al. 2009).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_714-6
The principle behind NOM fractionation by
LC-OCD is based on three separation processes,
namely, size exclusion, ion interaction, and
hydrophobic interaction. Since NOM constitu-
ents are highly heterogeneous in terms of size
and majority of which are hydrophilic and weakly
acidic, size exclusion is considered as the domi-
nant mechanism of separation (DOC-Labor
2006). Size exclusion chromatography (SEC) is
based on steric interactions or physical sieving
where the difference in speed of diffusion for
smaller and larger molecules is used to identify
the different NOM fractions in the mobile phase
(e.g., buffered water sample). The stationary
phase is a packing of porous beads which allows
smaller molecules to diffuse into the bead interior
while preventing the larger molecules to diffuse
through. As a consequence, larger molecules
have less volume to traverse and travel faster
through the chromatogram column (shorter elu-
tion time) than smaller molecules.
The modern LC-OCD technology is mainly
attributed to the works of Stefan Huber in the
early 1990s when he successfully improved the
sensitivity of the LC/DOC (predecessor of
LC-OCD) developed earlier at the Engler-Bunte
Institute in Karlsruhe, Germany (http://www.
doc-labor.de/). The current LC-OCD system has
an online organic carbon detector (OCD), UV
detector (UVD), and organic nitrogen detector
(OND) to continuously measure the relative sig-
nal response of organic carbon, UV, and organic
nitrogen, respectively, at different retention
2 Liquid Chromatography – Organic Carbon Detection (LC-OCD)

Liquid Chromatography – Organic Carbon Detection (LC-OCD), Table 1 Characteristics of different constituents
of NOM identifiable by LC-OCD (www.doc-labor.de; Huber et al. 2011; Batsch et al. 2005)
NOM fraction Typical size (Da) Typical composition
Biopolymers >20,000 Polysaccharides, proteins, amino sugars, polypeptides, TEPs, EPS
Aquatic humics 1000 Humic and fulvic acids
Building blocks 300–450 Weathering and oxidation products of humics
LMW neutrals <350 Mono-oligosaccharides, alcohols, aldehydes, ketones, amino acids
LMW acids <350 All monoprotic organic acids

12
OCD: organic carbon detection
Building Blocks UVD: UV detection at l=254 nm
Acids and OND: organic nitrogen detection
Humics LMW Humics
10

8
rel. Signal Response

Biopolymers

LMW-Neutrals
6

OCD
4

Inorganic
Colloids
2
UVD
Nitrate
OND
0
20 30 40 50 60 70 80
Retention Time in Minutes

Liquid Chromatography – Organic Carbon Detection (LC-OCD), Fig. 1 Typical LC-OCD chromatogram of NOM
in surface water (DOC-Labor 2006)

times. In principle, the analysis technique is as
follows: (1) injection of buffered particle-free
water sample to a chromatographic column to
separate fractions of NOM, (2) nondestructive
UV detection at 254 nm wavelength, (3) organic
carbon detection based on high-sensitivity TOC
analysis, and (4) simultaneous detection of
organic nitrogen in bypassed samples after the
UV detector (see detailed specifications by
Huber et al. 2011). The chromatogram data gen-
erated by the three detectors are processed using a
customized software program (ChromCALC,
DOC-Labor, Karlsruhe) to calculate organic car-
bon concentrations of biopolymers, humic sub-
stances, building blocks, low molecular weight
(LMW) acids, and neutrals fractions of NOM
based on area integration of the fractional peaks.
The lower limit of detection of this technique was
reported to be in the low-ppb range for individual
fractions (Huber and Frimmel 1991). The typical
size ranges and chromatograms of the different
NOM fractions detectable by LC-OCD are shown
in Table 1 and Fig. 1, respectively.
Liquid Chromatography – Organic Carbon Detection (LC-OCD)
Cross-References
▶ Extracellular Polymeric Substance (EPS)
▶ Humic Substances
▶ Natural Organic Matter
▶ Organic Fouling
▶ Size Exclusion Chromatography
▶ Transparent Exopolymer Particles (TEP)
References
Amy GL, Salinas-Rodriguez SG, Kennedy MD, Schippers
JC, Rapenne S, Remize P-J, Barbe C, Manes CLDO,
West NJ, Lebaron P, Kooij DVD, Veenendaal H,
Schaule G, Petrowski K, Huber S, Sim LN, Ye Y,
Chen V, Fane AG (2011) Water quality assessment
tools. In: Drioli E, Criscuoli A, Macedonio F (eds)
Membrane-based desalination – an integrated
approach (MEDINA). IWA Publishing, New York,
pp 3–32
Batsch A, Tyszler D, Br€ ugger A, Panglisch S, Thomas
M (2005) Foulant analysis of modified and unmodified
membranes for water and wastewater treatment with
LC-OCD. Desalination 178:63–72
DOC-Labor (2006) LC-OCD – Liquid chromatography
Organic Carbon Detection. Information Brochure
1/2006
Frimmel FH, Saravia F, Gorenflo A (2004) NOM removal
from different raw waters by membrane filtration.
Water Sci Technol Water Supply 4:165–174
Henderson RK, Subhi N, Antony A, Khan SJ, Murphy KR,
Leslie GL, Chen V, Stuetz RM, Le-Clech P (2011)
Evaluation of effluent organic matter fouling in ultra-
filtration treatment using advanced organic character-
isation techniques. J Membr Sci 382:50–59
Huang G, Meng F, Zheng X, Wang Y, Wang Z, Liu H,
Jekel M (2011) Biodegradation behavior of natural
organic matter (NOM) in a biological aerated filter
(BAF) as a pretreatment for ultrafiltration (UF) of
river water. Appl Microbiol Biotechnol 90:1795–1803
Huber SA (1998) Evidence for membrane fouling by
specific TOC constituents. Desalination 119:229–234
Huber SA, Frimmel FH (1991) Flow injection analysis for
organic and inorganic carbon in the low-ppb range.
Anal Chem 63:2122–2130
3
Huber SA, Frimmel FH (1994) Direct gel chromato-
graphic characterization and quantification of marine
dissolved organic carbon using high-sensitivity DOC
detection. Environ Sci Technol 28:1194–1197
Huber SA, Balz A, Abert M, Pronk W (2011) Character-
isation of aquatic humic and non-humic matter with
size-exclusion chromatography – organic carbon
detection – organic nitrogen detection
(LC-OCD-OND). Water Res 45:879–885
Jiang T, Kennedy MD, DeSchepper V, Nam S-N,
Nopens I, Vanrolleghem PA, Amy G (2010) Charac-
terization of soluble microbial products and their foul-
ing impacts in membrane bioreactors. Environ Sci
Technol 44:6642–6648
Kennedy MD, Chun HK, Yangali-Quintanilla VA,
Heijman BGJ, Schippers JC (2005) Natural organic
matter (NOM) fouling of ultrafiltration membranes:
fractionation of NOM in surface water and character-
isation by LC-OCD. Desalination 178:73–83
Kennedy MD, Kamanyi J, Heijman BGJ, Amy G (2008)
Colloidal organic matter fouling of UF membranes:
role of NOM composition %26 size. Desalination
220:200–213
Villacorte LO, Kennedy MD, Amy G, Schippers JC
(2009) The fate of transparent exopolymer particles
(TEP) in integrated membrane systems: removal
through pretreatment processes and deposition on
reverse osmosis membranes. Water Res 43:5039–5052
Villacorte LO, Schurer R, Kennedy MD, Amy G,
Schippers JC (2010) The fate of transparent
exopolymer particles in integrated membrane systems:
a pilot plant study in Zeeland, The Netherlands. Desa-
lination Water Treat 13:109–119
Villacorte LO, Ekowati Y, Winters H, Amy GL, Schippers
JC, Kennedy MD (2012) Characterisation of transpar-
ent exopolymer particles (TEP) produced during algal
bloom: a membrane treatment perspective. Desalin
Water Treat. doi:10.1080/19443994.2012.699359
Zheng X, Ernst M, Jekel M (2009) Identification and
quantification of major organic foulants in treated
domestic wastewater affecting filterability in dead-
end ultrafiltration. Water Res 43:238–244
Zheng X, Ernst M, Jekel M (2010) Pilot-scale investiga-
tion on the removal of organic foulants in secondary
effluent by slow sand filtration prior to ultrafiltration.
Water Res 44:3203–3213
S
Solubility and Partitioning
Maria Grazia De Angelis
Dipartimento di Ingegneria Civile, Chimica,
Ambientale e dei Materiali, Universitá di
Bologna, Bologna, Italy
When a solute is added to two immiscible
(or partially miscible) phases, it will distribute
unevenly between them, giving rise to the so-
called solute partitioning between the phases.
The distribution of a solute among coexisting
phases, in particular liquid phases, is a pheno-
menon of industrial importance in several purifi-
cation processes such as liquid extraction,
partition chromatography, etc.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_717-1
In membrane processes the partitioning occurs
between the fluid phase (feed, permeate) and the
membrane phase.
Partitioning of the solute i between the solute
(I) and membrane (II) phase can be defined with
the partition or distribution coefficient Ki,I/II
defined as the ratio between the concentration
(solubility) of solute in the membrane phase and
the concentration (solubility) of solute in the
external phase, that is normally lower than unity:
Ci, I
K i, I=II ¼
Ci, II
Partition coefficient of solute i between phase
I and phase II.
M
Membrane Distributor
Juergen Caro
Institute of Physical Chemistry and
Electrochemistry, Leibniz University Hannover,
Hannover, Germany
Synonyms
Distributor Reactor
A membrane distributor is a special type of a
membrane reactor with “distributed” feeding,
i.e., one or several reactants are fed through a
membrane to the reaction zone (Dittmeyer and
Caro 2008; Caro 2010). In general, a selectivity
increase can be expected. On the one hand, a
more uniform concentration of the dosed reac-
tants can be expected. On the other hand, also a
nonuniform but specific shape of a concentration
profile can be realized which can be beneficial for
kinetic reasons. Further, the total amount of reac-
tants that can be supplied without exceeding the
threshold for safe operation can also be increased.
One additional effect observed when applying a
distributed feed along the reactor is an increasing
flow rate downstream which shortens the contact
time on catalytic sites.
The concept of “membrane distributor reac-
tor” does not necessarily require a selective mem-
brane, provided that the transmembrane flux can
be properly controlled by the differential
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_718-5
pressure. Therefore, the distributed feeding can
be either (i) selective or (ii) nonselective:
(i) Selective supply: There are numerous exam-
ples for the selective feed supply. Examples
are the hydrogen supply through a hydrogen-
selective membrane (Pd, zeolite, MOF,
carbon, etc.) in partial hydrogenations or
the oxygen supply through an oxygen-
selective membrane (perovskite, other
oxygen-transporting ceramics) in partial
hydrocarbon oxidations. In both cases,
improved selectivities can be expected
since the hydrogenations or oxidations take
place at constant and low hydrogen/oxygen
partial pressure in, e.g., axial direction of a
tubular membrane reactor.
(ii) Nonselective supply: In the strong sense of a
membrane reactor, only the selective feeding
fulfills the definition of a membrane reactor
as a device combining membrane-based sep-
aration and a chemical reaction in one unit
(Koros et al. 1996). However, also in this
case, the transmembrane flux can be tuned
by the pressure difference, thus controlling
the partial pressure of the reactants resulting
in a higher selectivity. As an example,
porous membranes can be used to distribute
oxygen or air in a nonselective manner to the
reactor providing a low and uniform oxygen
partial pressure along the reactor. This
avoids large differences in the reaction rate
and selectivity along the reactor. The use of
2 Membrane Distributor
porous membranes as air distributor is usu-
ally not combined with an oxygen
enrichment.
References
Caro J (2010) Basic aspects of membrane reactors. In:
Drioli E, Giorno L (eds) Comprehensive membrane
science and engineering, vol 3. Elsevier, Amsterdam,
pp 1–108
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
In: Ertl G, Knözinger H, Sch€
uth F, Weitkamp J (eds)
Handbook of heterogeneous catalysis. Wiley-VCH,
Weinheim, pp 2198–2248
Koros WJ, Ma YH, Shimidzu T (1996) Terminology for
membranes and membrane processes. Pure Appl
Chem 68:1479–1489
M
Membrane Extractor
as a Configuration of Membrane
Reactor
Juergen Caro
Institut f€
ur Physikalische Chemie und
Elektrochemie der Leibniz, Universität
Hannover, Hannover, Germany
Numerous practice-relevant reactions like dehy-
drogenations, esterifications, steam reforming
Knoevenagel condensation, or thermal water
splitting take place in industry under thermody-
namic control. This means, there exists an equi-
librium between products and educts due to A +
B $ C + D defined by rRG = RT lnK with rRG
as the Gibbs Energy (Free Enthalpy) of the reac-
tion and K as the equilibrium constant. The
“membrane extractor” concept is based on the
selective in situ extraction of one or of both
products C and/or D under equilibrium controlled
reaction condition from the feed A, B. The main
advantage of this concept is an enhancement of
the conversion and increase of the yield
(Dittmeyer and Caro 2008; Caro 2010). By the
removal of C and/or D, sometimes also the selec-
tivity is influenced.
The reaction must be sufficiently fast com-
pared to the mass transport through the mem-
brane, a feature called “kinetic compatibility.”
Higher conversion – and thus yield – due to the
beneficial effect of product removal may lead to
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_719-3
savings on energy and raw materials, especially if
the component removed through the membrane is
pure enough for further applications. Histori-
cally, the selective hydrogen removal in alkane
dehydrogenations to the corresponding olefins
thus overriding the equilibrium constraint was
the most studied membrane extractor case. The
most prominent “membrane extractor reactors”
studied at present are reformers for the produc-
tion of fuel-cell-grade hydrogen from hydrocar-
bons or alcohols using Pd-based membranes. The
removal of water through hydrophilic mem-
branes in esterifications is another prominent
example of “membrane extractor reactors.”
Besides conversion enhancement, also selec-
tivity increase can take place in membrane
extractors. For example, in Fischer–Tropsch syn-
thesis, the removal of the by-product water has
several advantages on the reactor performance
like reduced catalyst deactivation or lowered
kinetic inhibition.
References
Caro J (2010) Basic aspects of membrane reactors. In:
Drioli E, Giorno L (eds) Comprehensive membrane
science and engineering, vol 3. Elsevier, Amsterdam,
pp 1–108
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
In: Ertl G, Knözinger H, Sch€
uth F, Weitkamp J (eds)
Handbook of heterogeneous catalysis. Wiley-VCH,
Weinheim, pp 2198–2248
M
Membrane Swelling
Annarosa Gugliuzza
Institute on Membrane Technology - Research
National Council, ITM-CNR, Rende (CS), Italy
Slow diffusion of solvents into polymer chains
causes a swelling phenomenon and leads to a
swollen polymeric membrane (Fig. 1). In this
case, an expansion of the polymer network is
promoted because polymer-polymer interactions
are over polymer-solvent forces and a complete
dissolution of the membrane is prevented
(Billmeyer 1984).
Different degrees of swelling can be achieved
depending on cross-linking, crystallinity, as well
as intermolecular forces involved. The choice of
the materials and their combination can direct the
swelling events and make the membrane perfor-
mance addressable at macroscopic level (Barton
1983). Membrane swelling over an area of 1 mm2
is indicated as a bulk swelling, while small
changes in dimension are classified as a micro-
scopic swelling and are detectable by small-angle
X-ray scattering (SAXS).
The macroscopic swelling is usually calcu-
lated by gravimetric measurements according to
this relation:
m  m0
Gð
=
Þ ¼
100
m0
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_720-6
where G is the percentage of swelling, m the mass
of the wet membrane, and m0 the mass of the dry
membrane. The gravimetric method is, however,
somewhat limited and inadequate when slow
anisotropic swelling equilibrium is reached or
swelling kinetics need to be detected in real-
time. In this case, in situ detection of the dimen-
sional membrane is requested when moving from
dry to wet state (Izak et al. 2007).
Robust network architectures of swelled
membranes with high surface-to-volume ratio
are generated when swelling takes place
along three directions, x, y, and z. This physical
expansion can be estimated by using the
following relation:
l  l0
tð
=
Þ ¼
100 (2)
l0
where t is the percentage of the membrane
dimension; l the dimension of the wet membrane
along the x, y, or z axis; and l0 the dimension of
dry membrane along the considered axis
(Gugliuzza and Drioli 2007). The swelling can
be isotropic when the expansion is equal in all
directions, whereas differential dimensional
changes in the plane (x, y) or along the vertical
axis (z) to the plane lead to an anisotropic swell-
ing (Fig. 2).
Reversible swelling is called as a deswelling.
(1) The cycle of swelling-deswelling is a mechanical
work, which is often used in actuation and
2 Membrane Swelling

Membrane Swelling,
Fig. 1 Reversible Shrinking Swelling
expansion and shrinking of
polymer chains after
solvent adsorption/
desorption

Solvent Polymer

x
Isotropically swollen system Original system Anisotropically swollen system

Membrane Swelling, Fig. 2 Isotropic and anisotropic expansion of 3D polymeric networks along three axes
(x, y, and z)

biosensing and drug delivery. In this case, References

switching swollen polymers are indicated as
smart gels (Diaconu et al. 2012).
In dense membranes, a large sorption of mol-
ecules can induce swelling of the matrix leading
to an increase in free volume. Higher mobility of
the polymer chains reduces the discriminating
power of the membrane, causing plasticization
when macroscopic segmental motion occurs. In
porous membranes, macroscopic swelling could
lead to an increase in the polymer volume with
closure of porous structures and subsequent
abatement of the flux.
Barton AFM (1983) Handbook of solubility parameters
and other cohesion parameters. CRC Press, Boca
Raton
Billmeyer FW Jr (1984) Textbook of polymer science.
Wiley, New York
Diaconu G, Gugliuzza A, Schäfer T (2012) Characteriza-
tion of PAA/PDDA-based stimuli responsive mem-
branes. Procedia Eng 44:1260–1261
Gugliuzza A, Drioli E (2007) PVDF and HYFLON AD
membranes: ideal interfaces for contactor applications.
J Membr Sci 300:51–62
Izak P, Hovorka S, Bartovský T, Bartovská L, Crespo JG
(2007) Swelling of polymeric membranes in room
temperature ionic liquids. J Membr Sci 296:131–138
M
Membrane-Cryogenic Hybrid
Processes
Marco Scholz
Aachener Verfahrenstechnik - Chemical Process
Engineering, RWTH Aachen University,
Aachen, Germany
Membrane-cryogenic hybrid processes are pro-
cesses in which membrane technology and con-
densation equipment are combined to achieve a
gas separation. This type of process is particu-
larly efficient, when at least one component is
condensable. Water vapor and higher hydrocar-
bons are typical gases which can easily be
removed from permanent gases by condensation
separation.
Membrane-cryogenic processes are particu-
larly interesting when the components which are
easy to liquefy permeate faster through the mem-
brane. Here only a fraction of the feed gas has to
be chilled. Concerning water almost all mem-
brane materials can be applied. When vapors are
to be separated, rubbery membrane materials
should be applied, as the vapor components will
permeate faster through the membrane.
The separation in a gas permeation module is
determined by kinetics, while the condensation
separation is governed by thermodynamic equi-
librium. Hence, the outlet concentration of the
condensable components from the condensation
equipment is determined by the vapor-liquid
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_721-6
equilibrium only. It is mainly determined by tem-
perature and pressure. Often, the concentrations
of the condensable components are low com-
pared to the concentration of the permanent
gases, and, thus, the vapor-liquid equilibrium
can be considered as independent of
concentration.
Two types of membrane-cryogenic processes
can be realized when vapor permeates faster
through the membrane than permanent gases. In
the first process, the membrane unit performs the
main separation, but the permanent gases which
should be rejected by the membrane also perme-
ate through the membrane. In order to enhance
the recovery of the permanent gases, chilling
equipment is applied on the permeate side.
Hence, the condensable gases will be removed
from the permeate gas and the permanent gases
will be recycled.
In the second process, the chilling unit and the
gas permeation unit are connected in series. The
chilling unit performs the bulk separation, and the
gas is further polished in the subsequent gas per-
meation unit. The permeate stream of the gas
permeation module is enriched in condensable
components, and this stream is recycled to the
chilling unit. Hence, the inlet concentration is
increased and the quantity of components which
are condensed increases.
2 Membrane-Cryogenic Hybrid Processes
Examples of Membrane-Cryogenic
Hybrid Processes
The separation of propylene and nitrogen is effi-
ciently done applying a hybrid process in which
cryogenic separation and membrane modules are
combined (Baker et al. 1998). Rubbery mem-
branes are used and propylene selectively perme-
ates through the membrane. In this process both
the propylene and the nitrogen are to be recov-
ered at high purities. The propylene is obtained
from condensation equipment in liquid state so
that it has a high purity. The nitrogen purity is
controlled by a gas permeation module.
Follmann investigated membrane-cryogenic
hybrid processes for carbon dioxide capture
(Follmann 2010). Here, chilling and gas perme-
ation membranes are combined to separate car-
bon dioxide and nitrogen in a postcombustion
process. However, driving this hybrid process
requires more energy than the conventional
amine absorption process.
In the purification of steam cracking products,
mixtures of mainly hydrogen, carbon monoxide,
methane, and ethylene have to be separated. The
hydrogen can be separated in a gas permeation
unit where the hydrogen selectively permeates
through the membrane (Hopkins et al. 1987).
The hydrogen-lean retentate stream is polished
in a subsequent cryogenic separation.
Air can be used to produce both high-purity
argon and nitrogen (Thorogood et al. 1991).
A chilling unit supplies two streams. One is
enriched in nitrogen and the other is enriched in
oxygen and argon. A gas permeation unit is
applied to separate oxygen and argon. Here, the
argon preferentially permeates through the mem-
brane, and at least two membrane stages are
required to obtain high argon purities.
References
Baker RW, Wijmans JG, Kaschemekat JH (1998) The
design of membrane vapor-gas separation systems.
J Membr Sci 151:55–62
Follmann PM (2010) Membrane gas separation processes
for post combustion CO2 caputre from coal fired power
plants, PhD-Thesis. RWTH Aachen University,
Aachen
Hopkins JA, DiMartino SP, Nicholas DM (1987) Hybrid
membrane/cryogenic process for hydrogen purifica-
tion, US Patent 4654047
Thorogood RM, Tsai W, Weimer RF, Ying DHS
(1991) Hybrid membrane-cryogenic generation of
argon concurrently with nitrogen, US Patent 5049174
O
Oxygen-Enriched Air (OEA)
Production by Membrane Reactors
Juergen Caro
Institut f€
ur Physikalische Chemie und
Elektrochemie der Leibniz, Universität
Hannover, Hannover, Germany
Air with increased oxygen content has different
applications ranging from sub-aqua diving and
medical treatments to processes like waste burn-
ing, FCC catalyst regeneration, preparation of
synthesis gas for ammonia production, Claus
plants, and high-temperature furnaces and kilns.
The reduction of the inert nitrogen as a ballast is
of advantage in several processes. When increas-
ing the oxygen content of air from 21 % to 30 %,
there is 40 % less nitrogen per oxygen unit, and
membranes of modest selectivity (3–5) and
higher oxygen flux are preferred.
OEA can be produced by mixing air with pure
oxygen from cryogenic air distillation after Linde
or by pressure swing adsorption. Membranes can
produce OEA in two different ways:
(i) There exists a variety of commercial organic
polymer membranes with a preferential oxy-
gen transport. Since oxygen has a slightly
smaller molecule size and it undergoes less
interaction than the quadrupolar nitrogen,
oxygen (plus carbon dioxide + water vapor)
permeates faster through the polymer film
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_728-4
than nitrogen and argon. This can be used
to produce nitrogen as retentate on the high-
pressure side and an oxygen-enriched air on
the low pressure permeate side. If the target
product is nitrogen on the high-pressure feed
side, the oxygen-enriched permeate is called
“waste gas.” It is estimated that for an oxy-
gen purity of 30 % and a capacity
<15,000 Nm3/h, the investment, operating,
and maintaining costs are two thirds to three
fourths of cryogenic and PSA technology.
Often, the spiral wound geometry is pre-
ferred and the pressure difference across the
membrane is maintained by a vacuum pump
on the permeate or a compressor/van on the
feed side (Puri 2011).
(ii) Recently, perovskite-type high-temperature
ceramic membranes have been proposed for
OEA production (Liang and Caro 2011).
Here the fee is slightly pressurized air of
about 2 bar (O2 partial pressure  0.4 bar).
As sweep gas, air of typically 1 bar (O2
partial pressure  0.2 bar) is applied.
Because of the difference in oxygen partial
pressure, there is an oxygen transport from
the feed to the permeate side until the O2
partial pressure on the permeate side also
reaches 0.4 bar, which is air with 40 % O2
at 1 bar (Wang et al. 2005; Hamel
et al. 2006).
2 Oxygen-Enriched Air (OEA) Production by Membrane Reactors
References
Hamel C, Seidel-Morgenstern A, Schiestel T, Werth S,
Wang HH, Tablet C, Caro J (2006) Experimental and
modeling study of the O2-enrichment by perovskite
fibers. AIChE J 52:3118–3125
Liang F, Caro J (2011) Perovskite membranes for high-
temperature oxygen separation. In: Drioli E, Barbieri
G (eds) Membrane engineering for the treatment of
gases. RSC Publishing, Cambridge, pp 192–222
Puri PS (2011) Commercial applications of membranes in
gas separations. In: Drioli E, Barbieri G (eds) Mem-
brane engineering for the treatment of gases. RSC
Publishing, Cambridge, pp 215–244
Wang HH, Werth S, Schiestel T, Caro J (2005) Perovskite
hollow-fiber membranes for the production of oxygen-
enriched air. Angew Chem Int Ed 44:6906–6909
O
Oil-Water Emulsion
Na Li
Department of Chemical Engineering, School of
Chemical Engineering and Technology, Xi’an
Jiaotong University, Xi’an city, China
Oil-water emulsion is a dispersion of one liquid in
another one with which it is immiscible or poorly
miscible. Liquids are normally an organic phase
(an “oil”) and an aqueous solution (a “water”),
respectively. The dispersed liquid is present in
the form of droplets in the continuous phase.
Direct emulsions are composed of droplets of an
organic liquid dispersed in an aqueous solution
(O/W), while inverse emulsions are composed of
aqueous droplets dispersed in an organic liquid
(W/O). Emulsions play an important role in the
formulation of various products such as foods;
examples of O/W emulsions are dressings, artifi-
cial milks, cream liqueurs, etc., and examples of
W/O emulsions are margarines and low-fat
spreads. In addition, there are numerous nonfood
emulsions like ore and petroleum recovery,
cleaning and polishing, pharmaceutical products,
cosmetics, pesticides for crop protection, bitu-
men (for road application), water-based paints,
photographic films, paper coatings, textiles,
leather, etc (Nazir et al. 2010).
Emulsions are thermodynamically unstable
systems, that is to say, their free energy of forma-
tion is greater than zero, and as such will show a
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_730-4
tendency to break (Capek 2004). Instability of
emulsion occurs by creaming and coalescence.
Creaming is exhibited if the two phases differ in
specific gravity and if the emulsion particles are
so large initially, or grow to such a size, that they
are not responsive to Brownian movement. Coa-
lescence of emulsion particles is often irrevers-
ible and is a case of true instability. Coalescence
occurs when the interfacial film ruptures at the
point of juncture of two particles of the discon-
tinuous or internal phase. It may be reversible if a
relatively large proportion of emulsifier is
employed and if the emulsifier has been chosen
so as to afford the greatest ease of emulsification
(Grayson et al. 1979). A most successful method
used to choose proper emulsifying agents for a
given system is HLB method. The HLB stands
for hydrophile-lipophile balance. HLB number is
assigned to each surface-active agent. Those
materials with HLB numbers in the range of 4–6
are suitable as emulsifiers for W/O emulsion,
while only those with HLB numbers in the
range 8–18 are suitable for the preparation of
O/W emulsion.
In the evaluation of emulsions, there are a
number of fairly standardized measurements.
For surface and interfacial tension, the measure-
ments include capillary-height method, drop-
weight method, ring method, etc. The viscosity
of an emulsion is an important factor in determin-
ing its stability as well as from the point of view
of ultimate use. Viscosity measurements may
also be a guide to the type of emulsion (O/W or
2 Oil-Water Emulsion
W/O). Three basic methods of viscosity measure-
ment are capillary tube methods, falling ball
methods, and rotational methods. It is important
to determinate the type of emulsion. Unfortu-
nately, an unequivocal determination may not
always be possible, and deductive reasoning
based on the data obtained from several methods
may be required. Desired information may be
obtained from five classic methods: dye solubility
method, phase dilution method, conductivity
method, fluorescence method, and wetting of fil-
ter paper. In studies of the stability of emulsions,
the change in the particle-size distribution with
time is often an important datum. There are, in
general, four distinct methods by which this
information may be obtained, i.e., by microscopic
observation, by various sedimentation tech-
niques, by light-scattering measurements, and
by instrumental counting (Becher 1965).
The emulsion is prepared by mechanical dis-
ruption of the dispersed phase into the continuous
phase. Conventional methods apply shear and
extensional stresses to the product. Popular
types of equipments are colloid mills, rotor-stator
systems, high-pressure homogenizers, and ultra-
sonic homogenizers, and these systems show
poor control over droplet size and distribution.
New methods for emulsification using
microstructured systems like membrane
emulsification and microchannel emulsification
have received much attention. For membrane
emulsification, two methods of operation are
used: cross-flow membrane emulsification and
premix membrane emulsification. In cross-flow
membrane emulsification, the emulsion is formed
by pushing the to-be-dispersed phase through a
membrane into the cross-flowing continuous
phase. Ideally, droplet size can be controlled pri-
marily by the choice of the membrane, the cross-
flow velocity, and the transmembrane pressure.
Contrary to cross-flow emulsification, premix
emulsification can be used to produce emulsions
with high dispersed phase fraction, albeit that the
size of the droplets is not as monodisperse as for
cross-flow emulsification (Nazir et al. 2010).
References
Becher P (1965) Emulsions-theory and practice, 2nd edn.
American Chemical Society, New York, pp 382–420
Capek I (2004) Degradation of kinetically-stable O/W
emulsions. Adv Colloid Interface 107:125–155
Kirk-Othmer (1979) Encyclopedia of chemical technol-
ogy. In: Grayson M, Eckroth D, Bickford M, Bushey
GJ, Eastman CL, Klingsberg A, Spiro L (eds) Diuretics
to emulsions, 3rd edn. Wiley, New York, p 900
Nazir A, Schroën K, Boom R (2010) Premix emulsifica-
tion: a review. J Membr Sci 362:1–11
O
Olefin and Paraffin Separation
A. Baudot
Physics and Analysis Division, IFP Energies
nouvelles, Solaize, France
Light olefins (alkenes), such as ethylene and pro-
pylene, are base chemical intermediates that are
used for the production of raw chemicals and
polymers. Those olefins are separated industrially
from their paraffin (alkane) counterpart in very
energy-consuming distillation operations. Mem-
brane separation could possibly constitute an
attractive highly modular and less energy-
consuming alternative option for olefin/paraffin
separation.
Since more than 20 years, the performances of
a very wide array of membrane materials for
olefin/paraffin separation have been studied at
lab scale mainly by academic teams. We provide
here a brief overview of the advantages and limits
of each membrane material family. For further
reading, extensive and detailed reviews
concerning the use of several types of membrane
materials for olefin/paraffin separation can be
found in various recent papers (Ravanchi
et al. 2009; Burns and Koros 2003; Azhin
et al. 2008).
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_731-2
Glassy Polymer Membranes
If compared to other glassy polymers offering
molecular sieving properties, phenylene
polyoxide offers the “best” selectivity/permeabil-
ity compromise for ethylene/ethane separation
(Tanaka et al. 1996; Ilinitch et al. 1992).
Concerning propylene/propane separation,
4,40 -hexafluoroisopylidenediphtalic dianhydride
(6-FDA)-based aromatic polyimides favor two
conditions that explain why, for comparable
selectivity values, such fluorinated polyimides
display higher permeabilities toward propylene
than the other types of polymers (Hoehn 1974):
– Rigid polymer chains that promote molecular
sieving selectivity. This can be achieved if the
monomers are connected to each other via
multiple chemical bonds – in order to limit
free rotation of monomers – and if the polymer
chains are mainly constituted of aromatic
groups
– High free volume in order to favor the perme-
ation of the fastest permeating compound
Facilitated Transport Membranes
Initially, academic research on ionic metal olefin-
selective facilitated transport membranes was
focused on liquid membranes, whether
immobilized liquid membranes containing silver
nitrate (Teramoto et al. 1989; Ravanchi
2 Olefin and Paraffin Separation
et al. 2009) or solvent-swollen membranes (Yang
and Hsiue 1996). The selectivity of this type of
membrane materials is based on a reversible spe-
cific interaction of the pi electrons of olefins with
certain metal ions, such as ionic silver, dissolved
in the polymer matrix, which results in facilitated
olefin transport of the ion-olefin coupling through
the membrane. Though offering good olefin/par-
affin separation performances at lab scale, those
materials were subject to a loss of solvent by
evaporation, which resulted in dramatic fall of
olefin/paraffin separation performances.
In the latter years, new attention was paid at
promising ionic silver-impregnated solid-state
polyelectrolyte membranes based on PVP, PAZ,
or PEO polymer which were not suffering from
desiccation phenomena when flowing dry gases
(Kim et al. 2002). Though the first results based
on pure compounds were very promising, i.e., an
ideal separation propylene/propane factor as high
as 15,000 (Kim et al. 2002), the mixed selectivity
of those types of materials was lower by orders of
magnitude (Kim et al. 2003). This significant
discrepancy between the ideal and the mixture
could be mainly attributed to a swelling-induced
plasticization of the membrane materials by short
olefins and paraffins (Ko et al. 2009).
Carbon Membranes
Carbon membranes are prepared by pyrolizing
polymeric precursors. The pyrolisis aims at
(1) enhancing the molecular sieving properties
of the processed polymer and (2) rendering
them less sensitive to plasticization. When they
are carbonized at high temperatures, the polymer
chains tend to transform to an inorganic structure
and the transfer mechanism of sorbents inside the
membrane materials switches from a solution-
diffusion mechanism to a molecular sieving
mechanism.
The main limit of carbon membranes is their
brittleness, resulting practically in a poor
mechanical strength (Yoshino et al. 2003). Sev-
eral authors managed to keep the pyrolized mem-
brane materials flexible by incorporating pendant
sulfonic acid groups in the precursor polymer and
keeping the pyrolisis temperature sufficiently low
in order to allow the decomposition of the sul-
fonic acid groups without decomposing the skel-
eton of the polymer matrix (Islam et al. 2005).
Zeolite Membranes
Several studies concerning the separation of pro-
pylene from propane base on faujasite (FAU zeo-
lite) membranes (Nikolakis et al. 2001) or
titanosilicate ETS (Tiscornia et al. 2008) have
been published recently. The olefin/paraffin
selectivity of all those materials was comparable
to glassy polymers and always below 10.
References
Azhin M, Kaghazchi T, Rahmani M (2008) A review on
olefin/paraffin separation using reversible chemical
complexation technology. J Ind Eng Chem
14(5):622–638
Burns RL, Koros WJ (2003) Defining the challenges for
C3H6/C3H8 separation using polymeric membranes.
J Membr Sci 211:299–309
Hoehn HH (1974) Treatment of membranes of selected
polyimides. US Patent 3,822,202
Ilinitch OM, Semin GL, Chertova MV, Zamaraev KI
(1992) Novel polymeric membranes for separation of
hydrocarbons. J Membr Sci 66:1–8
Islam MN, Zhou WL, Honda T, Tanaka K, Kita H,
Okamoto K (2005) Preparation and gas separation
performance of flexible pyrolytic membranes by
low-temperature pyrolysis of sulfonated polyimides.
J Membr Sci 261:17–26
Kim JH, Min BR, Kim CK, Won J, Kang YS (2002) New
insights into the coordination mode of silver ions
dissolved in poly(2-ethyl-2-oxazoline) and its relation
to facilitated olefin transport. Macromolecules
35:5250–5255
Kim JH, Min BR, Kim HS, Won J, Kang YS (2003) Facil-
itated transport of ethylene across polymer membranes
containing silver salt: effect of HBF4 on the photore-
duction of silver ions. J Membr Sci 212:283–288
Ko D, Kim JH, Kang SW, Lee DH, Won J, Kang YS
(2009) Propylene-induced plasticization in silver poly-
mer electrolyte membranes. J Ind Eng Chem 15:8–11
Nikolakis V, Xomeritakis G, Abibi A, Dickson M,
Tsapatsis M, Vlachos DG (2001) Growth of a
faujasite-type zeolite membrane and its application in
the separation of saturated/unsaturated hydrocarbon
mixtures. J Membr Sci 184:209–219
Ravanchi MT, Kaghazchi T, Kargari A (2009) Applica-
tion of membrane separation processes in petrochem-
ical industry: a review. Desalination 235:199–244
Olefin and Paraffin Separation
Tanaka K, Taguchi A, Hao JQ, Kita H, Okamoto K (1996)
Permeation and separation properties of polyimide
membranes to olefins and paraffins. J Membr Sci
121:197–207
Teramoto M, Matsuyama H, Yamashiro T, Okamoto
S (1989) Separation of ethylene from ethane by a
flowing liquid membrane using silver-nitrate as a car-
rier. J Membr Sci 45:115–136
Tiscornia I, Irusta S, Tellez C, Coronas J, Santamaria
J (2008) Separation of propylene/propane mixtures
by titanosilicate ETS-10 membranes prepared in
3
one-step seeded hydrothermal synthesis. J Membr Sci
311:326–335
Yang JS, Hsiue GH (1996) Novel dry poly
[(1-trimethylsilyl)-1-propyne]-AgClO4 complex
membranes for olefin/paraffin separations. J Membr
Sci 120:69–76
Yoshino M, Nakamura S, Kita H, Okamoto K, Tanihara N,
Kusuki Y (2003) Olefin paraffin separation perfor-
mance of carbonized membranes derived from an
asymmetric hollow fiber membrane of 6FDA/BPDA-
DDBT copolyimide. J Membr Sci 215:169–183
O
Oriented Immobilized Anti-hIgG via
Fc Fragment-Imprinted Cryogels
Nilay Bereli, Handan Yavuz and Adil Denizli
Department of Chemistry, Biochemistry
Division, Hacettepe University, Ankara, Turkey
Antibodies exhibit unique binding properties,
high affinity and specificity towards a wide
range of natural and synthetic targets. Because
of these properties, antibodies are utilized in
many applications including therapeutics, diag-
nostics, research in biology and biotechnology,
immunoaffinity chromatography, etc. (Huse
et al. 2002). For medical applications, immuno-
globulins (IgGs) have been purified using a com-
bination of various methods like precipitation and
chromatographic techniques including hydropho-
bic interaction, histidine affinity, ion exchange,
dye affinity, and metal-chelate affinity
(Tishchenko et al. 2002; Yavuz and Denizli
2005; Denizli 2011). Antibody immobilization
is an important step in the preparation of chro-
matographic immunoaffinity column. The recog-
nition part of the antibody has to be accessible to
maintain the antibody’s functionality and to
detect the analyte molecule. Therefore, during
immobilization, the proper orientation of anti-
bodies on the surface of the solid support is cru-
cial (Batalla et al. 2008). There are some more
specific techniques using immobilized protein
A or G for the immobilization of antibodies by
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_732-1
the Fc region. These are more efficient techniques
resulting to the oriented immobilization of anti-
bodies and thus giving rise to highly accessible
antigen-binding sites on the antibody and
increase in the activity of the immobilized anti-
body molecule (Hober et al. 2007). However,
despite their general use as effective ligands for
the oriented immobilization of antibodies, they
have some drawbacks in their economical value,
reusability, and concerns over the clearance of
leached ligand (Low et al. 2007). Small antibody
fragments can be evaluated as simple, inexpen-
sive, more stable, general purpose ligands to be
an alternative to protein A or G. In combination
with an oriented immobilization method, these
small antibody fragments allow an increased
degree of immobilization of well-oriented and
active antibodies per solid support surface area,
hence facilitating higher antibody–antigen com-
plex formation (Bonroy et al. 2006). Fc fragment-
imprinted poly(hydroxyethyl methacrylate)
cryogel (MIP) can be used for the oriented immo-
bilization of anti-hIgG for IgG purification from
human plasma. Non-imprinted poly
(hydroxyethyl methacrylate) cryogel (NIP) can
be also used for random immobilization of anti-
hIgG to compare the adsorption capacities of
oriented (MIP/anti-hIgG) and random (NIP/anti-
hIgG) cryogel columns. IgG adsorption capacity
is found to be three times higher than the NIP/
anti-hIgG column (29.7 mg/g) for the MIP/anti-
hIgG column (86.9 mg/g) (Fig. 1). Higher IgG
adsorption capacity was observed from human
2 Oriented Immobilized Anti-hIgG via Fc Fragment-Imprinted Cryogels
Oriented Immobilized
Anti-hIgG via Fc
Fragment-Imprinted
Cryogels, Fig. 1 IgG
adsorption amounts of
MIP/anti-hIgG (oriented)
and NIP/ anti-hIgG
(random) cryogel (Bereli
et al. 2013)
plasma (up to 106.4 mg/g) with the MIP/anti-
hIgG cryogel column. The results obtained are
promising and show that Fc fragments of anti-
bodies with an oriented immobilization method
can be considered as a potential candidate for IgG
purification human plasma (Bereli et al. 2013).
References
Batalla P, Fuentes M, Mateo C, Grazu V, Fernandez-
Lafuente R, Guisan JM (2008) Covalent immobiliza-
tion of antibodies on finally inert support surfaces
through their surface regions having the highest den-
sities in carboxyl groups. Biomacromolecules
9:2230–2236
Bereli N, Ert€urk G, Tumer MA, Say R, Denizli A (2013)
Oriented immobilized anti-hIgG via Fc fragment-
imprinted PHEMA cryogel for IgG purification.
Biomed Chromatogr 27:599–607
Bonroy K, Frederix F, Reeksmans G, Dewolf E, Palma
RD, Borghs G, Declerck P, Goddeeris B (2006)
Comparision of random oriented immobilisation of
antibody fragments on mixed self-assembled mono-
layers. J Immunol Methods 312:167–181
Denizli A (2011) Purification of antibodies by affinity
chromatography. Hacet J Biol Chem 39:1–18
Hober S, Nord K, Linhult M (2007) Protein
A chromatography for antibody purification.
J Chromatogr B 848:40–47
Huse K, Böhme HJ, Scholz GH (2002) Purification of
antibodies by affinity chromatography. J Biochem
Biophys Methods 51:217–231
Low D, O’Leary R, Pujar NS (2007) Future of antibody
purification. J Chromatogr B 848:48–63
Tishchenko G, Dybal J, Meszarosova K, Sedlakova Z,
Bleha M (2002) Purification of the specific immuno-
globulin G1by immobilized metal ion affinity chroma-
tography using nickel complexes of chelating porous
and nonporous polymeric sorbents based on poly
(methacrylic esters). Effect of polymer structure.
J Chromatogr A 954:115–126
Yavuz H, Denizli A (2005) Immunoadsorption of choles-
terol on protein A oriented beads. Macromol Biosci
5:39–48
O
Oxidative Coupling in Membrane
Reactors
Juergen Caro
Institut f€
ur Physikalische Chemie und
Elektrochemie der Leibniz, Universität
Hannover, Hannover, Germany
Oxidative coupling of methane according to
2CH4 þ O2 ! C2 H4 þ 2H2 O is a promising
way to transform natural gas into ethylene and
ethane. From numerous classical co-feed experi-
ments in packed bed reactors it follows that for a
high C2 selectivity of about 70 %, the CH4/O2
ratio must be high. To ensure a high C2 selectiv-
ity, the reaction has to be performed at low oxy-
gen partial pressure. This situation can be ensured
by applying the concept of distributed oxygen
dosing in “membrane distributor reactor” with
dense (perovskite-like ceramic, silver) or porous
membranes. The accepted reaction mechanism
assumes as first step the formation of CH3 radi-
cals on a heterogeneous catalyst. After this het-
erogeneous step, the combination of two CH3
radicals to ethane is proposed in a homogeneous
gas phase reaction, followed by an oxidehydro-
genation of the ethane to ethylene. This reaction
chain can be realized in a catalytic membrane
reactor with oxygen supply from surrounding air
applying established heterogeneous catalysts like
2 wt% Mn/5 wt% Na2WO4 on SiO2 for the CH3
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_734-6
formation (Kondratenko and Baerns 2008). By
supplying the oxygen through the reactor wall, a
rather low and constant oxygen partial pressure in
axial direction of a tubular reactor can be
achieved which should be beneficial for selectiv-
ity. Hot spots and explosive mixtures – like often
observed for co-feed reactors – can be avoided in
the case of the membrane distributor reactor
(Dittmeyer and Caro 2008; Caro 2010). How-
ever, whereas best C2 yields in classical packed
bed reactors with an oxygen/methane co-feed
reach 30 %, best membrane reactor data are of
the order of 15 % (Tan and Li 2006) or 17 %
(Czuprat et al. 2010).
References
Caro J (2010) Basic aspects of membrane reactors. In:
Drioli E, Giorno L (eds) Comprehensive membrane
science and engineering, vol 3. Elsevier, Amsterdam,
pp 1–108
Czuprat O, Schiestel T, Voss H, Caro J (2010) Oxidative
coupling of methane in a BCFZ Perovskite hollow
fiber membrane reactor. Ind Eng Chem Res
49:10230–10236
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
In: Ertl G, Knözinger H, Sch€
uth F, Weitkamp J (eds)
Handbook of heterogeneous catalysis. Wiley-VCH,
Weinheim, pp 2198–2248
Tan X, Li K (2006) Oxidative coupling of methane in a
perovskite hollow-fiber membrane reactor. Ind Eng
Chem Res 45:142–149
P
Parameter Estimation: Optimization
of Membrane Operation
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universität Dortmund,
Dortmund, Germany
Parameter estimation, in engineering applica-
tions, represents a problem which arises in
modeling and control when one wants to describe
physical reality (e.g., behavior of a system) by a
model.
Mathematically speaking, it is desired to
determine values of model parameters, p, which
minimize the difference between the set of
n measured data, y, and the set of data, y^,
predicted by a model. This problem can be writ-
ten as follows:
X
n treated in study of gas permeation in polymers
min ðyi  y^i Þ2
p
i¼1
s:t: f ðy^, pÞ ¼ 0
where Eq. 1b stands for the model, in general a set
of equations of different nature (e.g., linear,
nonlinear, dynamic, stochastic) which relates
predicted behavior of a system with estimated
parameters. If f() is linear and no other con-
straints for p exist, problem (1) has analytical
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_735-2
solution. In other cases, one exploits numerical
methods such as quadratic or nonlinear program-
ming to solve the problem.
Objective function (1a) represents the
so-called least squares estimation cost, and it is
recognized in statistics as a maximum likelihood
estimation under assumption of normal distribu-
tion of measurement error.
Parameter estimation finds its applications in a
field of membrane engineering and processes.
These include nonlinear estimation of parameters
of pervaporation (Caoa and Henson 2003),
reverse osmosis (Chatterjee et al. 2004), and
modeling and control of other membrane pro-
cesses (Selby and Shannon 2009; Madyastha
and Prasad 2011).
Problem of parameter estimation is closely
related to finding of intervals of confidence for
estimated parameters. In principle, this problem
is based on identifying the sensitivities of esti-
mated parameters to observed data and was
(1a) by (Scheichl et al. 2005).
(1b)
References
Caoa B, Henson MA (2003) Nonlinear parameter estima-
tion for solution-diffusion models of membrane
pervaporation. Ann N Y Acad Sci 984(1):370–385.
doi:10.1111/j.1749-6632.2003.tb06013.x, ISSN
1749-6632
Chatterjee A, Ahluwalia A, Senthilmurugan S, Gupta SK
(2004) Modeling of a radial flow hollow fiber module
2 Parameter Estimation: Optimization of Membrane Operation
and estimation of model parameters using numerical
techniques. J Membr Sci 236(1–2):1–16. doi:10.1016/
j.memsci.2004.01.006, ISSN 0376-7388
Madyastha VK, Prasad V (2011) Joint state and parameter
estimation for a membrane bioreactor system. Asia
Pac J Chem Eng 6(3):406–422. doi:10.1002/apj.578,
ISSN 1932-2143
Scheichl R, Klopffer MH, Benjelloun-Dabaghi Z,
Flaconneche B (2005) Permeation of gases in
polymers: parameter identification and nonlinear
regression analysis. J Membr Sci 254(1–2):275–293.
doi:10.1016/j.memsci.2005.01.019, ISSN 0376-7388
Selby JC, Shannon MA (2009) Inflation of a circular
elastomeric membrane into a horizontally semi-
infinite liquid reservoir of finite vertical depth: estima-
tion of material parameters from volume–pressure
data. Int J Eng Sci 47(5–6):718–734. doi:10.1016/j.
ijengsci.2009.01.007, ISSN 0020-7225
P
Polyether Block Amide (PEBAX)
Anja Car
Department of Chemistry, University of Basel,
Basel, Switzerland
Polyether block amide is a multiblock copoly-
mer with two types of segments, rigid polyamide
(PA) and flexible polyether known under the
trade name Pebax ® (http://www.pebax.com/
sites/pebax/en/home.page). It is obtained by
polycondensation reaction (Fakirov 2005) of a
carboxylic acid polyamide (PA6, P11, P12) with
an alcohol-terminated polyether either polytetra-
methylene glycol (PTMG) or polyethylene glycol
(PEG) with general chemical structure (Fig. 1):
Pebax ® consists of a linear chain of polyamide
and polyether segment (block) in an orderly pat-
tern and belongs to the group of thermoplastic
elastomers (Holden et al. 1996). The combination
of the rigid PA segment and the flexible polyether
segment yields a block copolymer that exhibits a
microphase-separated morphology (Bates 1991)
due to the polarity differences between them: a
crystalline PA and an amorphous polyether
phase. The crystalline phase allows the copoly-
mer to behave as a thermoplastic and the amor-
phous phase imparts elastomer characteristics.
The PA block melts in the range 130–200  C
(Rulkens et al. 2012); the exact value depends
on average molecular weight and content of the
PA in the copolymer. Polyether block crystallizes
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_736-2
at low temperatures, the value of which lies
between 30  C and 20  C mostly depending
on its molecular weight of the sequences
(Bailey and Koleske 1976). The glass-transition
temperature (Tg) is about 50  C due to the
flexible segment (Patel and Spontak 2004).
Through a proper combination of the polyamide
®
and the polyether blocks, a wide range of Pebax
grades with a variety of end-use characteristics
can be designed (Pebax ® Technical Data Sheets).
In general, these polymers possess a broad range
of flexibility without the use of additives while
maintaining high strength and toughness.
Because of the thermoplastic qualities, it can be
easily processed, extruded, and shaped at ele-
vated temperatures, and upon cooling, its elastic-
ity will allow it to return to its original length or
shape after being stretched, compressed, or
deformed. Depending on the nature and the rela-
tive content of both segments, certain grades of
Pebax ® copolymers have great film-forming abil-
ity; thus, they attracted greater attention as a
promising membrane material (Blume
et al. 1990). The material offers strong resistance
to a range of chemicals, and it is not affected by
exposure to saline or sulfuric acid (Carson
et al. 2010). It can be sterilized by a variety of
methods including gamma radiation and steam
autoclave. Pebax ® is considered as a high per-
former among its thermoplastic elastomer peers
because it is lightweight and because it offers a
wider range of flexibility and hardness, a higher
energy return, a greater resistance to fatigue, and
2 Polyether Block Amide (PEBAX)
Polyether Block Amide
(PEBAX), Fig. 1 Chemical
structure of Pebax ®
better dimensional stability under physical and
thermal stress (McKeen et al. 2010).
References
Bailey JFE, Koleske JV (1976) Poly(ethylene oxide).
Academic, New York
Bates FS (1991) Science polymer-polymer phase behav-
ior. 251:898–905
Blume I, Pinnau I (1990) Composite membrane, method
of preparation and use. US Patent 4,963,165
Carson C, Sik R (2010) Laser machining polyether block
amide tubing. Eur Med Device Technol
Fakirov S (2005) Handbook of condensation thermoplas-
tic elastomers. Wiley-VCH Verlag GmbH & Co,
Weinheim
Holden G, Legge NR, Quirk RP, Schroeder HE
(1996) Thermoplastic elastomers. Hanser Publishers,
Munich
McKeen LW (2010) Tribological properties of plastic and
elastomers, 2nd edn. Elsevier
Patel NP, Spontak RJ (2004) Mesoblends of polyether
block copolymers with Poly(ethylene glycol). Macro-
molecules 37:1394–1402
Pebax ® Technical Data Sheets. http://www.matweb.com/
search/GetMatlsByTradename.aspx?navletter=p&
tn=Pebax%C2%AE
Rulkens R (2012) Chemistry and technology of polyam-
ides. Polym Sci Compr Ref 5:431–467
P
Photolysis in Photocatalytic
Membrane Reactors
Palmisano Leonardo
Dipartimento di Energia, Ingegneria
dell’Informazione e Modelli Matematici
(DEIM), Universite di Palermo, Palermo, Italy
Photolysis is a chemical process which is able to
break down molecules into smaller units through
the absorption of light. It can be carried out in a
device combining also a membrane. Some results
obtained in various photocatalytic membrane
reactors are summarized in the following.
Some advanced oxidation processes (AOPs)
such as Fenton H2O2/Fe2+, photo-assisted Fenton
UV/H2O2/Fe2+, UV photolysis, and photo-
assisted Fenton like UV/O2/Fe2+ have been tested
for the degradation of gemfibrozil (a widely used
blood lipid and cholesterol-modifying drug) in
aqueous solution in a batch system and then in a
membrane reactor (Molinari et al. 2007).
A nanofiltration/reverse osmosis type cross-
linked polyamide UTC-60 (Toray) membrane
(19 cm2) was used. Gemfibrozil at an initial con-
centration equal to 5 mg/L was degraded in the
batch degradation tests by employing the four
AOPs, but numerous peaks of intermediates
were observed by HPLC analyses. Indeed
dissolved oxygen concentration (DOC) analyses
indicated a poor mineralization in the case of
photolysis (3.1 %) and UV/O2/Fe (10 %),
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_738-2
whereas values of 62 % and 24 % were obtained
by using photo-assisted Fenton and Fenton
AOPs, respectively. Thus, in the membrane reac-
tor, only the Fenton and the photo-assisted
Fenton were tested. In the latter case the results
showed a drug degradation higher than 92 %, a
mineralization higher than 55 %, and a membrane
retention of the catalyst in solution higher than
95 %.
The combination of a dialysis membrane and a
photochemical reactor into a membrane
photoreactor (MPR) to mineralize organic com-
pounds was described by Azrague et al. (2005).
A pollutant model (2,4-dihydroxy benzoic acid)
was mineralized from turbid waters in the
photoreactor by using VUV (vacuum ultraviolet)
irradiation (172 nm). A model based on diffusion
through the membrane and first-order reaction in
the reactor was in good agreement with the exper-
imental data, in a wide range of operating condi-
tions. This “advanced oxidation process”
produces high concentrations of hydroxyl radi-
cals and is a good method to mineralize organic
compounds.
The membrane efficiency to photodegrade
typical water pollutants was evaluated in a con-
tinuous flow water purification device, applying
UV irradiation on both membrane sides by
Romanos et al. (2012). The developed composite
NF membranes were highly efficient in the
decomposition of methyl orange exhibiting low
adsorption-fouling tendency and high water per-
meability. A chemical vapor deposition (CVD)-
2 Photolysis in Photocatalytic Membrane Reactors
based innovative approach was applied with the
purpose to develop composite TiO2
photocatalytic nanofiltration (NF) membranes.
The method involved pyrolytic decomposition
of titanium tetraisopropoxide (TTIP) vapor and
formation of TiO2 nanoparticles through homo-
geneous gas-phase reactions and aggregation of
the produced intermediate species. The grown
nanoparticles are diffused and deposited on the
surface of gamma-alumina NF membrane tubes.
The CVD reactor allowed for online monitoring
of the carrier gas permeability during the treat-
ment, providing a first insight on the pore effi-
ciency and thickness of the formed photocatalytic
layers. In addition the thin TiO2 deposits were
developed on both membrane sides without
sacrificing the high yield rates. Important inno-
vation was also introduced in what concerns the
photocatalytic performance evaluation.
Fulvic acids were removed from model solu-
tions by catalysis, photolysis, and photocatalysis,
as well as in the integrated process of
photocatalysis and ultrafiltration (Rajca et al.
2011). Experiments were carried out in the
Heraeus reactor, where model water of an
approximately 10 g/m3 content of fulvic acids
was treated. TiO2 was used as a photocatalyst.
The efficiency of fulvic acid oxidation, measured
in terms of dissolved organic carbon content and
UV absorbance (l = 254 nm), was related to the
pH of the water (3.5, 7.0 and 10.0) and to the
catalyst dose applied (100–600 gTiO2/m3). The
results indicated the efficiency of the
photocatalytic process for fulvic acid removal
from water and the usefulness of the ultrafiltra-
tion membrane in the recovery of the catalyst
used. The values of the reaction rate constant
and the halftime of fulvic acid degradation were
determined using a kinetic model based on a first-
order reaction. Relations between rate constant,
pH, and photocatalyst concentration in the reac-
tion environment were found.
References
Azrague J, Puech-Costes E, Aimar P, Maurette MT,
Benoit-Marquie FB (2005) Membrane photoreactor
(MPR) for the mineralisation of organic pollutants
from turbid effluents. J Membr Sci 258:71–77
Molinari R, Argurio P, Poerio T, Bonaddio F (2007) Photo
assisted Fenton in a batch and a membrane reactor for
degradation of drugs in water. Sep Sci Technol
42:1597–1611
Rajca M, Bodzek M, Cichy J (2011) Kinetics of fulvic acid
degradation in the integrated process photooxidation-
ultrafiltration. Ochrona Srodowiska 33:63–66
Romanos GE, Athanasekou CP, Katsaros FK,
Kanellopoulos NK, Dionysiou DD, Likodimos V,
Falaras P (2012) Double-side active TiO2-modified
nanofiltration membranes in continuous flow
photocatalytic reactors for effective water purification.
J Hazard Mater 211:304–316
P

Polarization in Membrane membrane techniques, such as microfiltration

Operations
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Poland
Polarization phenomena are inherent to all mem-
brane separation processes. Since a membrane
has the ability to transfer one component of a
mixture more readily than others or to retain
solutes completely, the rejected substances are
gradually accumulated at the membrane surface,
whereas a solvent permeates freely through the
membrane. This leads to the formation of a
boundary layer adjacent to the membrane,
where the concentration of the retained solutes
is higher than in a bulk solution (Fig. 1). This
difference in the concentration of solutes is
termed as concentration polarization (CP).
(MF) and ultrafiltration (UF), which are applied to
separate the macromolecular solutes, small parti-
cles, colloids, and emulsions. The concentration of
the accumulated molecules might be so high that a
gel layer can be formed on a membrane, which
induces an additional resistance to the mass transfer
on the feed side.
In reverse osmosis (RO), an increase of salt
concentration in the boundary layer can increase
the osmotic pressure and reduce the driving force.
The severity of CP in RO is lower than in MF or
mass transfer
boundary
layer
cm
J
bulk flow

The CP phenomenon causes a serious problem cB

in every membrane process because it reduces the
driving force of the mass transfer and thus leads dc cp
to a decrease in the permeate flux. JB = D
The extent of CP strongly depends on the type dx
of membrane process, its driving force, and the feed
composition. The CP effect is most severe when a
permeate flux is high and the mass transfer coeffi- membrane
cients (and diffusion coefficients) of the separated
Polarization in Membrane Operations,
species are low (Table 1). Thus, the CP is espe- Fig. 1 Concentration polarization. Concentration profile
cially severe in the case of pressure driven under steady-state conditions

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_742-2
2 Polarization in Membrane Operations

Polarization in Membrane Operations, Table 1 Effects of polarization concentration in various membrane

operations (based on Mulder 1991)
Membrane operation CP influence Mass transfer coefficient/diffusion coefficient Permeate flux
Reverse osmosis Moderate Large /10 9 m2/s Small/moderate
Nanofiltration Moderate Large Moderate
Ultrafiltration Strong Small/10 10 to 10 11m2/s Large
Microfiltration Strong Small/10 10 to 10 11m2/s Large
Gas separation Very low Large/10 4 to 10 5m2/s Small
Pervaporation Low Large Small
Electrodialysis Strong
9
Dialysis Low Large/10 m2/s Small
Membrane distillationa Low Large Small/moderate
a
Strong influence of temperature polarization

Polarization transfer of cations

in Membrane
Operations, boundary boundary
Fig. 2 Concentration layer layer
polarization in
electrodialysis in the
presence of cation-selective anion
concentration

membrane
anion
anode cb+ cathode

cm+

cation-selective
membrane

UF because the permeate flux is lower and the
mass transfer coefficients of salts are high. How-
ever, an increase of salt concentration in the layer
adjacent to the membrane results in their precip-
itation onto the membrane surface (scaling),
which contributes to a decrease of permeate flux
(Mulder 1991).
Scaling is also a serious problem in
nanofiltration (NF). The CP in NF causes a
reduction of a permeate flux mainly due to an
increase of osmotic pressure of the retained
salts. Moreover, similarly as in UF and MF, the
accumulated organic molecules can form a gel
layer (fouling or biofouling) (Schafer et al. 2005).
The concentration polarization also strongly
limits the efficiency of electrodialysis (ED). The
transport of charged molecules is the result of an
electrical potential difference (driving force)
through an ion-selective membrane. Cations are
driven to cathode and anions to anode. For exam-
ple, through a cation-selective membrane only
cations can be transferred at the potential differ-
ence. However, the transfer across the membrane
is faster than in boundary layers on both sides of
the membrane. Thus, the concentration of cations
will be lower at the membrane surface on the
anode side and higher at the membrane surface
on the cathode side (Fig. 2). Thus, CP appears on
both sides of the membrane. Moreover, a diffu-
sive flow occurs in the boundary layers (Mulder
1991).
The effect of CP on the membrane processes
such as gas separation, pervaporation, and dialy-
sis is low or very low (Table 1).
Polarization in Membrane Operations
In the case when a hydrophobic membrane
separates two solutions of different temperature
as in membrane distillation (MD), the tempera-
ture and concentration polarization phenomena
occur. In MD, only volatile components are trans-
ferred through a hydrophobic, porous membrane.
Therefore, the energy required for water evapo-
ration is supplied from hot feed solution on the
liquid-membrane interface. As a result the local
temperature in the boundary layer is gradually
decreasing. On the cold side, the water vapor is
condensed and energy (latent heat) is released,
therefore, the temperature in the boundary layer
increases. For this reason, the temperature of the
liquid-membrane interface on both sides of the
membrane is different from that in bulk solutions.
This difference is referred to as temperature
3
polarization. Additionally, an accumulation of
solutes on the feed side leads to the concentration
polarization.
The extent of CP can be reduced by increasing
flow rate of the stream over a membrane, appli-
cation of permeate pulsing, operation below a
critical flux, or using an ultrasound system
(Schafer et al. 2005).
References
Mulder M (1991) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
Schafer AI, Fane AG, Waite TD (2005) Nanofiltration:
principles and applications. Elsevier, Oxford
A
Al2O3 Porous Membranes
Sophie Cerneaux
UMR 5635 ENSCM, CNRS, UM, Institut
Européen des Membranes, Montpellier, France
Synonyms
Aluminum (III) oxide porous membranes or alu-
mina porous membranes
Characteristics
Al2O3 is an amphoteric oxide that exhibits poly-
morphic crystalline forms upon temperature
treatment. A wide variety of alumina powders
are commercially available with different particle
sizes.
Alumina porous membranes are commercially
available inorganic ceramic membranes widely
used in membrane processes related to water
treatment essentially. They are shaped in mono-
lith, honey comb, flat, monochannel, and
multichannel configurations or as thin films.
Alumina membranes may be prepared by
anodic oxidation of aluminum foil to design
well-ordered and straight pore channels in the
membrane or by sol-gel route using colloids or
Al molecular precursors to yield porous
supported membranes. In addition, alumina
macroporous supports are also used for
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_745-3
multilayered structures of other oxide or
non-oxide materials. More recently, alumina
porous membranes found a new application as
hard template for the fabrication of nanotubes
and nanowires through electrodeposition and alu-
mina membrane etching (Burggraaf and Cot
1996; Lee and Pope 1994).
The filtration process and therefore the elimi-
nation of different species from polluted water,
for example, strongly depend on the type of mem-
brane used, its porosity, and pore size. As
recommended by IUPAC, porous membranes
are classified according to their connected pore
size being microporous for pore diameters lower
than 2 nm, mesoporous for pore diameters in the
range 2–50 nm, and macroporous for pore sizes
superior than 50 nm (Koros et al. 1996). Respec-
tively, porous membranes will be applied to sep-
aration processes such as nanofiltration,
ultrafiltration, and microfiltration.
The synthesis of macroporous and
mesoporous membranes is often made by consol-
idation of particles followed by thermal removal
of organic additives. Going to nanofiltration
application, the microporous network is directly
prepared from a sol containing particles lower
than 10 nm followed by an appropriate
sintering step.
2 Al2O3 Porous Membranes

References Koros WJ, Ma YH, Shimidzu T (1996) Terminology for

membranes and membrane processes. Pure Appl
Burggraaf AJ, Cot L (1996) Fundamentals of inorganic Chem 68(7):1479–1489
membrane science and technology. Elsevier, Lee BI, Pope EJA (1994) Chemical processing of
Amsterdam ceramics. Marcel Dekker, New York
P
Process Control in Membrane
Operations
Radoslav Paulen
Department of Biochemical and Chemical
Engineering, Technische Universtät Dortmund,
Dortmund, Germany
Efficient automatic control system is an essential
part of every plant being operated in chemical
industry. It may be implemented for various rea-
sons: plant and environmental safety, fulfillment
of varying process demands, rejection of input
disturbances, optimal production desire, etc.
Process control is usually achieved via feed-
back policy. By measuring time-varying process
outputs y(t) (controlled variables), such as tem-
perature or concentration, one decides about pro-
cess inputs u(t) (manipulated variables), such as
input power to heating cell or valve position, to
attain some or all of the abovementioned goals.
Classical control theory defines a fashion in
which obtained measurements are used to iden-
tify value of input as a control law. Its basic form
can be stated as
uðtÞ ¼ f ðyðtÞÞ
where f() represents a function which can take
various forms and can be designed using analyt-
ical or numerical methods in order to establish
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_749-4
optimal, adaptive, robust, stochastic, or any other
type of process control.
Process control can be designed by exploiting
neural network or fuzzy logic approach. The lat-
ter technique was used to control microfiltration
process by Perrot et al. 1996.
However, the most popular control applica-
tions are accompanied with the use of
proportional-integral-derivative (PID) controller.
Its control law can be written as
ðt
d
uðtÞ ¼ K p eðtÞ þ K i eðtÞdt þ K d eðtÞ
0 dt
where Kp, Ki, and Kd are proportional, integral,
and derivative gains, respectively, and e(t) repre-
sents control error, a difference between desired
and actual value of the output. There are numer-
ous applications of PID controller in membrane
technology and processes (van Reis et al. 1997;
Smith et al. 2005; Blankert et al. 2007; Yee
et al. 2008).
References
Blankert B, Betlem BHL, Roffel B (2007) Development
of a control system for in-line coagulation in an ultra-
filtration process. J Membr Sci 301(1–2):39–45.
doi:10.1016/j.memsci.2007.05.033, ISSN 0376-7388
Perrot N, Trichard JM, Trystram G, Decloux M (1996)
Automatic control of the crossflow microfiltration pro-
cess using fuzzy logic. J Membr Sci 116(1):93–105.
doi:10.1016/0376-7388(96)00027-0, ISSN 0376-7388
2 Process Control in Membrane Operations

Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen
H (2005) Design of a generic control system for
optimising back flush durations in a submerged mem-
brane hybrid reactor. J Membr Sci 255(1–2):99–106.
doi:10.1016/j.memsci.2005.01.026, ISSN 0376-7388
van Reis R, Goodrich EM, Yson CL, Frautschy LN,
Whiteley R, Zydney AL (1997) Constant Cwall
ultrafiltration process control. J Membr Sci
130(1–2):123–140, ISSN 0376-7388
Yee KWK, Alexiadis A, Bao J, Wiley DE (2008) Effects
of multiple-stage membrane process designs on the
achievable performance of automatic control.
J Membr Sci 320(1–2):280–291. doi:10.1016/j.
memsci.2008.04.010, ISSN 0376-7388
P
Productivity and Footprint in Gas
Separation
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende (CS), Italy
The productivity to footprint compares the pro-
ductivity of the separation system with respect to
the installation area occupied by the system itself
(Eq. 1) (Criscuoli and Drioli 2007). Considering
the same area occupied by the units, this metric
identifies the most productive scheme to get a set
target. Future plants should be characterized by
high productivities and low sizes; therefore, a
high value of this index is highly desired.
To compare two different technologies that
can be used for the same separation, the ratio
between the values of productivity/footprint
ratio obtained for each of them can be defined
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_752-1
(Eq. 2). When the value of this ratio is higher than
1, membrane operations should be preferred,
whereas, for values lower than 1, traditional
units should be chosen.
Productivityi =Footprint
Productivity
¼ (1)
Footprint occupied by the installation
Productivity footprint ratio
ðProductivityi =FootprintÞMembranes
¼
ðProductivityi =FootprintÞTraditional technology
(2)
References
Criscuoli A, Drioli E (2007) New metrics for evaluating
the performance of membrane operations in the logic
of process intensification. Ind Eng Chem Res
46:2268–2271
R
Reliability in Gas Separation
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende (CS), Italy
The reliability takes into account the on-stream
factors which can cause unscheduled shutdowns.
It is an important project consideration, particu-
larly if the process is a primary source of make-up
hydrogen to a hydroprocessor or other main-
stream refinery processes (Miller and Stöcker
1989; Brunetti et al. 2010).
Membrane systems are extremely reliable
with respect to the on-stream factor. The mem-
brane separation process is continuous and has
few control components which can cause a shut-
down. Typically, the response to unscheduled
shutdowns is rapid. Absorption systems are mod-
erately reliable. The large equipment associated
with the process for avoiding the formation of
degradation and corrosion products and the pres-
ence of particles can cause unexpected
shutdowns.
PSA systems are also moderately reliable. The
numerous valves associated with the process can
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_753-1
induce unscheduled shutdowns. The new PSA are
designed with alternate modes of operation, in
which 100 % of design capacity can be achieved
while bypassing any failed valve or instrument,
with only a slight loss of recovery. Failures are
automatically detected and bypassed by the
microprocessor-based control system. However,
stronger and periodic control cycles are required.
The cryogenic process is considered by
refiners to be less reliable than the PSA or mem-
brane processes; this is mainly due not to the
process itself but to the need for feed pretreat-
ments. Failure of the pretreatment system usually
results in contaminants freezing in the cold box,
leading to shutdown. In this case, a “thaw” is
necessary prior to restart. The pretreatment sys-
tem itself is often more complex than the cryo-
genic system.
References
Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
brane engineering progresses and potentialities in gas
separations. In: Yampolskii Y, Freeman B (eds) Mem-
brane gas separation. Wiley, New York, pp 281–312
Miller GQ, Stöcker J (1989) Selection of a hydrogen
separation process NPRA Annual Meeting 19–21
Mar, San Francisco
G
Genotoxin Removal
Gyorgy Szekely
Department of Chemical Engineering, Imperial
College London, London, UK
Synonyms
Degenotoxification
Definition
Genotoxin removal by membranes is an emerg-
ing purification technology aiming to reach
ultralow genotoxic impurity levels in order to
address health and environmental regulations.
Characteristics
The main challenge of genotoxin removal by
membranes lies in the fact that most of them are
highly reactive species and thus can attack poly-
meric membrane framework at molecular level.
Degenotoxification of active pharmaceutical
ingredients (API) is of utmost importance to
drug manufacturers. Genotoxicity of pharmaceu-
tical impurities is being continuously evaluated
increasing the list of such highly toxic impurities.
Pharmaceutical regulatory authorities draw the
attention to API purification and strict the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_754-7
threshold limits of genotoxins via annually issued
guidelines. Besides the conventional API down-
stream processes such as recrystallization, frac-
tional distillation, chromatography, extraction,
and adsorbents, new technologies are being
implemented in the pharmaceutical industry.
Application of nanofiltration alone and combined
with adsorbents are proposed as alternative puri-
fication technologies assuring ultralow genotoxin
contaminations in drug products. API post-
reaction streams usually feature organic solvents,
limiting the selection of membranes to be used in
the process. Commercially available polymeric
and ceramic membranes stable in organic sol-
vents include Koch SelRO, Evonik DuraMem
series, SolSep NF series, Borsig GMT-oNF
series, as well as Inopor and Pervap ceramic
membranes. The feasibility of API degenotoxi-
fication by organic solvent nanofiltration (OSN)
has been successfully applied in diafiltration
mode where fresh solvent is continuously added
to the retentate in order to push the relatively
small genotoxic molecules through the mem-
brane, while the relatively large API molecules
are retained as depicted in Fig. 1 (Székely 2011).
The aim is achieving high genotoxin removal and
low API loss which mainly depends on the
molecular size gap between the impurity and the
API as well as the polarity of the impurity. Hybrid
processes featuring OSN and adsorbents have
been developed for the removal of genotoxic
palladium, impurity retained (Pink 2008), and
1,3-diisopropylurea, API retained (Székely
2 Genotoxin Removal
Genotoxin Removal,
Fig. 1 Scheme of
genotoxin removal by OSN
with potential reverse
osmosis for solvent
recycling
2012), from post-reaction solutions. In the former
case, the Suzuki post-reaction solution was
subjected to OSN, and the palladium was retained
by the membrane, while the API was collected in
the permeate. On the contrary, in the latter case,
the genotoxin was removed with the permeate,
while the API was retained. In both cases the
genotoxin levels were reduced further by using
commercially available adsorbents or tailor-
made molecularly imprinted polymers. Not only
has the combination of molecular imprinting and
membrane technology provided an efficient
genotoxin removal process but their fusion as
well. Molecularly imprinted membranes (MIM)
can also be used for API degenotoxification.
Potentially genotoxic 4,40 -methylenedianiline
has been applied as a template for MIM adsor-
bents (De Luca 2011). Environmental and eco-
nomic analysis proved the sustainability of API
degenotoxification by membrane processes in
comparison with conventional API purification
methodologies such as chromatography and
recrystallization (Székely 2013). Besides phar-
maceutical purification, control of genotoxins is
also an environmental concern. Nanofiltration
featuring DESAL 51 HL, DESAL 5 DL,
UTC-20, and UTC-60 membranes was applied
for the removal of genotoxic atrazine – banned
as a total herbicide in Europe since 1991 – from
different water matrices including distilled water,
tap water, and river water (Zhang 2004).
References
De Luca G, Donato L, Del Blanco SG, Tasselli F, Drioli
E (2011) On the cause of controlling affinity to small
molecules of imprinted polymeric membranes pre-
pared by noncovalent approach: a computational and
experimental investigation. J Phys Chem
B 115:9345–9351
Pink CJ, Wong H, Ferreira FC, Livingston AG
(2008) Organic solvent nanofiltration and adsorbents;
a hybrid approach to achieve ultra low palladium con-
tamination of post coupling reaction products. Org
Process Res Dev 12(4):589–595
Székely GY, Bandarra J, Heggie W, Sellergren B, Ferreira
FC (2011) Organic solvent nanofiltration: a platform
for removal of genotoxins from active pharmaceutical
ingredients. J Membr Sci 381(1–2):21–33
Székely GY, Bandarra J, Heggie W, Sellergren B, Ferreira
FC (2012) A hybrid approach to reach stringent low
genotoxic impurity contents in active pharmaceutical
ingredients: combining molecularly imprinted poly-
mers and organic solvent nanofiltration for removal
of 1,3-diisopropylurea. Sep Purif Technol 86:79–87
Genotoxin Removal
Székely GY, Gil M, Sellergren B, Heggie W, Ferreira FC
(2013) Environmental and economic analysis for
selection and engineering sustainable API degenotox-
ification processes. Green Chem. doi:10.1039/
c2gc36239b
3
Zhang Y, Van der Bruggen B, Chena GX, Braeken L,
Vandecasteele C (2004) Removal of pesticides by
nanofiltration: effect of the water matrix. Sep Purif
Technol 38:163–172
S

Screen Printing of Membranes technology, solar cells, fuel cells, membrane

switches, etc.
Tauqir A. Sherazi
Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad,
Applications
Pakistan
Membrane Switches
Screen printing is commonly used in manufactur-
Screen Printing
ing process of membrane switches where circuit
printing, graphic printing, and sometimes print-
Screen printing is simple, economical, and versa-
ing of industrial material such as adhesives and
tile than traditional printing techniques. This
spacer layers can be achieved. Since membrane
technique is more suitable for flat or relatively
switches are used to enter function commands,
flat surface; however, it could also work with less
they have wide range of applications in electron-
planar surfaces. A screen or fine mesh tightly
ics such as cellular phones, calculators, remote
stretched with a rigid frame is required. During
controls, machine controls, microwave ovens,
printing, the undesired area of the mesh or screen
and kitchen appliances, etc.
is masked out according to the desired printing
Screen printing offers a wide range of wet ink
sketch. The screen is then positioned over the
deposit thicknesses from which to create the cir-
object to be printed and the ink is applied onto
cuits (from a few microns to several hundreds of
the screen followed by pressing the ink through
microns). Moreover, printing of viscous conduc-
the screen using squeegee. The distribution of
tive, resistive, and adhesive materials could be
masked and unmasked area of the screen design
achieved. Inks used for membrane switches
the print on the object followed by drying or
include polymer thick film silver conductive and
curing. Proper postprint curing makes the print
resistive inks, adhesives, and solvent based
permanent and retains even under severe condi-
(vacuum forming) and graphic UV-curing inks.
tions. A variety of inks can be applied to a range
Substrate materials typically used in membrane
of materials such as ceramics, textile, glass,
switch fabrication include polyester foils for the
metal, paper, and plastic. Consequently, screen
circuit layers and polycarbonate for the graphic
printing is used in many industries including tex-
overlays (Membrane Switches 2013).
tile, medical devices, advertizing, snowboard
graphics, decals, printed electronics, thick film

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_757-1
2 Screen Printing of Membranes
Fuel Cell Membranes
Membrane electrode assembly (MEA) is an
important part of fuel cells. Fabrication of MEA
also involves the coating of catalyst layer onto
membrane or to the gas diffusion layer. Catalyst
layer structures can be modified by changing
coating methods which significantly affect the
performance of MEA. Spraying, screen printing,
brushing, and decal methods have been applied to
fabricate catalyst layers and carbon electrode
layers to find out the economic ways suitable for
mass production.
Spraying method and brushing method are
widely used at laboratory scale but these methods
are difficult to apply on large scale/mass produc-
tion (Yoon et al. 2003). Sputtering is another
interesting method for coating a small amount
of catalyst in a vacuum, although it shows low
single cell performance (Huang et al. 2006). The
coating performed by decal method showed low
electrochemical performance when applied to
hydrocarbon polymer electrolyte membrane
(PEM), which limits mass production and its
application to various types of PEMs (Cho
et al. 2009; Jeon et al. 2010). Owing to the advan-
tages of reproducibility, easy procedures, and
economic catalyst usage for mass production,
the screen-printing method is proved as an effi-
cient way to coat the membranes with catalyst
layer for fuel cells applications (Rajalakshmi and
Dhathathreyan 2007).
Sensors
Sensors can also be fabricated by screen-printing
technique. The chemical sensor consisting of
transducer, sensitive membrane, and housing
can be imagined as a system of layers. In such a
planar potentiometric electrode, one layer can
work as an electric contact of the electrode. The
sensitive membrane can be the next layer, and
finally the insulating layer that represents
(together with the substrate) an equivalent of a
conventional electrode body (Tymecki
et al. 2006; Koncki et al. 1999).
References
Cho JH, Kim JM, Prabhuram J, Hwang SY, Ahn DJ, Ha
HY (2009) Fabrication and evaluation of membrane
electrode assemblies by low-temperature decal
methods for direct methanol fuel cells. J Power
Sources 187:378–386
Huang KL, Lai YC, Tsai CH (2006) Effects of sputtering
parameters on the performance of electrode s fabri-
cated for proton exchange membrane fuel cells.
J Power Sources 156:224–231
Jeon S, Lee J, Rios GM, Kim H-J, Lee S-Y, Cho E (2010)
Effect of ionomer content and relative humidity on
polymer electrolyte membrane fuel cell (PEMFC) per-
formance of membrane-electrode assemblies (MEAs)
prepared by decal transfer method. Int J Hydrog
Energy 35:9678–9686
Koncki R, GøaÎ S, Dziwulsk J, Palchetti I, Mascini
M (1999) Disposable strip potentiometric electrodes
with solvent-polymeric ion-selective membranes fab-
ricated using screen-printing technology. Anal Chim
Acta 385:451–459
Membrane switches. www.sefar.com. Retrieved 14 Sept
2013
Rajalakshmi N, Dhathathreyan KS (2007) Catalyst layer
in PEMFC electrode se fabrication, characterisation
and analysis. Chem Eng J 129:31–40
Tymecki L, Glab S, Koncki R (2006) Miniaturized, planar
ion-selective electrodes fabricated by means of thick-
film technology. Sensors 6:390–396
Yoon YG, Park GG, Yang TH, Han JN, Lee WY, Kim CS
(2003) Effect of pore structure of catalyst layer in a
PEMF C on its performance. Int J Hydrog Energy
28:657–662
S
Seeding for Zeolite Membranes
Anne Julbe and Martin Drobek
Institut Européen des Membranes, Université de
Montpellier, Montpellier, France
The seeding process can be described as a method
in which a small piece of a single crystal/poly-
crystal (seed) is used to act as an active site
(nuclei) for growing a larger crystal when
exposed to the effect of nutrients (liquids or gas)
in a reaction system. The addition of seeds shifts
the equilibrium toward crystal formation and
avoids the undesirable random nature of sponta-
neous nucleation. This procedure is typically
applied for solutions during recrystallization pro-
cesses, thus eliminating the need for molecular
collision/interaction and decreasing significantly
the time required for nucleation. The seeding
strategy is also largely applied for growing uni-
form zeolite membranes on porous supports,
starting from a layer of closely packed seed crys-
tals which have been previously nucleated (Julbe
2007). The decoupling of the nucleation step
(at high supersaturation) from the crystal growth
(at low supersaturation) makes the formation of a
zeolite membrane very rapid as compared to
direct growth without any seeds. As the concen-
tration needed for secondary growth is lower than
that for nucleation, further homogeneous nucle-
ation is avoided and crystal growth occurs only
on the existing seeds. Additional benefits include
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_758-1
both the minimization or suppression of the crys-
tallization of undesired phases and limitation of
support dissolution (support etching might alter
both its mechanical integrity and zeolite compo-
sition), while in some cases controlling the rate
and direction of crystal growth. However, since
the support is porous, uncontrolled infiltration of
seeds in the pores might reduce membrane
permeance by creating longer effective diffusion
paths through the zeolite material (Hedlund
et al. 2002). Controlled support seeding is there-
fore of great importance for growing uniform and
good quality membranes, preferably with low
infiltration into the porous support (Fig. 1). Clas-
sical coating or seeding methods are dip coating,
slip casting, spin coating, rubbing, vacuum
seeding, and spray coating. Specific methods for
attaching zeolite seeds onto porous supports
include either covalent linkage or electrostatic
forces, using pH effects, cationic polymers, or
silane coupling agents (Lai et al. 2004). Seeding
with either commercial or homemade seeds is
considered as one of the most attractive methods
for preparing a variety of zeolite (e.g., LTA, MFI,
SOD, FAU, CHA, DDR) and zeolite-type (e.g.,
MCM, MOF) membranes. It confers improved
flexibility for controlling crystal growth and
film microstructure with high reproducibility
and scalability. In industry, the seeding process
is typically applied by Mitsui Engineering and
Shipbuilding Co. Ltd. for the preparation of zeo-
lite membranes, including LTA (Morigami
et al. 2001).
2 Seeding for Zeolite Membranes

Moor PP (2002) High-flux MFI membranes. Micropo-

rous Mesoporous Mater 52:179–189
Julbe A (2007) Zeolite membranes – synthesis, character-
ization and applications. In: van Bekkum H, Cejka J,
Corma A, Schuth F (eds) Introduction to zeolite sci-
ence and practice, studies in surface science and catal-
ysis. Elsevier, Amsterdam, pp 181–219
Lai Z, Tsapatsis M, Nicolich JP (2004) Siliceous ZSM-5
membranes by secondary growth of b-oriented seed
layers. Adv Funct Mater 14:716–729
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Technol 25:251–260
Motuzas J, Julbe A, Noble RD, van der Lee A,
Beresnevicius ZJ (2006) Rapid synthesis of oriented
silicalite-1 membranes by microwave-assisted hydro-
Seeding for Zeolite Membranes, Fig. 1 Layer of thermal treatment. Microporous Mesoporous Mater
silicalite-1 (MFI) zeolite nanoseeds deposited by slip cast- 92:259–269
ing on a macroporous a-Al2O3 tubular support provided
by Pall Exekia (Motuzas et al. 2006)

References

Hedlund J, Sterte J, Anthonis M, Bons AJ, Carstensen B,

Corcoran N, Cox D, Deckman H, de Gijnst W, de
S
Silica Gel for Membrane Preparation reaction is washed prior to the dehydration pro-
1,2 1,2
A. F. Ismail , M. H. D. Othman and M. A.
Rahman1,2
1
Advanced Membrane Technology Research
Centre (AMTEC), Universiti Teknologi
Malaysia, Skudai, Johor, Malaysia
2
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia
Silica Gel for Membrane Preparation
Silica gel is composed of silicon oxide
manufactured widely for moisture removal. It is
typically in solid form and possesses high ability
in water absorption. The used silica gel can be
regenerated by heat treatment at temperature
range of 100–120  C for several hours. In addi-
tion, it is also a stable material, nontoxic, and
easily available and inexpensive. Commercial
silica gel typically has high surface area, large
total pore volume, and broad pore size distribu-
tion (Wang et al. 2012). These characteristics
produce less resistance for gas/liquid to diffusion
into it and thus make this material potentially to
be used as a membrane material.
Silica gel can be prepared via a chemical reac-
tion between sodium silicate with an acidic solu-
tion at constant pH (Greenwood and Earnshaw
1997). To produce silica gel for commercial uses,
a gelatinous precipitate obtained from the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_760-2
cess to produce colorless silica gel. Typically,
cobalt chloride or ammonium tetrachloro-
cobaltate is added to silica gel to give a visible
indication of its moisture content (Greenwood
and Earnshaw 1997).
However, for membrane fabrication process,
silica gel can be synthesized using polyconden-
sation of hydrolyzed tetraethoxysilane (TEOS)
under acidic conditions through a sol-gel
approach (Lavorgna et al. 2007; Mishra
et al. 2012). This method is more favorable
because high-purity silicate glasses can be
obtained. Similar to other ceramic material, silica
gel has hydroxyl group on its outer surface which
enables anchoring process to be carried out effec-
tively. This process is also known as functiona-
lization which is a crucial step in the fabrication
of membrane on the top of silica gel support
which facilitates the intimidation between these
two layers.
Various organic chemicals are used to
functionalize silica gel, and the method to obtain
chemical bridge between support and membrane
might be different among research group. How-
ever, there is a general consensus in the way of
functionalizing silica gel such as removal of
moisture prior to functionalization process, stir-
ring and mixing process between precursor of
chemical bridge and silica gel, and washing and
drying cycle using alcohol (Lavorgna et al. 2007).
These preparation steps are rather simple without
2 Silica Gel for Membrane Preparation
the necessity of using complex methods and
advance equipments.
Silica gel has been recognized as a promising
additive material in polymeric membrane for fuel
cell application (Mishra et al. 2012). Due to its
high hydrophilicity in nature, it has been used to
increase proton conductivity of commercial fuel
cell electrolyte membrane, i.e., Nafion ®, and
retain humidity when the membrane is used at
temperature higher than 80  C (Mishra
et al. 2012). The incorporation of silica gel into
polymeric membrane can be accomplished by
adding the silica gel into polymeric solution
prior to the casting step and the drying process
(Mishra et al. 2012; Seo et al. 2006). This
approach enables the silica gel to be homoge-
neously dispersed across polymer matrix. How-
ever, the functionalization of silica gel should be
carried out prior to this process. On the other
hand, the silica-based composite membrane can
be fabricated by impregnation process (Mishra
et al. 2012; Mahreni et al. 2009). This can be
achieved by soaking the membrane by silica sol
followed by functionalization process. These two
approaches can be categorized as ex situ
approach in producing composite membrane for
fuel cell application. There is another approach
known as in situ technique which involves the
incorporation of either nanoparticles or their pre-
cursors into monomer solution with low viscosity
(Mishra et al. 2012). This approach ensures better
dispersion and physical properties but very little
information can be obtained from open literature
(Mishra et al. 2012). It is perhaps that this
technique is rather scarce compared to ex situ
approach. Furthermore, the incorporation of
hydrophilic silica gel with a monomer obscures
polymerization process causing a reduction in
membrane molecular weight and the formation
of undesirable cross-linking (Mishra et al. 2012).
Therefore, the fabrication of commercial com-
posite membrane for fuel cell application such
as Nafion ® uses an ex situ approach due to its
simplicity and controllability.
References
Greenwood NN, Earnshaw A (1997) Chemistry of the
elements, 2nd edn. Butterworth–Heinemann, Boston
Lavorgna M, Mascia L, Mensitieri G, Gilbert M,
Scherillo G, Palomba B (2007) Hybridization of
Nafion membranes by the infusion of functionalized
siloxane precursors. J Membr Sci 294:159–168
Mahreni A, Mohamad AB, Kadhum AAH, Daud WRW,
Iyuke SE (2009) Nafion®/silicon oxide/
phosphotungstic acid nanocomposite membrane with
enhanced proton conductivity. J Membr Sci 327:32–40
Mishra AK, Bose S, Kuila T, Kim NH, Lee JH (2012) -
Silicate-based polymer-nanocomposite membranes
for polymer electrolyte membrane fuel cells. Prog
Polym Sci 37:842–869
Seo WJ, Sung YT, Han SJ, Kim YH, Ryu OH, Lee HS,
Kim WN (2006) Synthesis and properties of polyure-
thane/clay nanocomposite by clay modified with poly-
meric methane diisocyanate. J Appl Polym Sci
101:2879–2883
Wang K, Shang H, Li L, Yan X, Yan Z, Liu C, Zha
Q (2012) Efficient CO2 capture on low-cost silica gel
modified by polyethyleneimine. J Nat Gas Chem
21:319–323
S
Stack of Single Cells in
Electrodialysis
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Electrodialysis is an electrochemical process (see
“▶ Electrochemical Processing, Electrochemis-
try”) for separating an aqueous feed solution into
a concentrate or brine and dilute or desalted water
by means of an electrical field and ion-selective
membranes. Electrodialysis takes place in an elec-
trodialysis stack. A schematic representation of
such a stack with anion- (A) and cation-
(C) exchange membranes arranged in an alternating
series pattern is shown in Fig. 1. For practical
application, number of membranes in an electrodi-
alysis stack is much higher than shown in Fig. 1.
For example, such stacks might contain up to
600 pairs of membranes (a unit cell is a combina-
tion of one cation-exchange membrane and one
anion-exchange membrane) (Seader and Henley
2006). The size of a membrane is usually between
0.4 and 1.5 m2 and they are separated from each
other by spacer gaskets. A typical voltage drop
across the unit cell is 0.5–1.5 V and typical current
densities are in the range of 5–50 mA cm
2. The
movement of ions in the electrodialysis stack is
dictated by the direction of an electrical field and
allowance of a membrane for an ion transport. For
example, in compartments 3, 5, and 7 (Fig. 1) under
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_763-2
influence of the electrical field cations will move
across cation-exchange membrane and anions
across anion-exchange membrane, resulting in for-
mation of dilute. On the other hand, in compart-
ments 2, 4, 6, and 8 the anion- and cation-exchange
membranes do not allow movement of ions in the
direction of electrical field, resulting in formation of
concentrate in this compartments. As in other elec-
trochemical processes, ionic current will be finally
transformed into electrical current by means of
electrochemical reactions taking place at the cath-
ode and anode. The main application of electrodi-
alysis is the desalination of brackish water. Other
applications include waste water treatment, separa-
tion of salts, and some food industry applications.
Typical ion-exchange membranes are made of
polystyrene, containing fixed sulfonate –SO3

groups (cation-exchange membrane) or quater-
nary ammonium groups such as –NH3+
(anionucexchange membranes) (2008). The
thickness of the membranes is 0.2–0.5 mm and
they are reinforced to provide better mechanical
stability. The membranes are wetted with water,
but due to the size of pore networks inside of
membranes water transport across the membrane
is largely prohibited. The selectivity of mem-
branes for an anion or cation is better than 90 %.
Stack of Fuel Cells in Electrodialysis
Alkaline fuel cell (AFC) is a fuel cell type which
utilizes alkaline electrolyte, usually potassium
2 Stack of Single Cells in Electrodialysis
Stack of Single Cells in Electrodialysis, Fig. 1 Schematic representation of the electrodialysis process. C cation-
exchange membrane, A anion-exchange membrane
hydroxide. It consumes hydrogen and oxygen
producing only water, heat, and electricity.
Depending on a concentration of potassium
hydroxide AFC can operate at temperatures
between 60  C and 250  C. The fuel cell reactions
are as follows:
Anode : H2 þ 2OH
⇄2H2 O þ 2e

Cathode : 1⁄2 O2 þ 2e
þ 2H2 O⇄2OH

Overall reaction : H2 þ 1⁄2 O2 ⇄H2 O
The main ionic charge carriers are OH
ions
which mitigate from the cathode to the anode.
Water is formed at the anode side and has to be
removed from the system in order to prevent
KOH dilution. The AFC has improved cathode
performance compared to acidic fuel cells due to
more favorable oxygen reduction reaction kinet-
ics. For this reason, AFC can achieve higher
efficiency, i.e., higher voltage at comparable cur-
rent densities than other fuel cell types. It has
very long operating life time, e.g., 15,000 h
have been demonstrated (Cifrain and Kordesch
2003). Furthermore, alkaline conditions allow
application of nonprecious metal catalysts
which could reduce significantly the material
costs of this fuel cell. One of the major disadvan-
tages of AFC is its low CO2 tolerance due to
formation of carbonates according to:
CO2 þ 2OH
⇄CO2 2
þ H2 O
The carbonates have low solubility in strong alka-
line environments forming crystals, capable of
blocking of electrolyte pathways. The low CO2
tolerance and the application of liquid electrolyte
are two main hurdles for the broader commercial-
ization of these systems. However, due to its high
efficiency and high power density AFC found
applications in aerospace industry, e.g., they
were employed on the Appollo missions as well
as on the space shuttle orbitals. For other exam-
ples of developed AFC systems please see
(Seader and Henley 2006; Electroseparations,
electrodialysis 2008).
Hydrogen and oxygen gases in the AFC are
separated by a membrane. Usually permeable
membranes also called diaphragms have been
used (G€ulzow 2012). A common diaphragm
material up to 1980s was asbestos which due to
health and environmental concerns is nowadays
abandoned. Alternative materials are different
polymer materials like porous polyethylene
plates, nonwoven polypropylene and similar.
Stack of Single Cells in Electrodialysis
Potassium hydroxide electrolyte wets the dia-
phragm pores in order to ensure its ionic conduc-
tivity. For a good fuel cell performance, the
electrolyte resistance induced by diaphragm has
to be minimized. This resistance is influenced by
the thickness of the diaphragm material, its pore
size and tortuosity, and the KOH concentration.
Since liquid electrolyte causes some practical
problems in AFC usage, new developments go
into direction of alkaline polymer electrolyte
membranes which in addition to separation pos-
sesses, similar to its acidic equivalent (e.g.,
Nafion), ionic conductivity in absence of liquid
electrolyte. Currently there is no long-term stable
membrane functioning without a liquid electro-
lyte phase.
3
References
Cifrain M, Kordesch K (2003) Hydrogen/oxygen (air) fuel
cells with alkaline electrolytes. In: Vielstich W,
Gasteiger HA, Lamm A (eds) Handbook of fuel
cells-fundamentals, technology and applications,
vol 1, Fundamentals and survey of systems. John
Wiley & Sons, Chichester
Electroseparations, electrodialysis (2008) In: Kirk-
Othmer separation technology, 2nd edn, vol 1. Wiley,
pp 779–792
G€
ulzow E (2012) Alkaline fuel cells. In: Stolten D, Emonts
B (eds) Fuel cell science and engineering: materials,
processes, systems and technology, vol 1. John Wiley
& Sons, Wiley-VCH, pp 97–129
Seader JD, Henley EJ (2006) Electrodyalysis. In: Separa-
tion process principles, 2nd edn. John Wiley & Sons
Inc, Hoboken, NJ, pp 518–521
U
Use of Streaming Potential
Measurements for Characterization
of Both Membrane/Electrolyte
Interface and Protein Fouling Effect
Juana Benavente
Departamento de Fisica Aplicada I, Facultad de
Ciencias, Universidad de Malaga, Malaga, Spain
Electrical nature of external and internal (pore-
wall) membrane surfaces is significant for salt
rejection and transport characterization of RO
and NF membranes or for filtration of solutions
containing macromolecules and colloids. Elec-
trokinetic measurements are usually performed
for characterization of membrane/electrolyte
interfaces and to estimate changes associated to
membrane fouling as a result of cake layer for-
mation (external fouling) or pore narrowing/
plugging (internal fouling).
Zeta potential (z) is the stationary electrical
potential at the shear plane between fixed and
mobile ions in the double layer associated to
solid-liquid charged interfaces. For weakly
charged walls or wide channels/pores, z-potential
is obtained from streaming potential coefficient
(Døst/DP)I = 0 by Helmholtz-Smoluchowski equa-
tion (Hunter 1988):
zH
S ¼ ðle Zeo eÞðDøst=DPÞI¼0
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_765-3
where le, Z, e, and eo are the solution conductiv-
ity, viscosity, membrane dielectric constant, and
vacuum permeability, respectively.
To show the potentiality of electrokinetic
characterization, z-potential results for clean
and BSA-fouled porous membranes, polymeric
(GR, polysulfone <rp>  0.1 mm) and ceramic
(Z100S, ZrO2/Al2O3 on stain steel support <rp>
 0.06 mm), by transmembrane measurements at
different pHs (Lara and Benavente 2009), and
tangential measurements changing NaCl concen-
tration for a dense regenerated cellulose
(RC) membrane are presented (Cañas
et al. 2001).
Figure 1a shows the comparison of z values as
a function of solution pH for GR and Z100S
membranes. Polysulfone GR membrane exhibits
electronegative character, but it is electropositive
for ceramic Z100S; moreover, z-potentials for
GR membrane slightly vary due to BSA fouling,
but they significantly change for the ceramic
sample (from positive to negative), and practi-
cally the same isoelectric point (z = 0) was
obtained with both fouled membranes, which
corresponds to the BSA isoelectric point. These
results indicate the BSA coverage of pore walls
for both fouled samples.
Figure 1b shows z-potential dependence on
solution concentration for clean GR (through
pores) and dense RC (along surface) membranes,
(1) indicating absorption of Cl-ions on internal
(GR) or external (RC) membrane surfaces.
2 Use of Streaming Potential Measurements
Use of Streaming Potential Measurements for Char-
acterization of Both Membrane/Electrolyte Interface
and Protein Fouling Effect, Fig. 1 z-potential as a
function of (a) pH for clean (D) and BSA-fouled (~)
Analysis of electrokinetic surface charge den-
sity or charge density at shear plane
(se = (2RTeoe k/F)sinh(Fz/2RT)) with the
molar fraction of ions (c-  Cn
MH2O) can
give information on adsorption parameters using
adequate models (homogeneous Langmuir model
or heterogeneous Freundlich model (Benavente
et al. 1993), and the following values for the
chemical part of free adsorption energy (DGch)
and total number of adsorption sites per mem-
brane area (N) were obtained for GR and RC
membranes assuming a Langmuir model:
Polysulfone GR: DGch ¼
ð18:9  0:7Þ
kJ=mol, N ¼ ð4:9  0:4Þ  1015 m
2 :
Cellulosic RC: DGch ¼
ð25:7  0:7Þ
kJ=mol, N ¼ ð1:4  0:5Þ  1016 m
2 :
GM membranes, clean (□) and BSA-fouled (■) Z100S
membranes; (b) concentration for clean GM (D) and RC
(◊) membranes
Differences associated to membrane material
can be obtained; the negative sign and low values
of DGch indicate spontaneous adsorption of
Cl-ions on membrane pore-wall or external
surface.
References
Benavente J, Hernandez A, Jonsson G (1993) Proper and
absorbed charges on the surface of polysulfone support
of a composite membrane from electrokinetic phe-
nomena. J Membr Sci 80:285–296
Cañas A, Ariza JM, Benavente J (2001) Electrokinetic and
electrochemical characterizations of a porous mem-
brane. Colloids Surf A 189:247–256
Hunter RJ (1988) Zeta-potential in colloid science. Prin-
ciples and applications. Academic, London
Lara R, Benavente J (2009) Use of hydrodynamic and
electrical measurements to determine protein-fouling
mechanisms for microfiltration membranes with dif-
ferent structures and materials. Sep Purif Technol
66:517–524
S
Sweep Gas in a Membrane Reactor
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende (CS), Italy
The sweep gas is a gas present in the permeate
side of a membrane reactor to lower the partial
pressure of the permeating species and increase
the driving force. This gas should be different
from any species produced by the reaction, and
permeating the membrane because of its back
permeation into the reaction side deflects the
reaction.
The permeation driving force, for any perme-
able species, is a function of the difference of
chemical potential on both reaction and perme-
ation sides of the membrane reactor. This is also
valid for membrane reactors used for gas-phase
reactions where the driving force can be
increased operating on partial pressure both
increasing the feed one and reducing permeate
pressure of the specific chemical species.
Specifically, the partial pressure of a permeating
species can be reduced in two ways: reducing the
total pressure on the permeate side, applying a
vacuum, for instance, and/or using a sweep gas on
the permeate side. Both ones have the same effect
since they increase the permeation driving force
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_768-1
improving, as a consequence, the membrane
reactor performance, that is, conversion and, if
we’re speaking about hydrogen production, the
hydrogen recovery on the permeate side. However,
depending on the used method, the permeate phase
will have a very different composition. It will
consist of the only permeable species in the case
the vacuum is applied. In the other case, the
concentration of the permeable species will be
lowered by the presence of the sweep gas; thus,
another separation stage is required for purifying
the permeate phase.
In a flow membrane reactor, the sweep stream
can flow in co- or countercurrent with respect to
the feed stream. The Fig. 1 shows the latter option
in the case of methane conversion for hydrogen
production.
Marigliano et al. (2003) demonstrated that in
hydrogen production from methane steam
reforming in palladium-based membrane reactor,
a high hydrogen partial pressure on permeate led
to a lower methane conversion, but a higher
sweep gas flow rate reduces the hydrogen partial
pressure increasing, in the meantime, the meth-
ane conversion.
The use of a sweep gas results in the dilution of
the permeated species concentration (Marigliano
et al. 2003). It is a drawback in many production
cycles such as hydrogen production since the
hydrogen permeating the membrane results
2 Sweep Gas in a Membrane Reactor

Q Feed Q Retentate
J Permeating
H2
Q Permeate QSweep
P Permeation
Me m b r a ne
SS- She l l
P Reaction Ca t a l y s t

Sweep Gas in a Membrane Reactor, Fig. 1 Scheme of a membrane reactor showing the four inlet/outlet stream,
including the sweep gas one

diluted and requires a concentration. Few cases, References

for instance, are exceptions: (a) hydrogen pro-
duced for ammonia synthesis is good if diluted
with nitrogen in a right feed ratio, and (b) the
reaction conversion plays a more significant role
than the permeated species.
Marigliano G, Barbieri G, Drioli E (2003) Equilibrium
conversion for a palladium membrane reactor. Depen-
dence of the temperature and pressure. Chem Eng
Process 42:231–236. doi:10.1016/S0255-2701(02)
00092-2
S
Sweep Gas Membrane Distillation
(SGMD)
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Poland
SGMD is a membrane distillation
(MD) configuration in which a stripping gas is
used as a carrier for the vapor transferred from a
warm aqueous feed through a porous hydropho-
bic membrane. The nature of the membrane pre-
vents from penetration of liquid into the pores;
therefore, the liquid/vapor interface is formed at
each pore entrance. The volatile molecules evap-
orate through the membrane pores, and a cold
inert gas flowing along the other side of the mem-
brane sweeps the permeate carrying it away from
the module. The condensation of the vapor occurs
in an external condenser (Fig. 1). The driving
force for the mass transfer in SGMD is the dif-
ference in the partial pressure of volatile sub-
stances on both sides of the membrane. Since in
MD heat is transferred from the feed side through
the membrane, thus the sweep gas temperature
increases considerably along a module. However,
SGMD combines a relatively low conductive
heat loss through the membrane with a reduced
mass transfer resistance. Hence, the resulting
high mass transfer coefficients provide higher
permeate flux than that in direct contact
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_769-2
membrane distillation (DCMD) (using the same
membrane).
Membranes used in SGMD are porous and
hydrophobic, similarly as in other MD configu-
rations. Air, humid air, or dry nitrogen can be
used as a sweep gas.
The permeate flux obtained in SGMD can be
in the range from ca. 1 to 25 kg/m2h, depending
on the membrane type, feed composition, and
operating conditions (Khayet and Matsuura
2011). Nonvolatile species present in an aqueous
solution are theoretically completely retained in
the feed, whereas volatile organic substances are
partially transferred through a membrane. The
separation performance in SGMD is determined
by a vapor/liquid equilibrium and depends
mainly on a difference in volatility of compo-
nents in a mixture. However, the differences in
the diffusion rates of components through the gas
in the membrane pores should be also taken into
account.
For the case when SGMD is applied for treat-
ment of an aqueous solution containing nonvola-
tile compounds and the permeate is swept away
using air or any other neutral gas, the equations
describing mass (J) and heat (Q) transfer in
DCMD can be adapted (Khayet and Matsuura
2011):


J w ¼ Bw p0w, f aw, f  pw, p
2 Sweep Gas Membrane Distillation (SGMD)

Feed Tf,in Sweep gas+vapor Conduction Sweep gas

Warm feed
Tp,out + vapor
Qc
Condenser Latent heat
Gas Qf Qp
Qv
Permeate
Qm
membrane Membrane

Sweep Gas Membrane Distillation (SGMD),

Fig. 2 Heat transfer resistances in SGMD
Tf,out Sweep gas Tp,in X

J¼ Bj p0j, f aj, f  pj, p
Tf,in > Tf,out Tp,in < Tp,out j
X

Sweep Gas Membrane Distillation (SGMD), ¼ Bj p0j, f gj, f xj, f  f j, p Pyj, p
Fig. 1 Schema of SGMD process j

where B is membrane permeability (depends on
membrane properties, e.g., thickness, porosity,
pore size) under the SGMD conditions, p is par-
tial pressure, and aw is water activity. The super-
script 0 denotes pure water, and subscripts w, f,
and p refer to water, feed, and permeate, respec-
tively. The p0w,f and aw, f depend on the feed tem-
perature, whereas Pw, p depends on the gas
temperature at the membrane surface,
respectively.
When volatile compounds are present in a
feed, both the water vapor and the molecules of
volatile compounds are transferred across a mem-
brane. The separation factor of volatile com-
pound i (ai) can be calculated as:
 
yi, p = 1  yi, p
ai ¼  
xi, f = 1  xi, f
where yi, p and xi, f are molar fractions of i species
in the gaseous permeate and liquid feed,
respectively.
In this case the total SGMD permeate flux (J)
(if coupling effects are not considered) can be
written as:
where gj, f, xj, f, and fj, p are the activity coefficient,
the mole fraction in the liquid and gas phase, and
the fugacity coefficient of species j, respectively.
The subscript j refers to all volatile compounds
including water.
Various models were applied for description
of mass transfer in SGMD. Nevertheless, it was
usually concluded that the transport occurred
according to a combined Knudsen/ordinary
molecular diffusion mechanism.
The heat transfer in SGMD (Q) is described by
the following steps: heat transfer through the
liquid boundary layer on a feed side (Qf), heat
transfer through a membrane (Qm) (through a
membrane material and gas-filling pores (Qc)
and with permeate stream Qv), and heat transfer
through the gas boundary layer (Qp) (Fig. 2).
Value of the permeate flux depends on the
SGMD operation conditions, e.g., the inlet tem-
peratures and the flow rates of both fluids, i.e.,
liquid feed and sweep gas, and membrane char-
acteristics. The permeate flux is strongly depen-
dent on a feed temperature because of
exponential growth of vapor pressure with tem-
perature. On the contrary, an increase in the
sweep gas temperature leads to a decrease of the
vapor pressure gradient thus the resultant perme-
ate flux is lower. The major disadvantage of
SGMD configuration is a very high increase of
the gas temperature along a module.
Sweep Gas Membrane Distillation (SGMD)
The permeate flux is practically independent
on the feed flow rate. The sweep gas flow rate is a
very important parameter. An increase in the
permeate flux with sweeping gas flow rate is
caused by improved hydrodynamic conditions
on the permeate side and a reduction of temper-
ature polarization effect. The thermal efficiency
of SGMD is higher than in DCMD because the
heat loss by conduction through a membrane is
lower (Charfi et al. 2010; Khayet and Matsuura
3
2011). It was found that the permeate flux is
higher for membranes with larger pore size.
References
Charfi K, Khayet M, Safi MJ (2010) Numerical simulation
and experimental studies on heat and mass transfer
using sweeping gas membrane distillation. Desalina-
tion 259:84–96
Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
S
Sweep Gas Membrane Distillation
(SGMD) Applications
Maria Tomaszewska
Faculty of Chemical Technology and
Engineering, West Pomeranian University of
Technology, Szczecin, Poland
SGMD is the least frequently used configuration
of membrane distillation (MD) because the exter-
nal condenser is required to collect the permeate.
Moreover, a little amount of the permeate is col-
lected by a large volume of a sweep gas. There-
fore, the system design is complicated and rather
expensive.
Similarly as the other MD configurations, the
SGMD can be used to treat the solutions
containing nonvolatile compounds, such as
salts. The salt rejection is practically 100 % and
high-purity water can be obtained. However,
since the volatile species permeate through the
membrane, a more profitable application of
SGMD is the removal of volatile organic sub-
stances (esters, ethers, chlorinated hydrocarbons,
aromatic compounds) or dissolved gases from
aqueous solutions. Thus, SGMD can be applied
in chemical and petrochemical industries, in bio-
technology, or in environmental engineering,
where the organic substances have to be recov-
ered/removed from very diluted solutions. More-
over, SGMD can be applied in the cases where
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_770-2
DCMD cannot be used due to the risk of the
membrane wetting.
Laboratory-scale studies have demonstrated a
high potential of SGMD for removal of organic
volatile compounds such as ethanol, isopropanol
(IPA), and acetone from wastewater (Khayet and
Matsuura 2011). A novel SGMD-based micro-
separator has been studied for the separation of
a mixture of methanol and water. A bioreactor
combined with SGMD for ethanol production
was also proposed, in order to enhance the etha-
nol productivity as well as to eliminate the fer-
mentation inhibitors. The produced ethanol was
free of bacteria, nutrients, and metabolites
(He et al. 2012).
SGMD was applied for treatment of IPA aque-
ous solutions (below 10 wt.%). The influence of
feed temperature on the selectivity and permeate
flux is presented in Fig. 1. It was found that the
selectivity decreased with an increase of sweep
gas flow rate and with IPA concentration in a
feed. Moreover, MgCl2 addition to the feed
increased significantly IPA selectivity, with
small reduction of the total permeate flux (Lee
and Hong 2001).
High effectiveness (97 %) of SGMD during
the removal of ammonia from synthetic industrial
wastewater (100 mg/l, pH 11) was also found
(Fig. 2). At higher feed temperature, the permeate
flux significantly increased, but the selectivity of
ammonia was reduced. For membranes with
smaller thickness and larger pore size, the mass
transfer coefficient of ammonia was higher,
2 Sweep Gas Membrane Distillation (SGMD) Applications

a 2 b 26
0.03 0.03
0.05
24 0.05
0.07 0.07
0.095 22 0.095

20
Flux(kg/m2hr)

18

Selectivity
1 16

14

12

Feed flow rate 12.9 kg/h 10 Feed flow rate 12.9 kg/h
Gas velocity 8.7 m/s Gas velocity 8.7 m/s
8
Gas temperature 25 °C Gas temperature 25 °C
0 6
15 20 25 30 35 40 45 50 15 20 25 30 35 40 45 50
Feed temperature (°C) Feed temperature (°C)

Sweep Gas Membrane Distillation (SGMD) Applica- concentrations (Reprinted from Lee and Hong 2001,
tions, Fig. 1 (a) SGMD flux and (b) IPA selectivity as a copyright (2001), with permission from Elsevier)
function of feed temperature at various feed

a 120 b 100

100
80
Ammonia removal (%)

Ammonia removal, %

80
60
60
40
40 0.4 L/min
50 °C 2 L/min
20
20 65 °C 3 L/min
Gas flow rate 2 L/min 75 °C Feed temp. 75 °C 5 L/min
0 0
0 50 100 150 200 0 50 100 150 200
Time (min) Time, min

Sweep Gas Membrane Distillation (SGMD) Applica- flow rate 250 mL/min (Reprinted from Xie et al. 2009,
tions, Fig. 2 (a) Effect of feed temperature and (b) flow copyright (2009), with permission from Elsevier)
rate of sweep gas on ammonia removal using SGMD, feed

whereas its selectivity was lower. The pH of was also used for the recovery of black currant
ammonia solution was very important for its sep- and cherry juice aroma compounds from a model
aration (Xie et al. 2009). solution and for the retention of anthocyanins in
Another SGMD application can be an indus- the juice. An increase in the feed temperature
trial fruit juice processing. Successful experi- improved the aroma flux; thus, their concentra-
ments were carried out using SGMD for the tion in the permeate was elevated. The highest
concentration of sucrose solutions as a model concentration factors for highly volatile aroma
fruit juice (Khayet and Matsuura 2011). SGMD compounds were in the range of 12.1–9.3 (black
Sweep Gas Membrane Distillation (SGMD) Applications 3

90 1,8-Clneole
1,8-clneole (exp.)
80 Ethyl butanoate
Ethyl butanoate (exp.)
Isoamyl acetate
70 Isoamyl acetate (exp.)
Recovered aroma (%)

4-Terplnenol
60 4-Terplnenol (exp.)
cls-3-Hexen-1-ol
50 cls-3-Hexen-1-ol (exp.)

40

30

20

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Feed volume reduction (%)

Sweep Gas Membrane Distillation (SGMD) Applica- (Reprinted from Bagger-Jørgensen et al. 2011, copyright
tions, Fig. 3 The experimental results and theoretically (2011), with permission from Elsevier)
predicted values of aroma fractions recovery by SGMD

currant juice) and 16.3–13.0 (model solution). In
the case of a black currant juice, the amount of
recovered aroma was 73–84 vol.% for the highly
volatile compounds (Fig. 3). However, during the
concentration of juice, a part of anthocyanins and
polyphenols in black currant juice was lost due to
the degradation of anthocyanin by oxidation
(Bagger-Jørgensen et al. 2011).
References
Bagger-Jørgensen R, Meyer AS, Pinelo M, Varming C,
Jonsson G (2011) Recovery of volatile fruit juice
aroma compounds by membrane technology: sweep-
ing gas versus vacuum membrane distillation. Innov
Food Sci Emerg Technol 12:388–39
He Y et al (2012) Recent advances in membrane technolo-
gies for biorefining and bioenergy production.
Biotechnol Adv. doi:10.1016/j.biotechadv.2012.01.015
Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
Lee CH, Hong WH (2001) Effect of operating variables on
the flux and selectivity in sweep gas membrane distil-
lation for dilute aqueous isopropanol. J Membr Sci
188:79–86
Xie Z, Duong T, Hoang M, Nguyen C, Bolto B (2009)
Ammonia removal by sweep gas membrane distilla-
tion. Water Res 43:1693–1699
T

Qt ¼ DðC2  C1 Þt=l
Time Lag Method for Mass Transport 2l X
1
C2 cos np  C1   
Properties Evaluation in GS þ 2 1  exp Dn2 p2 t=l2
p 1 n2
4C0 l X
1
1 n  o
þ 2 1  exp Dð2m þ 1Þ2 p2 t=l2
Donald R. Paul p 0 ð2m þ 1Þ 2

Department of Chemical Engineering, Texas (1)

Materials Institute, Austin, TX, USA
The most common situation is when
C1 = Co = 0 for which Eq. 1 simplifies to
The diffusion time lag method is a useful way to
obtain the diffusion, solubility, and permeability ¼
Q1 " #
coefficients from a single experiment when cer- 2X1
ð1Þn  
tain conditions are satisfied. It takes advantage of lC2 Dt=l  1=6  2
2
exp Dn2 p2 t=l2
p 1 n2
the initial transient portion of a permeation exper-
iment prior to the establishment of steady-state (2)
permeation. Considering a polymer membrane of
At long enough times, the exponential terms van-
thickness l with an initial concentration of pene-
ish, and Eq. 2 approaches the linear asymptotic
trant of Co throughout and at time t = 0, the
line given by
concentration of penetrant is set at C2 within the
upstream face of the membrane and C1 at the
DC2 
downstream face. The accumulative amount of Q1 ¼ t  l2 =6D (3)
l
penetrant per unit area exiting the downstream
surface of the membrane, Qt, versus time can be This steady-state line intercepts the time axis at
obtained from a solution to Fick’s second law t = q or the “time lag” given by
when the diffusion coefficient is constant
(independent of concentration and position in
y ¼ l2 =6D (4)
the membrane), and there are no chemical reac-
tions or adsorption processes (Crank 1975). The as illustrated in Fig. 1. The full solution for Qt ,
result is Eq. 2, becomes experimentally indistinguishable
from the asymptotic line for t3 3q. A common
error in using this method is not allowing enough
time to establish steady state.

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_772-4
2 Time Lag Method for Mass Transport Properties Evaluation in GS
Qt
Polymer
S.S.
c t
dQt
( )
dt S.S.
q t
Time Lag Method for Mass Transport Properties
Evaluation in GS, Fig. 1 A transient permeation exper-
iment illustrating the time lag and the steady-state region
(Paul 2010) (Reproduced with permission by Elsevier
(Copyright 2010))
For simple gases, the equilibrium concentra-
tion of gas in the polymer, C, for a given external
pressure p is given by Henry’s law, C = Sp,
where S is a solubility coefficient. The perme-
ability coefficient P can be calculated from the
slope of the steady-state portion of the graph of Qt
versus t by the definition
 fusion and solution of gases in composite rubber mem-
l dQt
P¼ ss (5)
p2 st
where p2 is the upstream gas pressure and when
the downstream pressure is essentially zero.
Since P = DS, it is possible to compute all three
coefficients from graphs like Fig. 1 using Eqs. 4
and 5.
Since in the above case the membrane is ini-
tially “empty,” i.e., Co = 0, gas must be absorbed
by the membrane to reach steady state so Eq. 4
defines what might be called the “absorption time
lag,” i.e., ya. For the alternate case where
Co = C2, gas must be desorbed to reach steady
state so there is a “desorption time lag” which is
given by
yd ¼ l2 =3D (6)
Petropoulos and Roussis have defined other time
lags and evaluated various relationships among
them for a wide variety of complex situations
(Petropoulos 1967). Barrie et al. evaluated the
time lag for laminated membranes using the
Laplace transforms (Barrie et al. 1963). Frisch
developed a useful mathematical procedure for
constructing asymptotic solutions for permeation
problems, hence time lags, for more complex
situations where full solutions to Fick’s second
law are not feasible (Frisch 1957), e.g., when the
diffusion coefficient depends on penetrant com-
position or position in the membrane or when
chemical reactions or adsorption processes occur.
References
Barrie JA, Levine JD, Michaels AS, Wong P (1963) Dif-
branes. Trans Faraday Soc 59:869–878
Crank J (1975) The mathematics of diffusion, 2nd edn.
Oxford University Press, Oxford
Frisch HL (1957) The time lag in diffusion. J Phys Chem
61:93–95
Paul DR (2010) Fundamentals of transport phenomena in
polymer membranes. In: Drioli E, Giorno L (eds)
Comprehensive membrane science and engineering,
vol 1. Academic, Oxford, pp 75–90
Petropoulos JH (1967) Study of “Non-Fickian” diffusion
anomalies through time lags. I. Some time-dependent
anomalies. J Chem Phys 47:1491–1496
T
Turndown in Gas Separation
Adele Brunetti
National Research Council, Institute for
Membrane Technology (ITM-CNR), The
University of Calabria, Rende (CS), Italy
Turndown is the capability of the system to oper-
ate at reduced capacity (Miller and Söcker 1989).
In gas separation, membrane systems are highly
capable of maintaining product purity even
though the capacity is reduced down to 10 % of
the initial design. This is done by either reducing
feed pressure, increasing permeate pressure, or
by isolating modules from the system. The first
two methods can be used for short-term operation
and the latter when operating at significantly
reduced capacity for extended periods. No pre-
visions are required in the design phase.
Absorption units can maintain both recovery
and product purity at throughputs of
ca. 30–100 % of design by adjustment of the gas
streams and solvent flow rates.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_774-1
Also PSA units can maintain both recovery
and product purity at throughputs of
ca. 30–100 % of design by adjustment of the
cycle time. Between 0 % and 30 % of design
product rates, purity can be maintained, but
recovery is reduced unless special provisions
are made in the design.
The turndown capability of cryogenic systems
strongly depends on the design. Partial conden-
sation units can maintain product purity at
slightly reduced recovery at flows down to
30–50 % of design.
References
Brunetti A, Bernardo P, Drioli E, Barbieri G (2010)
Membrane engineering progresses and potentialities
in gas separations. In: Yampolskii Y, Freeman
B (eds) Membrane gas separation. Wiley, New York,
pp 281–312
Miller GQ, Stöcker J (1989) Selection of a hydrogen
separation process NPRA annual meeting 19–21 Mar,
San Francisco
V
Vacuum Membrane Distillation
(VMD)
A. Criscuoli
Institute on Membrane Technology (ITM-CNR),
Rende (CS), Italy
Vacuum membrane distillation (VMD) is one
of the possible configurations of membrane dis-
tillation, where vacuum is applied at the distillate
side in order to create the driving force for the
water vapor and volatile transfer from the feed to
the permeate side (Fig. 1).
The vacuum is achieved by means of a vac-
uum pump, and the distillate is recovered outside
the membrane module in a refrigerated trap,
where it condenses (at lab scale, liquid nitrogen
is often used as condensing medium); see Fig. 2.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_776-2
As for the other membrane distillation configura-
tions, membrane properties like pore size, poros-
ity, and thickness affect the transmembrane flux,
together with the temperature profile in the
boundary layer of the liquid stream that makes
the temperature at the membrane surface (where
the evaporation takes place) lower than that of the
bulk. Nevertheless, it has to be pointed out that, in
this case, the polarization phenomena occur only
at the feed side, being the distillate one
completely under vacuum. Moreover, the heat
loss by conduction through the solid part of the
membrane is negligible. For these reasons, the
VMD is usually characterized by higher fluxes
and energy efficiency than the other configura-
tions. The high pressure difference established
across the membrane could, however, increase
the risk of membrane wetting.
2 Vacuum Membrane Distillation (VMD)

Closed side
Water vapour and volatiles

Feed Vacuum

Vacuum Membrane Distillation (VMD),

Fig. 1 Scheme of the vacuum membrane distillation

Feed tank

Vacuum pump

Membrane module Distillate condenser

Feed pump

Vacuum Membrane Distillation (VMD), Fig. 2 A typical setup used for carrying out vacuum membrane distillation
tests
V
Vacuum Membrane Distillation
(VMD), Applications of
A. Criscuoli
Institute on Membrane Technology (ITM-CNR),
Rende (CS), Italy
Vacuum membrane distillation (VMD) can be
applied to the treatment of aqueous streams for
recovering purified water or for extracting
specific volatile compounds. Concerning the
first type of application, many studies have
demonstrated the efficiency of the technique for
liquid streams contaminated by nonvolatile
species such as heavy metals or dyes discharged
by textile companies (Criscuoli et al. 2008): in all
cases, the distillate produced consists of purified
water (able to be reutilized inside the productive
plant or to be used for drinking/agriculture
purposes) with rejection values generally higher
than 99 %. Other positive performances are those
related to the treatment of olive mill wastewaters
(Garcia-Castello et al. 2010) and the recovery of
fully demineralized water starting from brackish
waters, seawaters, and reverse osmosis brines
(Li and Sirkar 2005; Safavi and Mohammadi
2009; Méricq et al. 2011). In particular, for the
application to salty solutions, two main benefits
are claimed: the recovery of purified water and
the production of a highly concentrated brine,
with a consequent reduction of its volume and,
therefore, of costs associated to its disposal.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_777-2
VMD can be also used for the concentration of
fruit/vegetable juices (Al-Asheh et al. 2006; Zhao
et al. 2008), again, with the aim of recovering
water as distillate while producing a high concen-
trated retentate that can be easily stored and
shipped.
Referring to the application of VMD to the
extraction of specific volatile compounds
contained in water streams, some examples are
the removal of ethanol (Izquierdo-Gil and
Jonsson 2003); the removal of ammonia
(El Bourawi et al. 2007) or VOCs from water,
like toluene, benzene, etc. (Couffin et al. 1998);
and the recovery of aroma compounds (Soni
et al. 2008; Diban et al. 2009).
Table 1 summarizes the main applications of
VMD.
Vacuum Membrane Distillation (VMD), Applications
of, Table 1 Main applications of VMD
Recovery of purified water from aqueous streams
containing nonvolatile pollutants like heavy metals,
dyes, etc.
Recovery of fully demineralized water from salty
solutions and concentration of reverse osmosis brine
Concentration of fruit and vegetable juices
Recovery of volatile compounds like ethanol, ammonia,
VOCs, etc., from aqueous solutions
2 Vacuum Membrane Distillation (VMD), Applications of
References
Al-Asheh S, Banat F, Qtaishat M, Al-Khateeb M (2006)
Concentration of sucrose solutions via vacuum mem-
brane distillation. Desalination 195:60–68
Couffin N, Cabassud C, Lahoussine-Turcaud V (1998)
A new process to remove halogenated VOCs for drink-
ing water production: vacuum membrane distillation.
Desalination 117:233–245
Criscuoli A, Zhong J, Figoli A, Carnevale MC, Huang R,
Drioli E (2008) Treatment of dye solutions by vacuum
membrane distillation. Water Res 42:5031–5037
Diban N, Voinea OC, Urtiaga A, Ortiz I (2009) Vacuum
membrane distillation of the main pear aroma com-
pound: experimental study and mass transfer model-
ing. J Membr Sci 362:64–75
El-Bourawi MS, Khayet M, Ma R, Ding Z, Li Z, Zhang
X (2007) Application of vacuum membrane distilla-
tion for ammonia removal. J Membr Sci 301:200–209
Garcia-Castello E, Cassano A, Criscuoli A, Conidi C,
Drioli E (2010) Recovery and concentration of poly-
phenols from olive mill wastewaters by integrated
membrane system. Water Res 44:3883–3892
Izquierdo-Gil MA, Jonsson G (2003) Factors affecting
flux and ethanol separation performance in vacuum
membrane distillation (VMD). J Membr Sci
214:113–130
Li B, Sirkar KK (2005) Novel membrane and device for
vacuum membrane distillation-based desalination pro-
cess. J Membr Sci 257:60–75
Méricq J-P, Laborie S, Cabassud C (2011) Evaluation of
systems coupling vacuum membrane distillation and
solar energy for seawater desalination. Chem Eng
J 166:596–606
Safavi M, Mohammadi T (2009) High-salinity water desa-
lination using VMD. Chem Eng J 149:191–195
Soni V, Abildskov J, Jonsson G, Gani R (2008) Modeling
and analysis of vacuum membrane distillation for the
recovery of volatile aroma compounds from black
currant juice. J Membr Sci 320:442–455
Zhao ZP, Ma FW, Liu WF, Liu DZ (2008) Concentration
of ginseng extracts aqueous solution by vacuum mem-
brane distillation. 1. Effects of operating conditions.
Desalination 234:152–157
V
Volume Index
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende (CS), Italy
The use of membrane reactors has several advan-
tages, the most important of which is related to
the gain in terms of conversion, with better mate-
rial exploitation and plant size reduction. In order
to compare membrane performance with that of
conventional operations, different parameters
were proposed (Criscuoli and Drioli 2007).
Behind them, the volume index is a new index,
introduced (Brunetti et al. 2007, 2011a, b, 2012a, b;
Barbieri et al. 2011) as an important parameter
when installing new plants, which must be char-
acterized by low sizes and high productivities. In
particular, it is an indicator comparing the mem-
brane reactor (MR) volume with that of a tradi-
tional reactor (TR) one, in order to achieve a set
conversion, Eq. 1:
for a membrane reactor to reach the set conver-
sion value is much lower with respect to that
required by a conventional reactor. Therefore,
the necessary catalyst weight in the membrane
reactor is significantly reduced.
The water-gas shift reaction can be considered
as an example:
CO þ H2 O ¼ CO2 þ H2
The volume index is a decreasing function of CO
feed pressure, at a set temperature (Fig. 1): when
an equimolecular (H2O:CO = 50:50) mixture is
fed into the reactor at 1500 kPa and a final con-
version of about 80 % (corresponding to 90 % of
the Traditional Reactor Equilibrium Conversion)
is considered, the MR volume is 25 % of that of a
TR and the volume index is equal to 1/4. With a
high feed pressure, more H2 permeates through
the membrane, causing the reaction to shift
toward further CO conversion. As a consequence
a lower catalyst amount is required to achieve a
set conversion.
When the mixture is fed at 600 kPa, the reac-

VolumeMR 
reaction 
tion volume of the membrane reactor is 75 % of
Volume Index ¼ TR  (1) the traditional reactor one, for the same CO
Volume Set Conversion
conversion.
The volume index ranges from 0 to 1: a low
volume index means that the reaction volume

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_780-1
2 Volume Index

100 95%

Traditional Reactor
Volume Index, %
75%

60%
50 40%
[35]
25%
20%

0
Pd-alloy Membrane Reactor
200 400 600 800 1,000 1,500 3,000
Feed Pressure, kPa

Volume Index, Fig. 1 Volume index as a function of feed pressure for an equimolecular H2O:CO mixture. Furnace
temperature = 280  C. Set CO conversion 90 % of the TREC (Brunetti et al. 2007)

References treatment of gases, vol 2, Gas-separation problems

Barbieri G, Brunetti A, Caravella A, Drioli E (2011)
Pd-based membrane reactors for one-stage process of
water gas shift. RSC Adv 1(4):651–661
Brunetti A, Caravella A, Barbieri G, Drioli E (2007) Sim-
ulation study of water gas shift reaction in a membrane
reactor. J Membr Sci 306(1–2):329–340
Brunetti A, Barbieri G, Drioli E (2011a) Membrane reac-
tors in hydrogen production, Chapter 12. In: Drioli E,
Barbieri G (eds) Membrane engineering for the treat-
ment of gases, vol 2, Gas-separation problems com-
bined with membrane reactors. The Royal Society of
Chemistry, Cambridge, UK, pp 87–109
Brunetti A, Barbieri G, Drioli E (2011b) New metrics in
membrane gas separation, Chapter 20. In: Drioli E,
Barbieri G (eds) Membrane engineering for the
combined with membrane reactors. The Royal Society
of Chemistry, Cambridge, UK, pp 279–301
Brunetti A, Caravella A, Drioli E, Barbieri G (2012a)
Process intensification by membrane reactors: high
temperature water gas shift reaction as single stage
for syngas upgrading. Chem Eng Technol
35:1238–1248
Brunetti A, Drioli E, Barbieri G (2012b) Medium/high
temperature water gas shift reaction in a Pd-Ag mem-
brane reactor: an experimental investigation. RSC Adv
2(1):226–233
Criscuoli A, Drioli E (2007) New metrics for evaluating
the performance of membrane operations in the logic
of process intensification. Ind Chem Eng Res
46(8):2268–2271. doi:10.1021/ie0610952
W

Wine Clarification by Membrane from polymeric material and inorganic mem-

Operations branes made from ceramics. Hollow fiber mem-
brane systems are generally preferred. This
Johannes De Bruijn membrane geometry is very compact, which
Department of Agroindustry, Food Engineering means that a large filtration area per unit of vol-
Group, Universidad de Concepcion, Chillan, ume will be available. Moreover, it does not
Chile require a large recirculation flow rate, giving
less mixing and heating of the wine.

Wine Clarification
Process Integration
Wine turbidity is caused by suspended material
like yeast residues and macromolecular com-
This relatively new concept involves the coupling
pounds with colloidal behavior. The clarification
of two or more unit operations that provide a
operation to remove this material is traditionally
more efficient separation than each operation
performed by diatomaceous earth filtration and
alone. The integration of adsorption and cross-
membrane operations have been relatively
flow microfiltration may reduce unstable protein
restricted because of possible removal of poly-
concentration in white wine, increasing at the
saccharides and other macromolecules that may
same time the permeate flux of microfiltration
be of major relevance to wine quality.
due to less severe membrane fouling. After
adsorption using a packed column of zirconium
oxide pellets and cross-flow microfiltration using
Cross-Flow Microfiltration
a ceramic membrane of zirconium oxide with a
pore size of 0.2 mm, an increase of 15–20 % of the
This more recent operation uses a selective
permeate flux has been observed. About 47 % of
porous membrane that filters a wine in order to
the total protein concentration and 15 % of the
achieve its purification or clarification, resulting
total polyphenol concentration have been lost
into a clear appearance and making the wine
during the adsorption stage. Only the percentage
microbiologically stable. By creating a turbulent
of total, volatile, and fixed acidity of wine
stream on the surface of the membrane, settling of
decreased after using the hybrid process without
filtered particles on the membrane will be
changing the other physicochemical wine prop-
prevented. Two main types of membranes are
erties (Salazar et al. 2007).
currently available: organic membranes made
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_781-2
2 Wine Clarification by Membrane Operations

Wine Clarification by Membrane Operations, Fig. 1 Cross-flow ultrafiltration of white wine

Cross-Flow Ultrafiltration tartrate crystallization and their removal may

This membrane operation may be a good alterna-
tive for white wine clarification instead of cross-
flow microfiltration in terms of productivity,
wine quality, and tartaric stability (Fig. 1). Use
of polymeric ultrafiltration membranes with a
molecular weight cut-off of 100 kDa proved to
have similar clarification performance for white
wine as polymeric microfiltration membranes
with 1.0 mm pore size. Polysaccharide removal
was low with both microfiltration and ultrafiltra-
tion membranes. Wine polysaccharides may act
as precipitation inhibitors of potassium hydrogen
decrease tartaric stability of wine (Gonçalves
et al. 2001).
References
Gonçalves F, Fernandes C, de Pinho MN (2001) White
wine clarification by micro/ultrafiltration: effect of
removed colloids in tartaric stability. Sep Pur Technol
22–23:423–429
Salazar FN, de Bruijn JPF, Seminario L, G€ uell C, López
F (2007) Improvement of wine crossflow
microfiltration by a new hybrid process. J Food Eng
79:1329–1336
ß-Lactoglobulin and Alpha-
Lactalbumin Separation
Andrew L. Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
b-Lactoglobulin and a-lactalbumin are the two
dominant proteins in whey (see Table 1).
Although whey protein concentrates are used as
food additives in the production of a variety of
dairy products, meats, and beverages, the unique
nutritional, therapeutic, and functional character-
istics of the individual whey proteins are largely
unrealized in these whey products. There has thus
been considerable commercial interest in the sep-
aration of b-lactoglobulin and a-lactalbumin to
take advantage of their functional and biological
properties. a-Lactalbumin is attractive as a nutra-
ceutical because of its high tryptophan content
(Cayot and Lorient 1997). a-Lactalbumin also
provides enhanced whippability in meringue-like
formulations and may have potential as a contra-
ceptive agent. b-Lactoglobulin is an effective
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_782-6
foam stabilizer and can be used in the production
of confections (Cayot and Lorient 1997).
There are two types of membrane systems that
have been explored for the separation of
b-lactoglobulin and a-lactalbumin: ultrafiltration
and membrane adsorbers (also referred to as
membrane chromatography). Cheang and
Zydney (2003) demonstrated that
b-lactoglobulin and a-lactalbumin could be sep-
arated using commercial ultrafiltration mem-
branes by adjusting the solution pH and ionic
strength to enhance the selectivity. These results
were subsequently extended to purify
b-lactoglobulin and a-lactalbumin from a whey
protein isolate using a two-stage ultrafiltration
process (Cheang and Zydney 2004).
Membrane chromatography is of potential
interest for the separation of b-lactoglobulin and
a-lactalbumin due to the high flow rates that can
be achieved in these systems. For example, Saufi
and Fee (2011) examined the use of a mixed mode
membrane chromatography system containing
both cation and anion exchange sites for the frac-
tionation of whey proteins. b-Lactoglobulin was
preferentially bound to the membrane, with the
a-lactalbumin collected in the flow through.
2 ß-Lactoglobulin and Alpha-Lactalbumin Separation

ß-Lactoglobulin and Alpha-Lactalbumin Separation, Table 1 Physical characteristics of major whey proteins
(From Zydney 1998)
Protein Concentration (g/L) Molecular weight (g/mol) Isoelectric pH
b-Lactoglobulin 2.7 18,362 5.2
a-Lactalbumin 1.2 14,147 4.5–4.8
Immunoglobulins 0.65 150,000–1,000,000 5.5–8.3
Bovine serum albumin 0.4 69,000 4.7–4.9
Lactoferrin 0.1 78,000 9.0
Lactoperoxidase 0.02 89,000 9.5
Glycomacropeptide 7

References Cheang B, Zydney AL (2004) A two-stage ultrafiltration

Cayot P, Lorient D (1997) Structure-function relation-
ships of whey proteins. In: Damodaran S, Paraf
A (eds) Food proteins and their applications. Marcel
Dekker, New York, pp 225–256
Cheang B, Zydney AL (2003) Separation of alpha-
lactalbumin and beta-lactoglobulin using membrane
ultrafiltration. Biotechnol Bioeng 83:201–209
process for fractionation of whey protein isolate.
J Membr Sci 231:159–167
Saufi SM, Fee CJ (2011) Simultaneous anion and cation
exchange chromatography of whey proteins using a
customizable mixed matrix membrane. J Chromatogr
A 1218:9003–9009
Zydney AL (1998) Protein separations using membrane
filtration: new opportunities for whey fractionation. Int
Dairy J 8:243–250
B
Biodegradation
Isabel Coelhoso1, Filomena Freitas2, Vitor D.
Alves3 and Maria A. M. Reis2
1
LAQV-REQUIMTE, Departamento de
Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
2
UCIBIO-REQUIMTE, Departamento de
Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
3
LEAF – Linking Landscape, Environment,
Agriculture and Food, Instituto Superior de
Agronomia, Universidade de Lisboa, Lisboa,
Portugal
Biodegradation is the process by which microor-
ganisms (bacteria, fungi, algae) change the chem-
ical structure of a material into naturally
occurring metabolic products, ultimately
resulting in its conversion into water, carbon
dioxide and/or methane, and new cell biomass
(Muller 2005). The biodegradation of polymeric
materials starts with their depolymerization to
generate lower molecular weight intermediates
that the microbial cells can then assimilate. The
general mechanism of the biodegradation process
includes three phases: (1) secretion of extracellu-
lar enzymes by the microorganisms; (2) genera-
tion of short intermediates by the action of the
secreted enzymes; and (3) conversion of the inter-
mediates into metabolic products (Fig. 1). Water
soluble polymers, such as the natural
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_783-1
polysaccharides xanthan, alginate, and pectin,
are usually more easily degraded, while water
insoluble polymers (e.g., polyesters) are more
difficult to degrade because the process is hetero-
geneous. Abiotic processes, such as chemical
degradation, thermal hydrolysis, or
photodegradation, coexist with the biotic process
and often directly induce it by making the mate-
rials more easily accessible to the microorgan-
isms. Hence, environmental conditions (e.g., pH,
temperature, moisture, salinity, presence/absence
of oxygen, nutrient supply) are important factors
that influence both the materials themselves and
the microbial activity. The complexity of the
materials, namely, the structure and composition
(single polymer or polymer blends), the presence
of additives (e.g., plasticizers), morphology, and
crystallinity, are also key issues that directly
influence their accessibility to the microbial
enzymes.
The standardized methods for testing the bio-
degradability of polymeric materials are based on
previously developed methods for low-molecular
weight substances. However, they have been
modified to consider their higher complexity.
Different biodegradability tests can be
performed, under both controlled laboratory con-
ditions and also natural environmental condi-
tions. In the laboratory tests, defined
environments are created using one of two
approaches: (1) inoculation of synthetic media
with individual microorganisms especially
selected for a given polymer or with a mixed
2 Biodegradation

microorganism microorganism

microorganism
CO2
extracellular low-molecular
enzymes CH H2O
4
weight
intermediates metabolic
products

polymer polymer polymer

(1) (2) (3)

Biodegradation, Fig. 1 General mechanism of the bio- intermediates by the action of the secreted enzymes, and
degradation process: (1) secretion of extracellular (3) conversion of the intermediates into metabolic
enzymes by the microorganisms, (2) generation of short products

Biodegradation, Laboratory tests Field tests

Fig. 2 Biodegradation
tests

Individual Lab reactor Natural

cultures with natural Environment
matrix (water, soil,
(water, soil, compost,
Mixed compost, landfill)
cultures landfill)

Synthetic Complex Complex

media media media

Defined conditions Variable conditions

microbial culture originating, for example, from
a wastewater treatment plant or (2) use of com-
plex materials collected from the environment
(e.g., water, soil, compost) as the matrix for the
tests (Fig. 2).
Some of the standard testing methods include
(Shah et al. 2008):
– Visual observations: macroscopic changes,
such as roughening of the surface, formation
of hole or cracks, changes in color, etc., can be
used as a first indication of microbial attack,
while more sophisticated observations using,
for example, scanning electron microscopy
(SEM) or atomic force microscopy (AFM)
can be made to obtain more information
about the degradation mechanism.
– Weight loss measurements: determination of
residual material after being exposed to the
biodegradation conditions.
– Changes in mechanical properties and
molar mass: properties, such as tensile
strength, can be used as indicators of degrada-
tion since they are related with the polymer’s
molar mass.
– CO2 evolution or O2 consumption: under aer-
obic conditions, the microorganisms use O2
for carbon oxidation, generating CO2 as one
of the major metabolic end product. Hence,
CO2 evolution or O2 consumption are good
indicators of polymer degradation.
– Radio labeling: materials containing a ran-
domly distributed 14C marker can be exposed
to the microbial environment and the amount
Biodegradation
of 14C generated is estimated. It is a high
precision test, but labeled materials are not
always available and are expensive.
– Clear-zone formation: the polymer is placed in
agar plates as very fine particles and inocu-
lated with the microbial culture, being the
formation of a clear halo the indication of
depolymerization.
3
References
Muller R-J (2005) Biodegradability of polymers: regula-
tions and methods for testing. In: Steinb€ uchel A
(ed) Biopolymers, vol 10, General aspects and special
applications. Wiley, Weinheim
Shah AA, Hasan F, Hameed A, Ahmed S (2008) Biolog-
ical degradation of plastics: a comprehensive review.
Biotechnol Adv 26:246–265
C

Corrosion
C. V. Vedavyasan
Desalination Process Specialist (Global),
Department of Technology, Annamalai
University, Chidambaram, Tamil Nadu, India
and not another, but the reverse may be true for
another type of water. An excellent method for
corrosion control in water heaters is cathodic
protection involving the use of a sacrificial
anode, usually composed of magnesium or alu-
minum. Chemical control of corrosion attempts
to retard electrode reactions.

Introduction
The Mechanism and Chemistry of Corrosion
Reactions
Corrosion is the gradual process of wearing,
Corrosion reactions are electrochemical in
weaning away, and thinning down the metal sur-
nature. They involve the transfer of charged
face by the fluid with which it is in contact.
ions across the surface between a metal and the
Millions of dollars are lost every year due to
electrolyte in which the metal is immersed. There
corrosion of iron and steel. Other metals do cor-
are two types of electrode reaction occurring at
rode. The oxide formed by oxidation does not
the metal surface: anodic and cathodic.
firmly adhere to the surface of the metal and
Corrosion occurs in the presence of moisture.
flakes off easily causing “pitting”. Continued
When iron is exposed to moist air, it reacts with
pitting causes structural weakness and disintegra-
oxygen to form rust. The amount of water http://
tion of the metal. Metals such as aluminum form
www.corrosion.com, precisely the number of
a tough oxide coating onto the surface to prevent
molecules of water, present determines the color
corrosion.
of rust varying from black to yellow to orange
In some circles, corrosion has been described
brown. The formation of rust is a very complex
as the tendency of a metal to revert to its natural
process which begins with the oxidation of iron to
stable state as an ore. The process may involve a
ferrous (+2) ions.
second step in which an oxide, hydroxide, or
In an anodic reaction, electrons appear on the
carbonate of the metal may form and deposit at
right-hand side. An example is shown below:
the corrosion site. Thus, corrosion takes place
when a metal dissolves in or is disintegrated by
Fe


> Feþ2 þ 2e
:
water.
Different metals have different tendencies to
corrode or not to corrode in the same water.
A certain type of water may corrode one metal
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_785-3
2 Corrosion
Corrosion, Fig. 1 The
mechanism of corrosion
Both water and oxygen are required for the
sequence of reactions. Iron (+2) ions are further
oxidized to form ferric ions (iron+3) ions:
Feþ2


> Feþ3 þ 1e

The electrons provided from both oxidation steps
are used to reduce oxygen as shown. Cathodic
reactions involve electrochemical reduction
wherein electrons appear on the left side:
O2 ðgÞ þ 2 H2 O þ 4e_


> 4 OH

The ferric ions then combine with oxygen to form
ferric oxide [iron (III) oxide] which is then
hydrated with varying amounts of water. The
reduction of oxygen at an electrode will cause a
rise in pH due to production of hydroxide ion.
The equation for rust formation is
4Feþ2 ðaqÞ þ O2 ðgÞ þ ½4 þ 2  H2 OðlÞ






> 2Fe2 O3  H2 O þ 8 Hþ ðaqÞ :
The formation of rust can occur at some distance
from the actual pitting or erosion of iron. The
electrons produced via the initial oxidation of
iron can be conducted through the metal, and the
iron ions can diffuse through the water layer to
another point on the metal surface where oxygen is
available. This process results in an electrochem-
ical cell in which iron serves as anode, oxygen gas
as the cathode, and iron solution as “salt bridge”.
The involvement of water accounts for the fact
that rusting occurs much more rapidly in moist
environment as compared to dry one. The mecha-
nism of corrosion is shown in Fig. 1 below.
Influence of Salt on Corrosion
The presence of salt enhances the rate of corro-
sion. As the dissolved salt increases, the conduc-
tivity of the aqueous solution at the metal surface
enhances the rate of electrochemical corrosion.
Hence iron and steel corrode more rapidly when
exposed to salt or moist salty air near the ocean.
Factors Associated Mainly with the Metal
• Effective electrode potential of a metal in a
solution
• Overvoltage of hydrogen on the metal
• Chemical and physical homogenity of the
metal surface
• Inherent ability to form an insoluble protective
film
Factors Varying with the Environment
• pH of the solution
• Influence of oxygen in solution adjacent to the
metal
Forms of Corrosion
Galvanic Corrosion
This is an electrochemical action of two dissim-
ilar metals in the presence of an electrolyte and an
electron conductive path. It occurs when
Corrosion 3

dissimilar metals are in contact. It is recognizable

by the presence of a buildup of corrosion at the
joint between the dissimilar metals. When alumi-
num or magnesium alloys are in contact with
carbon or stainless steel, galvanic corrosion
occurs and accelerates the corrosion of aluminum
or magnesium (Fig. 2).

Galvanic Series in Sea Water

(Least Active)
Gold
Graphite
Silver
18-8-3 stainless steel, type 316 (passive)
18-8 stainless steel, type 304 (passive)
Titanium
Thirteen percent Cr stainless steel, type
410 (passive) Corrosion, Fig. 2 Galvanic corrosion
7 Ni- 33 Cu alloy
75Ni – 33 Cu alloy Galvanized steel
75Ni – 16 Cr – 7 Fe alloy (passive) Zinc
Nickel (passive) Magnesium alloys
Silver solder Magnesium
M-Bronze
G- Bronze
Anodic (Most Active) The natural differences
70-30 cupro-nickel
in metal potentials produce galvanic differences,
Silicon bronze
such as the galvanic series in sea water. If elec-
Copper
trical contact is made between any two of these
Red brass
materials in the presence of an electrolyte, current
Aluminum bronze
must flow between them. The farther apart the
Admiralty brass
metals are in the galvanic series, the greater the
Yellow brass
galvanic corrosion effect or the rate. Metals or
76 Ni-16 Cr-7 Fe alloy (active)
alloys at the upper end are noble while those at
Nickel (active)
the lower end are active. The more active metal is
Naval brass
the anode or the one that will corrode. The anode
Manganese bronze
must be chosen from the above material list
Muntz
which is lower on the list than the material to be
Tin
protected.
Lead
Control of galvanic corrosion is achieved by
18-8-3 stainless steel, type 316 (active)
using metals closer to each other in the galvanic
18-8 stainless steel, type 304 (active)
series or by electrically isolating metals from
Thirteen percent chrome stainless steel, type
each other. Cathodic protection can be used to
410 (active)
control galvanic corrosion effects.
Cast iron
The following practices are recommended to
Mild steel
keep galvanic corrosion to a minimum.
Aluminum 2024
Cadmium
Aluminum 6053
4 Corrosion
Corrosion,
Fig. 3 Isolation flanges to
prevent galvanic
• Avoid the use of widely dissimilar metals in
direct contact.
• When dissimilar metals must come into con-
tact, they should be separated by using
nonconductive barrier materials, a paint coat-
ing, or by plating.
• The anode should be as large as feasible in
relation to cathode.
• Coat both the anode and the cathode with the
same material.
• Install fasteners that have been dipped in
epoxy mastic coatings.
• Seal threaded inserts with epoxy mastic coat-
ings prior to insertion into castings.
• Avoid the use of lock or toothed washers over
plated or anodized surfaces.
The scuba tank above suffered galvanic corro-
sion when the brass valve and the steel tank were
wetted by condensation. Electrical isolation
flanges (Fig. 3) like those shown on the right are
used to prevent galvanic corrosion. Insulating
polymeric gaskets are inserted between the
flanges, and insulating sleeves and washers iso-
late the bolted connections.
Pitting Corrosion
The most common effect of corrosion on alumi-
num and magnesium alloys is pitting. First is
noticeable as a white or gray powder, similar to
dust, which blotches the surface. When the
deposit is cleaned away, tiny pits or holes can
be seen in the surface. Passive metals such as
stainless steel resist corrosive media and can per-
form well over long periods of time. However, if
corrosion does occur, it forms at random pits.
Pitting may be a serious type of corrosion because
it tends to penetrate rapidly into the metal section.
It is most likely to occur in the presence of chlo-
ride ions, combined with such depolarizers as
oxygen or oxidizing salts. Methods that can be
used to control pitting include maintaining clean
surfaces, application of a protective coating, and
use of inhibitors or cathodic protection for
immersion service.
Sometimes pitting corrosion can be quite
small on the surface and very large below the
surface. The figure below left shows this effect
common on stainless steel and other film-
protected metals. Pitting shown on the right
(white arrow) led to the stress corrosion fracture
shown by the black arrows (Fig. 4).
Pitting corrosion can lead to unexpected cata-
strophic system failure. The split tubing below
left was caused by pitting corrosion of stainless
steel. A typical pit on this tubing is shown below
right (Fig. 5).
Stress Corrosion Cracking
Stress corrosion cracking (SCC) is caused by the
simultaneous effects of tensile stress and corro-
sion. Stress may be internally or externally
Corrosion 5

Corrosion, Fig. 4 Same images for pitting corrosion

Corrosion, Fig. 5 Pitting corrosion for stainless steel tube

applied. Internal stresses are produced by • Remove stress risers from counter bores,
nonuniform deformation during cold working, grooves, etc.
by an unequal cooling from high temperatures,
and by internal structural rearrangement involv-
Crevice Corrosion
ing volume changes. Stresses induced when a
Crevice or contact corrosion is produced at the
piece is deformed, those induced by press and
region of contact of metals with metals or metals
shrink fits, and those in rivets and bolts are inter-
with nonmetals. It may occur at washers, under
nal stresses. Concealed stress is more important
barnacles, at sand grains, under applied protec-
than design stress, especially because stress cor-
tive films, and at pockets formed by threaded
rosion is difficult to recognize before it has over-
joints. Whether or not stainless steels are free of
come the design factor. Few guidelines in
pit nuclei, they are always susceptible to this kind
avoiding the problem are:
of corrosion because a nucleus is not necessary.
Crevice corrosion may begin through the action
• Use metal alloys at no greater than 75 % of
of an oxygen concentration cell and continue to
their yield strength and use exotic materials
form pitting. Cleanliness, the proper use of seal-
only where they are actually required.
ants, and protective coatings are effective means
• Avoid assemblies where high-tensile loads are
of controlling this problem.
concentrated in a small area.
6 Corrosion

Intergranular Corrosion used are grinding, chipping, sanding, or wire

This is an attack on the grain boundaries of a brushing.
metal or alloy. A highly magnified cross section Remove corrosion by mechanical method
of any commercial alloy will show its granular such as wire brushing or abrasive blasting as
structure. This structure consists of quantities of appropriate. Failure to adequately clean all resi-
individual grains, and each of these tiny grains dues will permit corrosion to continue. Light
has a clearly defined boundary that chemically corrosion may be removed from thin
differs from the metal within the grain center. members – ducts and tubing – with a nonwoven,
One example of this type of corrosion is in nonmetallic abrasive mat in accordance with
unstabilized 300-series stainless steels sensitized MIL-A-9962 or number 400 aluminum oxide or
by welding or brazing and subsequently silicon carbide grit abrasive paper or cloth. Do
subjected to a severe corrosion environment. not use steel wool.
Another example of intergranular or grain bound-
ary corrosion is that which occurs when alumi-
Chemical Method
num alloys are in contact with steel in the
Chemical corrosion-removal methods can be
presence of an electrolyte. The aluminum alloy
used when no danger exists that the chemical
grain boundaries are anodic to both the aluminum
used will become entrapped in recesses and
alloy grain and the steel. In the later case,
when there is no danger that adjacent material
intergranular corrosion of the aluminum alloy
will be attacked. The chemical method should be
occurs. Some austenitic steels are unstable when
used on complex shapes and machined surfaces.
heated in the temperature range 470–915  C.
Chemical rust removers are of two types: acid or
Decreased corrosion resistance in austenitic
alkaline. The acid type is used in removing rust
stainless steels is due to depletion of chromium
and black oxide by immersion or brush applica-
in the area near the grain boundaries, caused by
tion. This is a phosphoric acid-type remover and
the precipitation of chromium carbide. This con-
must not be used on high-strength steel heat
dition can be eliminated by the use of stabilized
treated above 1.24 gigapascals (GPa) tensile
stainless steel, such as columbium-, tantalum-, or
strength due to possible stress corrosion or hydro-
titanium-stabilized stainless steels (types
gen embrittlement problems. The alkaline type
321/347), or by the use of low-carbon stainless
(sodium hydroxide base) is suitable for use by
steels. Molybdenum additions as in type
immersion only. Use on machined surfaces where
316 stainless steels decrease the sensitivity to
a dimensional change would be objectionable.
and the severity of the intergranular attack.
Scale conditioners are used as necessary to
Intergranular corrosion can be prevented by:
facilitate oxide scale removal by acid cleaning.
The use of scale conditioners shall not cause
• Select an alloy type that is resistant to
pitting, intergranular attack, or reduction of
intergranular corrosion.
mechanical properties below the minimum
• Avoid heat treatments or service exposure that
values as specified in the applicable material
makes a material susceptible. Normally this
specification for the alloy, gage, and heat-treat
occurs with austenitic stainless steels when
condition.
they are held for some time in the sensitizing
When acid cleaning is used to remove heat-
temperature range of 470–915  C
 treat scale, flux, corrosive media, stains, and other
(800–1600 F).
contaminants, it shall be within the limits speci-
• Apply a protective coating.
fied. Acid cleaning shall not result in
intergranular attack that would be detrimental to
Corrosion Removal the fabrication or use of the material or part. Acid
Abrasive blasting is the preferred method of cleaning shall not result in pitting or smutting,
removing corrosion; other mechanical methods which will not be readily removed by subsequent
Corrosion
processing. Cleaning shall be accomplished in
the following bath:
1. Nitric acid (HNO3) (42 Baume)
225–375 kg/m3
2. Hydrofluoric acid (HF) or NH4HF2
9–52 kg/m3
3. Temperature: room 60  C (140  F)
4. Metal content, HF ratio = 1: 1.8 (replenish
bath when the metal concentration >1 part of
metal to 1.8 parts of HF)
Stainless Steel Alloys
Stainless steels owe their inherent corrosion
resistance to a condition known as passivity – as
a result of the presence of their oxide films called
“passive films.” Under favorable conditions, such
films are protective; however, unfavorable con-
ditions deficient in oxygen will destroy the films
and leave the surface in an “active” state with
corrosion resistance comparable to carbon steel.
The presence of hygroscopic salt deposits, dirt,
dust, and other foreign matter all serve to destroy
passivity. Underground exposure of bare stain-
less steel will result in unacceptable quality.
Where localized corrosion occurs, rapid penetra-
tion (pitting) at the point of initiation can occur as
an electrolytic cell is formed between the large
cathodic (passive) area and the small anodic area
under attack. This attack is particularly severe in
the presence of halide salts. Localized attack will
also occur in crevices, such as under sleeves on
tube fittings.
Superior resistance to pitting is attainable with
type 904 L unified numbering system (UNS)
N08904 stainless steel over other commonly
used steels. However, this is only a matter of
degree and localized attack can still occur.
Maintaining clean surfaces will greatly reduce
the opportunity for corrosion, regardless of the
alloy employed.
Typical Problem Areas
• Sharp edges. Sharp edges of metal structures
will often be deficient of proper coating thick-
ness; sharp edges should be rounded when
possible with the National Association of Cor-
rosion Engineers (NACE). A stripe coat or
7
brush coat of primer prior to spray will assist
in getting adequate coverage.
• Nuts and bolts. Premature coating failure and
corrosion on nuts and bolt heads are common
and can be reduced by conscientious surface
preparation prior to application of a protective
coating. A brush coat of primer prior to spray
will ensure adequate coverage.
• Tube clamps. Carbon steel clamps for interior
applications are either zinc plated or painted.
Stainless clamps shall be used for all exterior
applications. Corrosion at the interface
between the stainless steel tubing and the
clamp can occur due to dissimilar metal and
crevice corrosion. Corrosion at the interface
between tubing and clamps is controlled by
application of protective coatings.
• Unistrut channels. Use of unistrut channels
should be avoided in exterior locations. When
the exterior use of unistrut cannot be avoided,
selection of appropriate material shall be uti-
lized, such as stainless steel or fiber glass.
Where corrosion is noted, mechanically clean
the member to remove corrosion products
followed by application of a zinc-rich coating.
Stainless Steel Components
General Stainless steel, although very corrosion
resistant, is susceptible to localized corrosion
(e.g., pitting, crevice corrosion, etc.) when
exposed to marine environment. A mistake fre-
quently made is to conclude that the corrosion
noted on stainless steel tubing and bellows is only
superficial. This conclusion is improperly
reached when removal of external corrosion
products leaves the surface in a condition that
appears almost like new except for what appears
to be a very tiny pit. A cross section taken through
such a typical pit frequently discloses a void
considerably greater in diameter than the surface
pit diameter. Failure to arrest the apparent super-
ficial corrosion will result in ultimate penetration
of thin wall members.
Application of Protective Coatings
Stainless steel tubings shall be treated in the
following way:
8 Corrosion
• Accumulated dirt and oil shall be removed by
rinsing with water followed by rinsing with
methyl ethyl ketone (MEK).
• Remove corrosion products by mechanical
means, such as power tool cleaning or hand-
tool cleaning.
• Clean surfaces with methyl ethyl ketone using
clean rags.
• Apply by spraying, brushing, or dipping
75 mm (3 mils) minimum of the coating
Aerocoat AR-7 manufactured by B.F.
Goodrich.
Tubing assemblies shall be abrasive blasted.
When tubing assemblies are in close proximity to
carbon steel structural members that are to be
abrasive blasted and coated with inorganic zinc-
rich primer, the tubing assemblies shall be simi-
larly treated.
• Using clean rags, accumulated dirt and oil
shall be removed with water followed by wip-
ing with methyl ethyl ketone.
• Apply a zinc-rich coating in accordance with
the manufacturer’s recommendations to a
DFT (dry film thickness) of 100–150 mm
(4–6 mils).
Cathodic Protection
Cathodic protection (CP) is a technique used to
control the corrosion of a metal surface by mak-
ing it the cathode of an electrochemical cell. CP is
carried out by connecting the metal to be
protected with a piece of another more easily
corroded “sacrificial metal” to act as the anode
of the electrochemical cell. The sacrificial metal
then corrodes instead of the protected metal. For
structures where passive galvanic CP is not ade-
quate, like in long pipelines, an external DC
electrical current is applied. Cathodic protection
systems are used to protect a wide range of metal-
lic structures in various environments. Common
applications are steel water or fuel pipelines and
storage tanks such as home water heaters, steel
pier piles, ship and boat hulls, offshore oil plat-
forms and onshore oil well casings, and metal
reinforcement bars in concrete buildings and
structures. A common application is in galva-
nized steel, in which a sacrificial coating of zinc
on steel protects them from rust.
Cathodic protection can, in some cases, pre-
vent stress corrosion cracking.
Applications Pipelines are routinely protected
by a coating supplemented with cathodic protec-
tion. An ICCP – impressed current cathodic
protection – system for a pipeline would consist
of a DC power source, which is often an
AC-powered rectifier and an anode, or array of
anodes buried in the ground (the anode ground
head)
Ships: cathodic protection on ships is often
implemented by galvanic anodes attached to the
hull, rather than using ICCP. Since ships are
regularly removed from the water for inspections
and maintenance, it is a simple task to replace the
galvanic anodes. Galvanic anodes are generally
shaped to reduced drag in the water and fitted
flush to the hull to also try to minimize drag.
How to Prevent Metal Corrosion
• Choose products that are made of
noncorrosive metals like stainless steel and
aluminum.
• Maintain a dry environment using appropriate
moisture barriers.
• Ensure the electrical connections are clean.
• On a car or truck, apply a thin coating of
petroleum jelly after cleaning the terminal.
• Coat metals with oil, paint, grease, or varnish
because it can prevent corrosion.
• Make use of cleaning agents like soaps, sol-
vents, emulsion compounds, and chemicals to
efficiently get rid of oil, grease, dirt, and other
unwanted foreign deposits and follow the cor-
rect procedures in applying them.
• A mixture of cola and baking soda paste will
remove metal corrosion on car batteries.
• To prevent soil corrosion, install correctly
copper or copper alloy plumbing under-
ground. The main causes of copper corrosion
are poor drainage and moisture. A loose layer
of backfill such as limestone or pea level must
be put down in the trench before laying copper
pipes.
Corrosion
• Galvanizing also provides metal corrosion
protection. This is the process of giving a
thin coating of zinc or steel material by
immersing the object in a bath primarily of
molten zinc. Galvanizing is an efficient way
to protect steel because even if the surface is
scratched, the zinc still protects the underlying
layer. This process is widely used in the auto
industry.
Summary
Corrosion is effectively controlled by cathodic
protection or by appropriate selection of inhibi-
tors, provided the chemical and electrical condi-
tions are scientifically monitored. Understanding
of the mechanism is the key in handling the
condition of the metals and structures. Every
scenario is site specific and needs to be addressed
on its associated factors of pH of the medium,
9
environment, and temperature. Accordingly
adopt the right protection techniques out of the
available:
• Removal of oxidizing agent
• Prevention or inhibition of surface reaction
• Application of protective coatings – organic/
metallic/nonmetallic
• Modification of the metal or the surface
conditions
References
VIII- Met J Corros Prot
TM 584 Revision C. http://www.corrosioncontrol.com.
Accessed Nov 1994
Corrosion Technology Laboratory – Galvanic corrosion.
http://corrosion.ksc.nasa.gov/galcorr.htm. http://corro
sion.ksc.nasa.gov/pitcor.htm. http://corrosion.ksc.
nasa.gov/stresscor.htm. http://corrosion.ksc.nasa.gov/
crevcor.htm
I
Imprinting
Masakazu Yoshikawa1 and Kalsang Tharpa2
1
Department of Biomolecular Engineering,
Kyoto Institute of Technology, Kyoto, Japan
2
Department of Chemistry, University of
Mysore, Mysore, India
Imprinting, which is often called “molecular
imprinting,” is a facile way to introduce molecu-
lar recognition sites into polymeric membranes
(materials) (Sellergren 2001; Komiyama
et al. 2003; Alexander et al. 2006). In other
words, the molecular memory, such as a shape
of the target molecule and an alignment of the
functional moieties to interact with those in target
molecule, is memorized in the polymeric mem-
branes (materials) for the recognition or separa-
tion of target molecule from others during the
formation of polymeric membranes (materials).
Such molecularly imprinted materials are pre-
pared by adopting two ways; one is “molecular
imprinting,” the other “alternative molecular
imprinting.” The former is a pioneering method
to prepare polymeric materials with molecular
recognition sites from functional monomer,
crosslinker, and print molecule (template)
(Wulff and Sarhan 1972; Arshady and Mosbach
1981); the molecular imprinting is further divided
into two methods, covalent molecular imprinting
(Wulff and Sarhan 1972) and non-covalent
molecular imprinting (Arshady and Mosbach
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_786-1
1981) as schematically shown in Fig. 1. The latter
is an alternative way to obtain polymeric mem-
branes bearing molecular recognition sites
directly from candidate polymeric materials and
print molecule (Yoshikawa et al. 1995, 2011).
The scheme of the alternative molecular imprint-
ing is shown in Fig. 2. In Step 1, the polymeric
material, which is a candidate material to con-
struct molecular recognition sites, is interacted
with a print molecule by specific interaction
before and during the formation process of
molecular recognition materials so that molecu-
lar memory can be introduced into the polymeric
materials. In Step 2, the print molecule is
extracted from the molecularly imprinted mate-
rials. When the molecularly imprinted material
thus constructed is in contact with the print mol-
ecule or print molecule analogue, the molecular
recognition sites preferentially interact with them
or incorporate them into the molecular recogni-
tion sites (Step 3 and Step 4). Contrary to the
pioneering molecular imprinting method, molec-
ular recognition sites are formed at the same time
as the molecularly imprinted materials are pre-
pared from polymer solution or polymer melt. In
other words, any polymeric materials, such as
synthetic polymers, oligopeptide derivatives,
derivatives of natural polymer, and natural poly-
mers, can be directly converted into molecular
recognition material by applying the alternative
molecular imprinting (Yoshikawa 2001).
The similar approach was proposed by
Michaels et al. in 1962 (Michaels et al. 1962).
2 Imprinting

Covalent Molecular Imprinting

Synthesis of Removal by
Polymerizable Chemical Molecular
Print Molecule Polymerization Cleavage Recognition

Noncovalent Molecular Imprinting

Removal by
Solvent Molecular
Self-assembly Polymerization Extraction Recognition

Imprinting, Fig. 1 Schemes of the covalent and non-covalent molecular imprinting (Cited from Yoshikawa et al. 2011
with permission. Copyright 2012 Elsevier Inc.)

Alternative Molecular Imprinting

Step 2
Step 1 Removal of print molecule
Interaction between print
molecule and candidate
material

Step 4 Step 3
Recognition of print molecule Formation of recognition
(print molecule analogue) site and permeation path

Imprinting, Fig. 2 Scheme of the alternative molecular imprinting (Cited from Yoshikawa et al. 2011 with permission.
Copyright 2012 Elsevier Inc.)

This study is the first report on the alternative
molecular imprinting and the first application of
molecularly imprinted polymeric membranes to
membrane separation. Michaels’ paper is the
commemorable paper in molecular imprinting
and membrane separation. In addition to this,
molecularly imprinted polymeric membranes
prepared by non-covalent molecular imprinting
was reported in 1990 (Piletskii et al. 1990). Since
then, various molecularly imprinted membranes
were studied by adopting non-covalent molecular
imprinting. A wet phase inversion process was
applied to an alternative molecular imprinting to
prepare asymmetric membranes (Trotta
et al. 2002).
As described above, applying molecular
imprinting, such as conventional molecular
imprinting or alternative molecular imprinting,
Imprinting
molecular recognition sites are easily introduced
into polymeric membranes (Ulbricht 2004). From
this, it is easy to enhance permselectivity of a
given membrane by applying those molecular
imprinting techniques. The enhancement of flux
without a reduction in permselectivity is indis-
pensable so that molecularly imprinted mem-
branes can be applicable to industries.
Molecularly imprinted membranes with a
higher surface area and a higher porosity are
required to give higher flux and permselectivity.
Electrospun nanofiber membranes with molecu-
lar recognition sites is a suitable or the best mem-
brane morphology to attain high flux and high
permselectivity. Possibility of the enhancement
of flux without a concurrent reduction in
permselectivity was proved by molecularly
imprinted nanofiber membranes, which were fab-
ricated by simultaneously applying an
electrospray deposition and an alternative molec-
ular imprinting (Yoshikawa et al. 2011).
References
Allexander C, Andersson HS, Andersson LI, Ansell RJ,
Kirsch N, Nicholls IA, O’Mahony J, Whitcombe MJ
(2006) Molecular imprinting science and technology:
a survey of the literature for the years up to and includ-
ing 2003. J Mol Recognit 19:106–180
3
Arshady R, Mosbach K (1981) Synthesis of substrate-
selective polymers by host-guest polymerization.
Makromol Chem 182:687–692
Komiyama M, Takeuchi T, Mukawa T, Asanuma
H (2003) Molecular imprinting. Wiley-VCH,
Weinheim
Michaels AS, Baddour RF, Bixler HJ, Choo CT (1962)
Conditioned polyethylene as a permselective mem-
brane. Separation of isomeric xylenes. Ind Eng
Chem Process Des Dev 1:14–25
Piletskii SA, Dubei IY, Fedoryak DM, Kukhar VP (1990)
Substrate-selective polymeric membranes Selective
transfer of nucleic acid components. Biopolim Kletka
6:55–58
Sellergren B (ed) (2001) Molecularly imprinted polymers
man made mimics of anti bodies and their applications
in analytical chemistry. Elsevier, Amsterdam
Trotta F, Drioli E, Baggiani C, Lacopo D (2002) J Membr
Sci 201:77–84
Ulbricht M (2004) Membrane separations using molecu-
larly imprinted polymers. J Chromatogr
B 804:113–125
Wulff G, Sarhan A (1972) The use of polymers with
enzyme-analogous structures for the resolution of
racemates. Angew Chem Int Ed 14:341 [Über die
Anwendung von enzymanalog gebauten Polymeren
zur Racemattrennung. Angew Chem 84: 364]
Yoshikawa M (2001) Molecularly imprinted polymeric
membranes. Bioseparation 10:277–286
Yoshikawa M, Izumi J, Kitao T, Koya S, Sakamoto
S (1995) Molecularly imprinted polymeric membranes
for optical resolution. J Membr Sci 108:171–175
Yoshikawa M, Tanioka A, Matsumoto H (2011) Molecu-
larly imprinted nanofiber membranes. Curr Opin
Chem Eng 1:18–26
N

Nanotechnology Membrane • Vertically aligned nanotube membranes

• Isoporous block copolymer membranes
Abaynesh Yihdego Gebreyohannes and Lidietta
Giorno
Institute on Membrane Technology, National
Hybrid Inorganic-Organic
Research Council of Italy, ITM-CNR, University
Nanocomposite Membranes
of Calabria, Rende (CS), Calabria, Italy
Mixed matrix membranes present the synergistic
advantage of both the low cost and ease of fabri-
Over the last decade, nanotechnology has rapidly
cation of organic polymeric membranes and
evolved from an academic research to commer-
mechanical strength and functional properties of
cial reality. The concept of nanotechnology led to
inorganic materials (Dong et al. 2013). The con-
the development of innovative nanotechnology-
cept was first introduced in the 1990s by
based membranes that surpass the state-of-the-art
Zimmerman et al., as a strategy to overcome the
performance and enable new functionality such
limitations of polymeric membranes for gas sep-
as high permselectivity, catalytic reactivity, and
aration. The most commonly exploited inorganic
fouling resistance. Nanotechnology is used to
fillers are alumina, carbon nanotubes, iron-
enhance performance of traditional ceramic and
palladium particles, silica, and titania, which are
polymeric membrane materials through various
embedded within the polymeric matrix. The par-
strategies (Pendergast and Hoek 2011). Nano-
ticle size covers broader ranges from 0.5 to
technology membranes include:
300 nm, while the general composition ranges
from 0.01 to 40 wt.% (Pendergast and Hoek
• Zeolite and catalytic nanoparticle-coated
2011). Generally, inclusion of the inorganic par-
ceramic membranes
ticle imparts change in the polymeric membrane
• Hybrid inorganic-organic nanocomposites
surface property (hydrophilicity/hydrophobicity,
membranes
roughness, increased or decreased water perme-
• Bio-inspired nanotechnology membranes
ability and selectivity depending on the type,
• Bio-hybrid immobilized enzyme
size, and weight fraction of the inorganic particle,
membranes
improved thermal and mechanical stability, as
• Bio-hybrid magnetic-responsive
well as enhanced antifouling property).
membranes
• Aquaporin membranes

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_787-1
2 Nanotechnology Membrane
In addition to microparticles, nanoparticles
have been added to polymeric membranes, e.g.,
the inclusions to the thin films of thin-film com-
posite (TFC) reverse osmosis membrane have
been of great interest to impart the properties of
the nanomaterials. Embedding smaller
nanoparticles increases permeability more by
increasing the characteristic pore size. One of
the main reasons attributing to the enhanced per-
meability of the TFC membranes with embedded
nanoparticles is the presence of limited cross-
linking than pure polyamide TFC counterparts.
Overall, the addition of nanoparticles can be tai-
lored to particular membrane applications with
the selection of nanoparticle size, shape, and
type. Furthermore, inclusion of the nanoparticles
such as silver in the TFC could inhibit biofouling
growth due to the antimicrobial property of
nanosilver (Basri et al. 2010).
Nevertheless, improved permselectivity
through inclusion of nanoparticle to the TFC
may not be a general fact. It is theoretically
predicted that the permeability of TFC, which
have impermeable nanoparticles like titania,
reduces, while those containing permeable
nanoparticles like SOD-zeolite increases.
A nanoparticle with higher water permeability
relative to the polymer matrix can increase the
permeability of the resulting nanocomposite
membrane, while impermeable nanoparticles
can only reduce the water permeability of a mem-
brane because they reduce the area available for
permeation through the polymer film. The only
time impermeable particle can enhance perme-
ability is when they cause defect in the thin-film
layer which also compromises their solute rejec-
tion capacity (Pendergast and Hoek 2011).
For the impermeable particles, even with the
presence of loss in permeability, inclusion of the
nanofillers could be desirable to induce hydro-
philic or antimicrobial properties that signifi-
cantly reduce membrane fouling. In addition to
performance, one also has to take the cost of the
nanofillers into consideration for practical appli-
cation. For instance, antimicrobial and zeolite
nanoparticles are expensive, yet zeolite
nanofillers can bring about a considerable flux
improvement at extremely low loadings such
that the cost increase may be minimal.
Other interesting features one can induce by
inclusion of nanofillers into polymeric mem-
branes are stimuli-responsive properties. One of
the main strategies that follows the research on
stimuli-responsive organic-inorganic (O/I)
hybrid membranes is the incorporation of
superparamagnetic nanoparticles (NPsSP). It is
an emerging field that holds numerous
unexplored interesting avenues (Daraei
et al. 2013; Sanchez et al. 2011). It leads to
stimuli-responsive “smart” polymeric membrane
with properties that can be modulated in a revers-
ible manner. For example, recently magnetic-
responsive micro-mixing nanofiltration mem-
brane is developed. The membrane was prepared
by grafting magnetic-responsive nanolayers
consisting of hydrophilic poly(2-hydroxyethyl
methacrylate) (polyHEMA) flexible polymer
chains with NPSP attached to the chain ends.
The chain oscillates in an oscillating magnetic
field, induced mixing at the membrane-fluid
interface that maximized the disruption of con-
centration polarization layer (Himstedt
et al. 2011).
NPSP has also been used as inorganic
nanofillers in a PVDF membrane to impart
desired surface functionality (Huang
et al. 2012). The hybrid membrane has controlled
porosity, texture, and chemical composition that
can provide real prospect to an efficient mem-
brane filtration. The presence of the NPSP also
induces magnetic property in the membrane that
can be controlled by an external magnetic field
through remote on-off switches (Daraei
et al. 2013; Thevenot et al. 2013). This responsive
behavior, for example, is useful to manipulate the
deposition of magnetic nanoparticle on the mem-
brane surface to prevent direct membrane-foulant
interaction (Gebreyohannes et al. 2015). In addi-
tion to inducing magnetic properties, inclusion of
the NPSP is reported to enhance the membranes’
hydrophilicity, mechanical strength, compaction
resistance, improved permselectivity, and anti-
fouling property (Daraei et al. 2013; Huang
et al. 2012). Therefore, these membranes have
Nanotechnology Membrane
broad function ranging from environmental
remediation to smart product manufacturing. Par-
ticularly, the synergistic antifouling property and
improved permselectivity give the membrane a
big prospect to be utilized in water purification.
NPSP-coated membranes, for example, have been
used for effective removal of natural organic
matter (Yao et al. 2009), arsenic (Sabbatini
et al. 2010), and copper (Daraei et al. 2012) dur-
ing water treatment.
Bioinspired Nanotechnology
Membranes
Biomimetic nanostructured membranes are
formed either through directly embedding bio-
molecule into synthetic materials or by using
functional molecules to modify synthetic mate-
rials to impart specific biological property. These
hybrid biomimetic membranes combine the accu-
rate structure of a biological pore with the dura-
bility, robustness, and the possibility to control
the pore size and shape of solid-state nanopore
membrane (Shen et al. 2014).
Biohybrid Magnetic-Responsive Membranes
Superparamagnetic nanoparticles (NPsSP) are
most often superparamagnetic iron oxide with
zero memory of their magnetic property in the
absence of an external magnetic field (Yeon
et al. 2009). Polymer coatings and the introduc-
tion of various surface functional groups facili-
tate the anchorage of biomolecules on the surface
of these particles (Miguel-Sancho et al. 2012;
Brullot et al. 2012; Xiao-Ming and Wainer
1993). The resulting bionanocomposites repre-
sent an important material with a versatile appli-
cation in the biotechnology, fine chemicals, drug
delivery, cell transplantation, or cell immobiliza-
tion. These nano-sized particles exhibit biocom-
patibility, high surface-to-volume ratio which
makes them a good candidate for enzyme immo-
bilization to make biohybrids. The high surface-
to-volume ratio assists with higher enzyme load-
ing capacity and enhanced mass transfer effi-
ciency. Hence this material with its excellent
mechanical, optical, electrical, ionic, and
3
catalytic properties is a good candidate to revers-
ibly immobilize enzyme on the surface of a poly-
meric membrane to mimic hybrid protein-
polymer biomimetic membranes.
Alternative to direct integration of the enzyme
within the polymer matrix, stimulus-responsive
programmable layers on membrane can be
formed through the attraction of NPSP through
reversible magnetic force. These biomimetic
smart layers will enable development of adaptive
enzyme membrane reactors. For instance, once
an enzyme is immobilized on NPSP, they can be
easily dispersed in a reaction medium in the
absence of an external magnetic field. However,
by applying an external magnetic field, it is pos-
sible to relocate the bionanocomposites toward
the surface of a membrane using an external
magnetic field. The method is promising to
resolve pertinent issues related to the direct inte-
gration of enzyme within the polymeric matrix.
Overall, tuning reversible enzyme immobiliza-
tion using NPSP helps in:
1. Easy recovery, recycling, and removal of
immobilized enzyme
2. Formation of dynamic layer between mem-
brane and feed preventing membrane-
pollutant interaction
3. Activation of the monolayer with biocatalyst
to achieve biocatalysis at the membrane-
solution interface
4. Easy regeneration of membrane whenever the
membrane is oversaturated with substrate
This approach has recently been demonstrated
to form an enzyme membrane reactor
(Gebreyohannes et al. 2015). The method is
novel for it has used NPSP as a carrier to anchor-
age various enzymes as well as nanofiller to form
magnetic-responsive hybrid membrane. When an
external magnetic field has been applied to the
system, the magnetic-responsive polymeric
membrane gets magnetized. Subsequently, the
NPSP with the immobilized enzyme was dis-
persed in the upper stream. These particles were
then attracted toward the surface of the mem-
brane. The magnetic-responsive membrane acts
as magnetic field actuators that eventually help
4 Nanotechnology Membrane
with uniform dispersion of the NPSP on the sur-
face of the membrane. Hence it has potentially
mimicked the micro-nanoarchitecture of the
direct integration of enzyme into the membrane.
The method has shown an interesting perfor-
mance when it was applied to treat a feed rich in
polysaccharides. After depositing 1–2 g/m2 of
pectinase activated NPSP with an average diame-
ter of 8 nm, 40 % to 100 % reduction in the
pressure required to keep flux constant at 17 L/
m2 h was observed. Moreover, thanks to the easy
recycling of enzyme, both membrane and
immobilized enzyme were used over several
cycles, adding a considerably extended lifetime
to the membrane as well as the enzyme
(Gebreyohannes et al. 2015).
Modulating reversible enzyme immobiliza-
tion through combinatorial stimulus-responsive
enzyme immobilization technique holds a great
potential in bioseparations, antifouling surfaces,
and creating self-cleaning membranes. Hence,
the future innovations on the basis of stimulus-
responsive enzyme immobilization holds a big-
ger prospect to “reengineer” membrane biocatal-
ysis that will lead to the design of more complex
membrane systems that are capable of mimicking
the nature.
Aquaporin Membranes
Aquaporins are the protein channels that control
water flux across biological membranes. Water
movement in aquaporins is mediated by selec-
tive, rapid diffusion caused by osmotic gradients
(Agre 2006; Meinild et al. 1998). According to
Zhu et al. (nd), the two major factors that control
water transport are:
(a) Osmotic permeability: molecular movement
due to concentration differences resulting in
net mass transfer
(b) Diffusion permeability: random movement
of molecules with no net mass transfer
In the first case, the water molecules transport
in a single file through a narrow aquaporin chan-
nel, while in the second case, permeation occurs
due to the movement of two molecules between
opposite pools. Hence, the ratio of the osmotic
permeability to diffusion permeability is the
number of effective steps a water molecule shall
move in order to permeate through a channel.
Since aquaporin channels have high water selec-
tivity, a membrane with 75 % aquaporin coverage
is predicted to have an order of magnitude higher
water permeability compared to commercial sea-
water RO membranes (Kaufman et al. 2010).
There already are interesting research activi-
ties on the inclusion of aquaporins in polymeric
membranes. For instance, the use of aquaporin-Z
from E. coli bacterial cells used to form a protein-
polymer membrane exhibited an order of magni-
tude higher water permeability as compared to a
counterpure polymeric membrane. However,
practical application of these proteins is highly
limited by lack of large quantities of protein
production. Nevertheless, with a continued
research and effort, techniques to simplify the
fabrication and production of mechanically
sound membranes aquaporin-based biomimetic
membranes are inevitable.
Vertically Aligned Carbon Nanotubes
Carbon nanotubes (CNTs) exhibit the fast mass
transfer resemblance to aquaporin water channels
in which water transport is two to five times
higher than theoretically predicted by Hagen-
Poiseuille equation (Holt et al. 2006). Molecular
dynamic simulation studies attributed this out-
standing flow rate to atomic smoothness and
molecular ordering. In particular, water mole-
cules permeate through the CNTs in a
one-dimensional single file resulting in very
small driving force use. Moreover, CNT-based
membrane represents excellent mechanical prop-
erties that impart longer lifetime than conven-
tional membrane materials.
The most commonly utilized mechanism used
to produce uniformly aligned nanotube arrays is
chemical vapor deposition (CVD). The CNTs are
adapted by fixing surface functional groups to
mimic aquaporin structure or by CVD and a
simultaneous solid-state reaction (Holt
et al. 2006). The pore densities of the CNTs
made by fixing negative surface functional
groups are as high as 0.25*1012/cm2 while
representing three order of magnitude higher
Nanotechnology Membrane
water flux relative to what is predicted theoreti-
cally. However, CNTs’ alignment via CVD has a
number of limitations such as its costliness, sen-
sitivity, and difficulty for large-scale application.
Alternative to CVD, magnetic alignment, self-
assembly, and passing single-walled CNT sus-
pensions through polymeric filters are
approaches to form CNT-aligned membranes.
Although CNT mimicked biological
aquaporin channels with a material producible
in large amount, no large-scale CNT-aligned
membranes have been produced yet. However,
one can resolve these challenges similar to the
challenges faced by reverse osmosis membranes
50 years ago when performance improvements
lead to the practical necessity of CNT-aligned
membrane application.
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Thorac Soc 3:5–13
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Dornez E, Giorno L, Curcio E, Vankelecom IFJ
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AB, Grigoropoulos CP, Noy A, Bakajin O (2006) Fast
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(2012) The performance of the PVDF-Fe3O4 ultrafil-
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Martinez G, Arruebo M, Santamaria J (2012) Synthe-
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treatment membrane nanotechnologies. Energy Envi-
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arsenic removal. Water Res 44:5702–5712
Sanchez C, Belleville P, Popall M, Nicole L (2011) Appli-
cations of advanced hybrid organic-inorganic
nanomaterials: from laboratory to market. Chem Soc
Rev 40:696–753
Shen Y-x, Saboe PO, Sines IT, Erbakan M, Kumar
M (2014) Biomimetic membranes: a review.
J Membr Sci 454:359–381
Thevenot J, Oliveira H, Sandre O, Lecommandoux
S (2013) Magnetic responsive polymer composite
materials. Chem Soc Rev 42:7099–7116
Xiao-Ming Z, Wainer IW (1993) On-line determination of
lipase activity and enantioselectivity using an
immobilized enzyme reactor coupled to a chiral sta-
tionary phase. Tetrahedron Lett 34:4731–4734
Yao P, Choo KH, Kim MH (2009) A hybridized
photocatalysis-microfiltration system with iron oxide-
coated membranes for the removal of natural organic
matter in water treatment: effects of iron oxide layers
and colloids. Water Res 43:4238–4248
Yeon KM, Lee CH, Kim J (2009) Magnetic enzyme car-
rier for effective biofouling control in the membrane
bioreactor based on enzymatic quorum quenching.
Environ Sci Technol 43:7403–7409
Zhu, F, Tajkhorshid, E, Schulten, K (nd) Theory and
simulation of water permeation in aquaporin-1.
Biophys J 86:50–57
B
Boric Acid Separation by Membrane
Contactor
A. Criscuoli
Institute on Membrane Technology (ITM-CNR),
Rende (CS), Italy
Boron is usually found in water as boric acid, and
its concentration ranges from few ppb in river
water up to around 7 ppm in seawater and can
be even higher in wastewaters discharged from
some industrial plants. Due to its toxic effects on
both humans and plants, the World Health Orga-
nization (WHO) has fixed at 0.3 ppm the maxi-
mum allowed concentration of boron in water.
Different are the techniques that can be used for
controlling the boric acid content of water, like
adsorption, ion-exchange resins, solvent extrac-
tion, electrodialysis, multiple stages of reverse
osmosis units (working at different pH), and
membrane contactors. In particular, the effective-
ness of membrane contactors has been confirmed
using various configurations to treat waters
containing boric acid.
Boric acid was selectively separated through
supported liquid membranes containing inside
micropores 1,3-diols (carrier) dissolved into
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_791-1
o-dichlorobenzene. The membranes were hydro-
phobic and separated the aqueous stream
containing boric acid from an alkaline aqueous
phase, representing the so-called receiving phase;
see Fig. 1 (Bachelier et al. 1996).
The removal of boric acid was also obtained
by employing hydrophilic microporous mem-
branes, sending distilled water as extractant
phase. In this case, the membrane pores were
filled with the aqueous feed, and, by properly
acting on the pressures of the two phases, the
interface was located at the membrane surface-
extractant side, so that the boric acid removal
occurred by simply diffusion from the feed to
the extractant (Fig. 2). For practical
implementations, an integrated membrane sys-
tem where the extractant was continuously
regenerated and recycled to the membrane
contactor was also proposed and designed
(Criscuoli et al. 2010a, b).
Successful performances of hydrophilic
microporous membranes using distilled water as
extractant were also observed by Park and Lee
(1995). Moreover, they found good efficiencies
of anion exchange membrane contactors for the
removal of boric acid from liquid radioactive
wastes.
2 Boric Acid Separation by Membrane Contactor

Boric Acid Separation by Organic-filled

Membrane Contactor, micropore
Fig. 1 Transport of boric
acid through a supported
liquid membrane

Boric acid

Feed water Alkaline aqueous phase

Boric Acid Separation by

Membrane Contactor,
Fig. 2 Transport of boric
acid in a hydrophilic
membrane
Boric acid

Distilled water
Feed water

References Criscuoli A, Rossi E, Cofone F, Drioli E (2010b) Boron

Bachelier N, Chappey C, Langevin D, Mètayer M,
Verchère J-F (1996) Facilitated transport of boric
acid through supported liquid membranes. J Membr
Sci 119:285–294
Criscuoli A, Rossi E, Cofone F, Drioli E (2010a) Boron
removal by membrane contactors: the water that
purifies water. Clean Technol Environ Pol 12:53–61
removal by membrane contactors: the water that
purifies water. Additional information. Clean Technol
Environ Pol 12:63
Park JP, Lee KJ (1995) Separation of boric acid in liquid
waste with anion exchange membrane contactor.
Waste Manag 15:283–291
D
Direct Fluorination of Polymer
Membranes: Gas Separation
Properties
A. P. Kharitonov
Talrose Branch of the Institute of Energy
Problems of Chemical Physics of the Russian
Academy of Sciences, Moscow Region, Russia
Polymeric membranes can be used for the sepa-
ration of gas mixtures such as He-CH4, H2-CH4,
CO2-CH4, H2-N2, etc. There is, however, a com-
mon problem in a gas separation when a poly-
meric membrane is used: membranes with high
gas permeability often have low gas separation
factor, and on the contrary, membranes with high
separation factor have low permeability (Fig. 1)
(Robeson 2008). The direct fluorination can be
effectively used to improve gas separation prop-
erties of polymer membranes when the gas mix-
ture consists of gases with markedly different gas
kinetic diameters. In this case substantial increase
of separation selectivity (up to several tens times
for the case of He/CH4 mixture) is accompanied
with a relatively small decrease (or no change) of
permeability of a gas with smaller gas kinetic
diameter (He, H2, etc.). Direct fluorination of
polymers is a heterogeneous reaction of gaseous
F2 mixtures with a polymer surface. This is a
method of the surface modification: only upper
surface layer is modified (~0.01 to several
microns in thickness), but the bulk properties
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_794-5
(e.g., tensile strength) remain unchanged. The
direct fluorination proceeds spontaneously at
room temperature with sufficient for industrial
applications rate. Fluorination results in a substi-
tution of H-atoms for F-atoms, saturation of
double (conjugated) bonds with fluorine, and
disruption of majority of C-N and C-Si bonds
followed with formation of C-F bonds. The
chemical composition of fluorinated layer
depends on composition and pressure of fluori-
nating mixture and treatment duration. Treatment
at mild fluorination conditions does not cause
disruption of C-C bonds in the main polymer
chain. Direct fluorination is a dry technology.
Polymer hollow fibers, fabricated membrane
modules, and composite membranes can be
treated. For the case of hollow fibers and com-
posite membranes, only the dense separation
layer can be fluorinated and the porous support
will remain untouched, so the tensile strength of
membrane element will not be decreased. There
are safe and reliable methods to neutralize
(by converting into the solid phase) unused F2
and the end product HF.
The direct fluorination was used to enhance
gas separation properties of several polymer
membranes (both homogeneous and composite)
and hollow fiber modules: polyimide (PI),
polyvinyltrimethylsilane (PVTMS), poly
(1-trimethylsilylpropyne) (PTMSP), poly
(phenylene oxide), polysulfone, poly(4-methyl-
pentene), polycarbonatesiloxane, etc. (Langsam
et al. 1988; Le Roux et al. 1994; Amirkhanov
2 Direct Fluorination of Polymer Membranes: Gas Separation Properties
Direct Fluorination of Polymer Membranes: Gas
Separation Properties, Fig. 1 Separation selectivity a
for the He/CH4 mixture vs. permeability of He for various
polymer membranes in logarithmic scale. Filled
points – literature data (Robeson 2008). Empty triangle,
square, and diamond correspond to pristine polyamide
Matrimid ® 5218 hollow fiber module (points correspond
to different treatment conditions) and PVTMS
(Kharitonov 2007, 2008) and PTMSP (Langsam
et al. 1988) flat membranes. Filled symbols represent
transport properties of fluorine treated membranes
et al. 1998; Kharitonov 2007, 2008). Figure 1
illustrates the influence of direct fluorination on
separation selectivity for He/CH4 mixture. As it
is evidenced by Fig. 1, direct fluorination results
in a very remarkable increase (by a factor of
several tens times or more than hundred times)
of separation selectivity. The permeability of He
and H2 is not practically changed after fluorina-
tion. Hence the direct fluorination of PVTMS and
polyimide Matrimid 5218 provides the possibil-
ity to “overjump” the Robeson boundary (straight
line in Fig. 1). The direct fluorination can sub-
stantially improve the separation selectivity of
CO2/CH4, He/N2 and He/CH4 mixtures (Fig. 2).
References
Amirkhanov DM, Kotenko AA, Tul’skii MN (1998) Tech-
nological characteristics of the manufacture and use of
Direct Fluorination of Polymer Membranes: Gas
Separation Properties, Fig. 2 Influence of treatment
conditions of PVTMS flat membrane on the separation
selectivity of CO2/CH4, He/N2, and He/CH4 mixtures.
Treatment condition (from left to right in each group at
the plot): virgin PVTMS, treatment with 2 % F2 + 98 %
He mixture, treatment with 33 % F2 + 67 %He mixture,
treatment with 2 % F2 + 98 % He mixture followed by a
grafting of acrylonitrile, treatment with 60 % F2 + 40 %
O2 mixture
fluorine-modified graviton hollow gas-separation
fibres. Fibre Chem 30:318–324
Kharitonov AP (2007) Chapter 2: direct fluorination of
polymers – from fundamental research to industrial
applications. In: Gardiner IV (ed) Fluorine chemistry
research advances. Nova Science Publishers, New
York, pp 35–103
Kharitonov AP (2008) Direct fluorination of polymers.
Nova Science Publishers, New York
Langsam M, Anand M, Karwacki EJ (1988) Chemical
surface modification of poly[1-(trimethylsilyl)
propyne] for gas separation membranes. Gas Sep
Purif 2:162–170
Le Roux JD, Paul DR, Kampa J, Lagow RJ (1994) Modi-
fication of asymmetric polysulfone membranes by
mild surface fluorination. Part I. Transport properties.
J Membr Sci 94:121–141
Robeson LM (2008) Upper bound revisited. J Membr Sci
320:390–400
P
Protein Purification by Membrane
Operations
Andrew L. Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
Synonyms
Proteins separation by membrane operations
Membrane systems are used extensively in the
purification of high-value proteins from natural
sources (e.g., milk and blood plasma) and from
the biotechnology industry. This includes the use
of normal flow microfiltration for sterile filtration
and bioburden reduction, depth filtration for the
removal of cell debris and aggregated material,
tangential flow microfiltration for initial product
recovery, and virus removal filtration (van Reis
and Zydney 2007). Ultrafiltration is used for pro-
tein concentration and buffer exchange, both for
the conditioning of the feed between other unit
operations and in the final product formulation.
However, actual protein purification, which typ-
ically refers to the separation of a desired protein
product from other protein impurities, is accom-
plished using either membrane chromatography
or high-performance tangential flow filtration.
Membrane chromatography provides highly
selective separations by exploiting differences
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_801-3
in protein adsorption/binding interactions, analo-
gous to what is done in column chromatography
(Ghosh 2002). The membrane adsorbers used in
these systems typically have relatively large pore
size with the functional ligands attached to the
inner pore surface throughout the membrane.
Separations can be accomplished using ion
exchange (i.e., charged) ligands, affinity ligands,
and hydrophobic interactions. Zeng and
Ruckenstein (1999) have reviewed the different
base materials and surface modification chemis-
tries that can be used to generate chromato-
graphic membranes.
Transport through membrane adsorbers is typ-
ically dominated by the pressure-driven convec-
tive flow; diffusional limitations are much less
pronounced than in conventional chromato-
graphic beads. This can be particularly important
in the purification of large biomolecules and
viruses that can have difficulty accessing the
internal pore space in chromatographic beads.
Membrane adsorbers can be operated at much
higher flow rates and with lower pressure drops
than conventional chromatography columns,
potentially reducing the processing time (Zhou
and Tressel 2006).
There has been significant interest in using
membrane chromatography for bioprocessing
for more than 20 years, but there have been rela-
tively few large-scale commercial installations.
However, recent improvements in membrane
materials and chemistries, coupled with a greater
appreciation of appropriate target applications,
2 Protein Purification by Membrane Operations
have generated renewed interest in this technol-
ogy. This is particularly true for flow-through
applications in which impurities are bound to
the membrane while the product flows directly
through the membrane (Zhou and Tressel 2006).
This includes the removal of trace DNA, viruses,
and endotoxins. Flow-through applications can
take full advantage of the high linear velocities
possible with membranes. Single-use membrane
adsorbers can be very attractive in these applica-
tions because of the small amount of impurities
that need to be captured. This eliminates the need
for reuse studies at small scale and for regenera-
tion and sanitization at large scale, both of which
facilitate the development of flexible
manufacturing processes (van Reis and Zydney
2007).
High-performance tangential flow filtration
(HPTFF) is an emerging technology that uses
ultrafiltration membranes for the separation of
proteins without limit to their relative size (van
Reis and Zydney 2007). This is in sharp contrast
to conventional ultrafiltration processes that are
generally thought to require a tenfold difference
in size between the product and impurity for
effective separation. HPTFF has been used to
separate monomers from oligomers based on
their difference in size, protein variants differing
at only a single amino acid residue based on the
difference in charge, an antigen-binding frag-
ment from a similar size impurity, and a mono-
clonal antibody from host cell proteins (van Reis
and Zydney 2007).
The high selectivity in HPTFF processes is
obtained by exploiting a number of different
phenomena. As originally described, HPTFF
devices are operated in the pressure-dependent
regime at or below the “transition point” in a
plot of filtrate flux versus transmembrane pres-
sure. This minimizes membrane fouling and takes
advantage of concentration polarization effects to
increase performance (Zeman and Zydney,
1996). Further increases in selectivity are
obtained by using charged ultrafiltration mem-
branes and by adjusting the solution pH and
ionic strength to exploit differences in protein
charge between the product and impurity. High
degrees of purification and yield are obtained
using a diafiltration process in which the impuri-
ties are washed through the membrane and away
from the highly retained product. It is also possi-
ble to collect the product in the permeate solution
with the impurities retained by the membrane.
References
Ghosh R (2002) Protein separation using membrane chro-
matography: opportunities and challenges.
J Chromatogr A 952:13–27
van Reis R, Zydney AL (2007) Bioprocess membrane
technology. J Membr Sci 297:16–50
Zeman LJ, Zydney AL (1996) Microfiltration and ultrafil-
tration: principles and applications. Marcel Dekker,
New York
Zeng X, Ruckenstein E (1999) Membrane chromatogra-
phy: preparation and applications to protein separa-
tion. Biotechnol Prog 15:1003
Zhou JX, Tressel T (2006) Basic concepts in q membrane
chromatography for large-scale antibody production.
Biotechnol Prog 22:341
P

Protein Recovery by Membrane Protein recovery by membrane operations is syn-

Operations onymous with protein purification by membrane
operations and is discussed under that listing.
Andrew Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA

# Springer-Verlag Berlin Heidelberg 2012

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_802-2
P
Protein Separation by Charged UF
Membranes
Andrew Zydney
Department of Chemical Engineering, The
Pennsylvania State University, University Park,
PA, USA
Charged ultrafiltration membranes can be used to
significantly enhance the membrane selectivity,
making it possible to use these membranes for the
separation of similarly sized proteins (Zydney
and van Reis 2011). Charged ultrafiltration mem-
branes can provide very high retention of like-
charged proteins, enabling uncharged proteins
and smaller impurities to be removed in the per-
meate (Zeman and Zydney 1996). Separations
are typically performed at relatively low ionic
strength (<10 mM) to enhance the electrostatic
exclusion of the charged protein from the charged
membrane.
The effect of membrane charge on the separa-
tion of bovine serum albumin (MW = 67 kDa,
pI = 4.8) and an antigen-binding fragment (Fab)
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_804-3
from a monoclonal antibody (MW = 45 kDa,
pI = 8.4) is shown in Table 1. Data were
obtained using an unmodified (negatively
charged) polyethersulfone membrane and a pro-
totype positively charged membrane. The Fab
has a significant positive charge at pH 5, enabling
a highly selective separation using the positively
charged membrane, with the weakly charged
albumin passed into the filtrate. In contrast, albu-
min has a significant negative charge at pH 8.4,
with the negatively charged membrane providing
high selectivity with the weakly charged Fab
collected in the filtrate. These high selectivities
were completely lost when using the membrane
with the “wrong” charge at the given pH.
Electrically charged ultrafiltration membranes
have been successfully used to separate protein
variants differing at only a single amino acid
residue, an antigen-binding fragment from
E. coli host cell proteins, a monoclonal antibody
from mammalian cell host proteins, and a model
pegylated protein from the unreacted protein and
polyethylene glycol, among others (van Reis and
Zydney 2007; Rohani and Zydney 2010).
 Protein Separation by Charged UF Membranes

Protein Separation by Charged UF Membranes, Table 1 Effect of membrane charge and solution pH on the
selectivity for separation of albumin and an antigen-binding fragment. Impurity and product refer to the less and more
retained proteins, respectively. Thus, selectivity is defined as Salbumin/SFab at pH 5 and as SFab/Salbumin at pH 8.4
Solution pH Negative membrane Positive membrane
5.0 3 120
8.4 200 5
Table adapted from Rohani and Zydney (2010)

References Zeman LJ, Zydney AL (1996) Microfiltration and ultrafil-

Rohani MM, Zydney AL (2010) Role of electrostatic
interactions during protein ultrafiltration. Adv Colloid
Interf Sci 160:40–48
van Reis R, Zydney AL (2007) Bioprocess membrane
technology. J Membr Sci 297:16–50
tration: principles and applications. Marcel Dekker,
New York
Zydney AL, van Reis R (2011) Bioseparations: membrane
processes. In: Moo-Young M (ed) Comprehensive bio-
technology, 2nd edn. Academic, Burlington,
pp 499–520
A
Aquaporin-Incorporated Biomimetic
Membranes
Chung Tai-Shung Neal1, Honglei Wang2,
Guofei Sun3, Hoang Hanh Phuoc Duong4 and
Pei Shan Zhong5
1
National University of Singapore, Singapore,
Singapore
2
Department of Chemical & Biomolecular
Engineering, jMedtech Pte Ltd, Singapore,
Singapore
3
Chemical and Biomolecular Engineering,
Aquaporin Asia Pte. Ltd, Singapore, Singapore
4
King Abdullah University of Science and
Technology (KAUST), Biological and
Environmental Science and Engineering
Division (BESE), Thuwal, Saudi Arabia
5
Functionalized Materials and Nanostructures/
Global Research Center Singapore (GMM/F),
BASF South East Asia Pte Ltd., Singapore,
Singapore
Aquaporin, a transmembrane protein, has
attracted attention globally since its serendipitous
discovery by Peter Agre in 1992 (Agre 2006). Its
facilitation in rapid and selective water transport
has inspired many scientists to utilize this unique
function for water treatment applications
(Kaufman et al. 2010; Wang et al. 2012). Much
effort has been devoted to build and overcome the
challenges faced in fabricating the synthetic bio-
mimetic membrane housing the water channel
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_812-3
(Kumar et al. 2012). It is envisioned that this
technology will bring about higher efficiency
for desalination (Kaufman and Freger 2011) and
hence lower cost.
Membrane Preparation Methods
Aquaporin-incorporated membranes can be pre-
pared via the (1) Langmuir-Blodgett (LB) and
Langmuir-Schaefer (LS) monolayer transfer
techniques, (2) vesicle rupture of aquaporin-
incorporated materials onto a porous support, or
(3) autopainting membrane (APM) method.
LB and LS monolayer transfer (Sun
et al. 2012): The first monolayer of amphiphilic
materials (lipids or copolymers) is deposited onto
a solid support by the LB method. The second
monolayer, which contains aquaporin-
incorporated amphiphilic materials, is subse-
quently deposited onto the first layer by the LS
method.
Vesicle rupture: Aquaporins are first incorpo-
rated into liposomes (Borgnia et al. 1999; Wang
et al. 2011) or polymersomes (Kumar et al. 2007)
through a typical transmembrane protein incor-
poration method (Borgnia et al. 1999). Subse-
quently, these aquaporin-incorporated vesicles
are ruptured onto a porous support via charge
interaction (Wang et al. 2011; Kaufman
et al. 2010; Li et al. 2012) or covalent conjugation
between the vesicles and the support (Wang
et al 2012; Zhong et al. 2012; Duong et al. 2012).
2 Aquaporin-Incorporated Biomimetic Membranes

scaffolds (about 300 mm diameter each aperture)

(Hansen et al. 2009; González-Pérez et al. 2009;
Rein et al. 2011). This membrane array can be
stabilized with the support of a highly permeable
hydrogel layer (Lander et al. 2011; Ibragimova
et al. 2012).
The supported lipidic/polymeric membranes
with aquaporins have been designed for several
applications, such as forward osmosis (FO),
nanofiltration (NF), and reverse osmosis (RO).
Detailed information on the materials and prelim-
inary performance is summarized in Table 1.

Characterization of Water Transport

Through the Aquaporin-Incorporated
Membranes

Aquaporin-Incorporated Biomimetic Membranes, The permeability of reconstituted aquaporin in ves-

Fig. 1 Schematic graph of free-standing lipidic/poly-
meric membranes
icles is characterized mainly by the stopped-flow
spectroscopy technique. In a stopped-flow experi-
APM method: Free-standing aquaporin- ment, the osmotic permeability Pf (m3/m2/s)
incorporated lipid/polymeric membranes can be can be calculated by using the equation
formed analogous to the conventional black lipid (Borgnia et al. 1999)
membrane preparation method (Hansen
et al. 2009; González-Pérez et al. 2009). Pf ¼ k=Cosm V w ðSo =V o Þ
A mixed solution of aquaporins and amphiphilic
materials is smeared across the hydrophobic where k is the rate constant obtained from light
array’s apertures in electrolyte conditions. The scattering signal and So(m2) and Vo(m3) are the
membranes are spontaneously formed on the initial surface area and volume of the vesicle,
apertures at the interface of organic and aqueous respectively. Vw is the molar volume of water
phases. (18  106 m3/mol) and Cosm is the osmolarity
difference that drives the vesicle shrinkage.
The hydraulic permeability coefficient Lp
(m/s/bar) represents the rate of water movement
Aquaporin Biomimetic Membrane
across a given area, per unit of osmotic gradient,
Designs
and can be calculated from the equation (Hillyard
2012):
According to their conformations, the designs of
aquaporin-embedded biomimetic membranes
Lp ¼ Pf V w =RT
can be classified into two categories, namely,
(1) free-standing lipidic/polymeric membranes
where R and T are gas constant and temperature,
(Fig. 1) and (2) supported lipidic/polymeric
respectively. When the biomimetic membrane
membranes (Fig. 2).
transforms from a sphere to a flat surface, the
The free-standing lipidic/polymeric mem-
intrinsic water volume flux Jv (m3/s) can be
brane is fabricated by assembling black lipid/
obtained by using equation (Hillyard 2012):
block copolymer domains across multiple aper-
tures in the ethylene tetrafluoroethylene (ETFE)
Aquaporin-Incorporated Biomimetic Membranes 3

Aquaporin-Incorporated
Biomimetic Membranes,
Fig. 2 Schematic graph of
supported lipidic/
polymeric membranes
incorporated with
aquaporins

Aquaporin-Incorporated Biomimetic Membranes, Table 1 Demonstration of aquaporin-incorporated biomimetic

membranes
Material of active layer and support Membrane performance Reference
PMOXA-PDMS-PMOXAa (with acrylate ends), aquaporin FO Wang et al. (2012)
Z (molar ratio 1:50) Draw solution: 2M NaCl
Methacrylate-functionalized PCTE support (average pore size Feed solution: water
50 nm) Water flux: >100 L/m2/h
Salt reverse flux: <10 g/m2/h
PMOXA-PDMS-PMOXAa (with acrylate ends), aquaporin NF Zhong et al. (2012)
Z (molar ratio 1:50) Feed: 200 ppm NaCl
Methacrylate-functionalized CA support (average pore size Pressure: 5 bar
19 nm) PWPb: 34 L/m2/h/bar
Salt rejection: 32 %
PMOXA-PDMS-PMOXAa (with disulfide ends), aquaporin NF Duong et al. (2012)
Z (molar ratio 1:100) Feed: 200 ppm NaCl
Gold-coated porous alumina support (average pore size Pressure: 5 bar
55 nm) Water flux: 8 L/m2/h/bar
Salt rejection: 45 %
DOPCc and DOTAPd RO Li et al. (2012)
Aquaporin Z (molar ratio 1:200) Feed: 1 mM NaCl
Commercially available NF-270 support Pressure: 1 bar
Water flux: 3 L/m2/h/bar
Salt rejection: 20 %
a
Poly(2-methyloxazolineb-dimethylsiloxane-b-2-methyloxazoline)
b
Pure water permeability
c
1,2-dioleoyl-sn-glycero-3- phosphocholine
d
1,2- dioleoyl-3-trimethylammonium-propane (chloride salt)

J v ¼ ALp ðslRTDC  DPÞ References

where A is the membrane area, in m2. s is the
reflection coefficient and is assumed to be 1. l is
the molecularity. DP is the hydrostatic pressure
difference across the membrane, in bar. DC is
concentration difference across the membrane,
in mol/m3.
Agre P (2006) The Aquaporin water channels. Proc Am
Thorac Soc 3:5–13
Borgnia MJ, Kozono D, Calamita G, Maloney PC, Agre
P (1999) Functional reconstitution and characteriza-
tion of AqpZ, the E. coli water channel protein. J Mol
Biol 291:1169–1179
Duong PHH, Chung TS, Jeyaseelan K, Armugam A,
Chen Z, Yang J, Hong M (2012) Planar biomimetic
aquaporin-incorporated triblock copolymer
4 Aquaporin-Incorporated Biomimetic Membranes
membranes on porous alumina supports for
nanofiltration. J Membr Sci 409–410:34–43
González-Pérez A, Stibius KB, Vissing T, Nielsen CH,
Mouritsen OG (2009) Biomimetic triblock copolymer
membrane arrays: a stable template for functional
membrane proteins. Langmuir 25(18):10447–10450
Hansen JS, Perry M, Vogel J, Vissing T, Hansen CR,
Geschke O, Emnéus J, Hélix-Nielsen C (2009) Devel-
opment of an automation technique for the establish-
ment of functional lipid bilayer arrays. J Micromech
Microeng 19:025014
Hillyard SD (2012) Sensing meets separation: water trans-
port across biological membranes. In: Hélix-Nielsen
C (ed) Biomimetic membranes for sensor and separa-
tion applications. Springer, Netherlands, pp 2–4
Ibragimova S, Stibius K, Szewczykowski P, Perry M,
Bohr H, Helix-Nielsen C (2012) Hydrogels for in situ
encapsulation of biomimetic membrane arrays. Polym
Adv Technol 23(2):182–189
Kaufman Y, Freger V (2011) Supported biomimetic mem-
branes for pressure-driven water purification. On biomi-
metics. InTech. http://www.intechopen.com/books/on-
biomimetics/supported-biomimetic-membranes-for-press
ure-driven-water-purification
Kaufman Y, Berman A, Freger V (2010) Supported lipid
bilayer membranes for water purification by reverse
osmosis. Langmuir 26:7388–7395
Kumar M, Grzelakowski M, Zilles J, Clark M, Meier
W (2007) Highly permeable polymeric membranes
based on the incorporation of the functional water
channel protein Aquaporin Z. Proc Natl Acad Sci
U S A 104:20719–20724
Kumar M, Payne MM, Poust SK, Zilles JL (2012)
Polymer-based biomimetic membranes for
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membranes for sensor and separation applications.
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Geschke O, Perry M, Helix-Nielsen C (2011) Biomi-
metic membrane arrays on cast hydrogel supports.
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Torres J, Fane T (2012) Preparation of supported
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Nielsen C (2011) Free-standing biomimetic polymer
membrane imaged with atomic force microscopy.
Langmuir 27(2):499–503
Sun G, Zhou H, Li Y, Jeyaseelan K, Armugam A, Chung
TS (2012) A novel method of Aquaporin
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layers. Colloids Surface B 89:283–288
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Hong M, Jeyaseelan K, Armugam A (2011) Prepara-
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metic membranes embedded with Aquaporin Z on
carboxylated polyethylene glycol polymer cushion.
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Armugam A, Chen Z, Hong M, Meier W (2012)
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A
Air Bubbling in Membrane
Distillation
Chunrui Wu
State Key Laboratory of Hollow Fiber Membrane
Materials and Membrane Processes, Institute of
Biological and Chemical Engineering, Tianjin
Polytechnic University, Tianjin, China
Air bubbling is a common method that is used in
membrane separation process to alleviate mem-
brane fouling and improve flux. It also is a kind of
membrane cleaning method. Till now, gas-liquid
two phase flow has been well studied and widely
used in microfiltration, ultrafiltration (Cabassud
et al. 1997), membrane bioreactor (Psoch and
Schiewer 2005), and other traditional membrane
separation technologies.
Based on the above advantages of air bub-
bling, it has been introduced into membrane dis-
tillation (MD) process to alleviate membrane
fouling and improve the heat and mass transfer
efficiency. Researchers have introduced air bub-
bling into MD process and developed several new
kinds of MD process.
The first application of air bubbling in MD
process was firstly reported in 2008 (Ding
et al. 2008) to concentrate the extract of tradi-
tional Chinese medicine (TCM). Air bubbling
was used in direct contact membrane distillation
(DCMD) and the flow sheet is shown in Fig. 1.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_813-1
The TCM extract was heated to 43–62
C and
pumped to the module; another pump was used to
circulate the permeate water (maintained at
25
C) at the permeate side of the membrane
module. The velocity of the feed and permeate
flow in the membrane module ranged from 0.07
to 0.13 m/s. To mitigate membrane fouling, a fan
was used to create gas bubbling at the feed side of
the membrane module. This fan was also utilized
to generate gas sparging at the permeate side for
gas backwashing of the membrane. The concen-
tration ratio (CR) was defined as the ratio of the
volume of initial extract to the volume of con-
centrated extract to indicate the concentrating
performance of the experiments.
The result showed that a sharp flux decline
right after the air was introduced into the feed
circulation, and the flux remained at much lower
level when air was continuously injected. The
explanation authors gave was that the bubbles
occupied part of the liquid-contacting area in
the membrane, thus reducing the effective mem-
brane area, and when gas entered the membrane
pores, this reduced the partial pressure of water
vapor within the pores, thus reducing the driving
force. To reduce these effects, intermittent gas
sparging at the feed side at intervals of 20 min
and lasting only 2 min was applied.
The effect of gas bubbling on the DCMD
performance was shown in Fig. 2. It could be
seen that flux declined rapidly in the beginning
of the experiment and then slowly as a result of
the very low-flux level at this time. The
2 Air Bubbling in Membrane Distillation

Air Bubbling
in Membrane 9
Distillation,
Fig. 1 Schematic of
DCMD apparatus. (1)
Thermostatic bath, (2) tank
of TCM extract, (3) gear
pump for extract
circulation, (4) chiller, (5)
gear pump for permeate, (6)
permeate tank, (7) electric
balance, (8) fan for gas
bubbling, and (9) flat sheet
membrane module
3 4 6 8
2 5
7
1

Air Bubbling 24
in Membrane C0 =1.35g/l, tf=60°C, u f=u p=0.102m/s
Distillation, 22 The gas bubbling lasted for 2 min every 20 min
Fig. 2 Performance of 20 1L/min gas flowrate
DCMD using gas bubbling 2L/min gas flowrate
on the feed side 18
without gas bubbling
16
N, kg/m2h

14
12
10
8
6
4
2
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
CR

introduction of gas bubbling at the feed side
resulted in a higher flux in the beginning of the
experiment and a much slower flux decline. Very
similar trends were observed with gas bubbling at
1 and 2 L/min which meant that increasing the
gas flow rate did not result in further process
enhancement.
A novel air-bubbling vacuum membrane
distillation (AVMD) process was constructed
in 2011 (Wu et al. 2011) to investigate the
enhancement effect of air bubbling on traditional
VMD process. Compressed air was pressed into
the lumen side of the hollow fiber membranes
together with the hot feed solution just at the
inlet of membrane module to form gas-liquid
two phase flow, as shown in Fig. 3.
The results showed that the permeate flux
increased with the air flow rate and/or feed tem-
perature increasing. For the VMD process, the
permeate flux was 22 kg/(m2h) when tested at
75
C with a feed flow rate of 120 L/h and a
vacuum pressure of 0.0085 MPa. While, the flux
of AVMD process could reach 40 kg/(m2h) when
gas was introduced into feed solution at the rate
of 60 L/h, as shown in Fig. 4. For the two pro-
cesses, flux both declined gradually as the feed
concentration increased from 3.5 to 300 g/L, but
it was much slower for AVMD process. SEM
Air Bubbling in Membrane Distillation 3

Air Bubbling
in Membrane
Distillation,
Fig. 3 Theoretic diagram
of ABMD process Vacuum

Membrane Module
Hollow Fiber
Gas-Liquid two phase
flow

Hot Solution Compressed Air

Air Bubbling 50 4500

in Membrane N
Distillation, Fig. 4 Effect Re
of feed gas flow prate on the 40
performance of AVMD 4000
process
N (kg/m2h)

30

Re
3500
20

3000
10

0 2500
0 10 20 30 40 50 60 70
Gas flow rate (L/h)

pictures showed that membranes used in AVMD
process had lighter fouling than that in VMD
process.
For elevated salt concentrations in the feed
steam, gas bubbling was introduced into direct
contact membrane distillation (DCMD) in 2013
(Chen et al. 2013) to examine its effect on the MD
performance. In the paper, to characterize the
performance improvement achieved by gas bub-
bling, the flux enhancement ratio F is defined:
J gas
F¼
J nogas
where Jgas and Jnogas are the permeate fluxes in
the DCMD process with and without bubbling,
respectively.
Gas bubbling is supplied by an air pump. The
air inlet at the feed side entrance of the membrane
module and the air nozzle for dispersing the air
are shown in Fig. 5.
The results showed that the introduction of gas
bubbling could effectively enhance MD flux, and
the flux enhancement ratio could reach 1.72 at an
optimized gas flow rate. When the condition was
either a high feed operating temperature, low feed
and permeate Reynolds numbers, or a module
with 45
inclined orientation, shorter fiber length,
or lower packing density, a higher flux
4 Air Bubbling in Membrane Distillation

Air Bubbling a
in Membrane
Distillation, Fig. 5 (a)
Air inlet connected to the
membrane module; (b) Air
nozzle

Feed

Air

Air Bubbling 1.8

in Membrane Laminar flow, Ref = 842
Distillation, Fig. 6 Effect Turbulent flow, Ref = 2808
of gas flow rate on F in
laminar and turbulent flows 1.6

1.4
F

1.2

1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Gas flowrate (L.min–1)

enhancement ratio could be achieved. Because
air bubbling could enhance the turbulence of
feed solution, temperature polarization was
effectively reduced. However it was not that the
bigger the gas flow rate, the higher the enhance-
ment ratio. It was observed that beyond an opti-
mal gas flow rate, the enhancement ratio fell,
possibly due to excessive flow bypassing.
The effect of gas flow rate on F in laminar and
turbulent flows was shown in Fig. 6. In the figure,
it was observed that these two F curves had a
similar trend. At first, F increased with increasing
gas flow rate in the range of 0 Qg 0.2 L min1
for the laminar flow and 0 Qg 0.5 L min1 for
the turbulent flow, while F decreased when gas
rate was higher. Furthermore, the Ф value of the
laminar condition was much higher than that of
the turbulent flow when other conditions were the
same.
In 2009, air bubbling was used in a hybrid
process combining membrane distillation in a
submerged membrane bioreactor (MDBR) to
mitigate severe fouling and flux decline
(Phattaranawik et al. 2009). The result showed
that adding two inlets for air sparging at 2.5 L/min
each near the potting at the center of the
membrane bundle induced more turbulence at
the membrane surface. Over 15 days, fluxes were
still relatively stable with an average value of
5.16 L/(m2h).
Air Bubbling in Membrane Distillation
To sum up, air bubbling was an effective
method in membrane distillation to enhance the
performance of MD process. Due to the role of
increasing turbulence of feed solution, air bub-
bling could promote the agitation and mix of feed
solution to decrease the temperature and concen-
tration polarization effect. In addition, the
enhancing surface shear rate increases the
remove of foulant from membrane surface at the
feed side to inhibit the influence of membrane
fouling.
References
Cabassud C, Laborie S, Lainé JM (1997) How slug-flow
can improve ultrafiltration flux in organic hollow
fibres. J Membr Sci 128(1):93–101
5
Chen GZ, Yang X, Wang R, Fane AG (2013) Performance
enhancement and scaling control with gas bubbling in
direct contact membrane distillation. Desalination
2013(308):47–55
Ding Z, Liu L, Yu J, Ma R, Yang Z (2008) Concentrating
the extract of traditional Chinese medicine by direct
contact membrane distillation. J Membr Sci
310(1–2):539–549
Jirachote P, Fane AG, Pasquier ACS, Wu B (2009) Exper-
imental study and design of a submerged membrane
distillation bioreactor. Chem Eng Technol
32(1):38–44
Psoch C, Schiewer S (2005) Long-term study of an inter-
mittent air sparged MBR for synthetic wastewater
treatment. J Membr Sci 2005(260):56–65
Wu CR, Yue J, HuaYan C, Xuan W, QiJun G (2011) Study
on air-bubbling strengthened membrane distillation
process. Desalination Water Treat 34(1–3):2–5
H
Heat and Mass Transfer
in Membrane Distillation
Chunrui Wu
State Key Laboratory of Hollow Fiber Membrane
Materials and Membrane Processes, Institute of
Biological and Chemical Engineering, Tianjin
Polytechnic University, Tianjin, China
Membrane distillation (MD) is a membrane
seperation process based on the principle of evap-
oration which uses hydrophobic membrane as
separating medium. Unlike the membrane pro-
cess of ultrafiltration (UF) and reverse osmosis
(RO) which only contain mass transfer, MD also
contains heat transfer and the heat transfer is a
key factor affecting mass transfer efficiency. So
the investigation of heat and mass transfer in MD
process is the key to explore the mechanism of
MD process. Many scientists have made signifi-
cant progress in the study of heat and mass trans-
fer in MD process.
Heat Transfer
The heat transfer of MD consists of three steps, as
shown in Fig. 1. First, heat transfer by the way of
convection in the feed boundary layer. Second,
heat transfer by the way of conduction through
the membrane and the heat flows together with
the vapor through the membrane pores, i.e., the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_814-1
latent heat of vaporization. Third, heat transfer by
the way of convection in the permeate boundary
layer. All types of MD contain the first two steps,
while for the third step, other types of MD do not
contain it except DCMD.
At steady state, the overall heat transfer coef-
ficient (H) of the MD process can be expressed by
a resistance in series model (M. Khayet
et al. 2000):
1 1 1 1
¼ þ þ
H hf hm þ JDH v =DT m hp
where hf, hm, and hp are the individual heat trans-
fer coefficients of liquid feed phase, membrane,
and permeate, respectively; DHv is the heat of
vaporization and DTm is the temperature drop
across the membrane.
For MD process, heat and mass transfer occur
simultaneously and result in complex heat trans-
fer mechanisms. So the mass transfer can affect
both heat transfer rates and heat transfer coeffi-
cients. The heat transfer model has been proposed
to describe the heat transfer mechanisms in MD
and facilitates the evaluation of the membrane
surface temperatures. In most literatures, the
heat transfer model for MD was developed
based on the assumption of linear temperature
profile and isenthalpy flow of vapor (Figs. 2, 3,
and 4).
The effective energy transfering from the feed
bulk to the membrane surface is:
2 Heat and Mass Transfer in Membrane Distillation

Heat and Mass Transfer Conduction

in Membrane
Distillation, Fig. 1 Heat
transfer resistances in
membrane distillation Tb,f TI,f TI,p Tb,p

Thermal boundary Thermal boundary

layer layer

Latent heat of vaporisation

Heat and Mass Transfer Membrane

in Membrane
Distillation, Fig. 2 Direct Tf Permeate
contact membrane
distillation
T1
T2
Feed
Tp

Mass flux (J)

Heat flux (q)

Heat and Mass Transfer

in Membrane
Distillation, Fig. 3 Air
gap membrane distillation
Heat and Mass Transfer in Membrane Distillation 3

Heat and Mass Transfer

in Membrane Liquid−vapour
Distillation, interface Aqueous
Fig. 4 Vacuum membrane Retentate Vacuum &
solution
cooling
distillation

Vapour

Suction and
condenstation Porous membrane

Permeate
Aqueous solution (warm)

Qf ¼ hf T f  T fm the MD process, except in AGMD (Curcio and
Drioli 2005).
The energy transfering across the membrane
is:
Mass Transfer
hm

Qm ¼ JDH þ T fm  T pm
d The mass flux (J) in MD process is assumed to be
proportional to the vapor pressure difference
For the VMD process, the contribution of heat
across the membrane and is given by:
conduction in the membrane matrix can be
neglected due to the high vacuum degree in the

J ¼ C m Pf  P p
vacuum side (Li and Sirkar 2005).
At steady state, the overall heat transfer flux
where Cm is the membrane coefficient, Pf and Pp
through the membrane is given by:
are the vapor pressure at the membrane feed and
permeate surfaces, which can be calculated from
Q ¼ Qf ¼ Qm ¼ Qp
the Antoine equation (Fig. 5). For different types


of MD processes, the obtainment of Cm is based
km
hf T f  T f , m ¼ JDH þ T fm  T pm on different models:
d

For DCMD process, mass transfer through the
¼ hp T p , m  T p membrane can be divided into three models.

These models relate the mass transport with col-
Q ¼ H Tf  Tp lisions between molecules, and/or molecules
with membrane. Knudsen diffusion takes place
It is worth pointing out that the heat conduc- when the pore size is too small, such that the
tion can be neglected for nonsported thin mem- collision between the molecules and the inside
brane and high operating temperature as well walls of the membrane suitably expresses the
(Phattaranawik and Jiraratananon 2001). More- mass transport and the collision between mole-
over, the heat transfer by convection is ignored in cules can be ignored (Zhongwei et al. 2003).
4 Heat and Mass Transfer in Membrane Distillation
Heat and Mass Transfer
in Membrane
Distillation, Fig. 5 Mass
transfer resistances in
membrane distillation
xb,f
Concentration boundary
layer
Molecular diffusion occurs when the molecules
move corresponding to each other under the influ-
ence of concentration gradients. In Poiseuille
flow (viscous flow), the gas molecules act as a
continuous fluid driven by a pressure gradient.
In AGMD process, the molecular diffusion
theory is used to describe the transfer of vapor
molecules through the membrane and the air gap.
A stagnant gas film (air) is assumed to lie inside
the membrane at the air gap side.
For VMD process, in order to remove air
trapped in the membrane pores, the deaeration
of the feed solution or a continuous vacuum in
the permeate side should be applied. Conse-
quently, the ordinary molecular diffusion resis-
tance is neglected. The Knudsen mechanism is
used to express the mass transfer (Bandini and
Sarti 1999), Poisseille flow, or both together
(Banat and Simandl 1994).
Viscous
xI,f xI,p xb,p
Cocentration boundary
layer
Knudsen Molecular
References
Banat FA, Simandl J (1994) Theoretical and experimental
study in membrane distillation. Desalination
95(1):39–52
Bandini S, Sarti GC (1999) Heat and mass transport resis-
tances in vacuum membrane distillation per drop.
AIChE J 45:1422–1433
Curcio E, Drioli E (2005) Membrane distillation and
related operations – a review. Sep Purif Rev
34(1):35–86
Ding Z, Ma R, Fane AG (2003) A new model for mass
transfer in direct contact membrane distillation. Desa-
lination 151(3):217–227
Khayet M, Godino P, Mengual JI (2000) Theory and
experiments on sweeping gas membrane distillation.
J Membr Sci 165:261–272
Li B-A, Sirkar KK (2005) Novel membrane and device for
vacuum membrane distillation-based desalination pro-
cess. J Membr Sci 257:60–75
Phattaranawik J, Jiraratananon R (2001) Direct contact
membrane distillation: effect of mass transfer on heat
transfer. J Membr Sci 188(1):137–143
H
Hollow Fiber Modules
for Desalination
Chunrui Wu
State Key Laboratory of Hollow Fiber Membrane
Materials and Membrane Processes, Institute of
Biological and Chemical Engineering, Tianjin
Polytechnic University, Tianjin, China
The desalination of brine is commercially
implemented by reverse osmosis (RO), multi-
effect evaporation (MED), and multistage flash
(MSF) distillation. Although such conventional
processes are widely used, there is a need for
novel desalination techniques such as membrane
distillation (MD) which may be much cheaper
and have other distinct advantages. The mem-
branes used in MD processes can be divided
into two forms: flat sheet membrane and hollow
fiber-based membrane. Most of the work on
hydrodynamic improvement in MD studies has
focused on flat sheet membrane modules. They
have small membrane areas and thus are limited
to laboratory research. In industry, hollow fiber-
based membrane modules are preferable due to
their lager membrane area per unit volume and
reduced vulnerability to temperature polariza-
tion. Based on the MD mechanism, the obtained
flux depends both on the membrane permeation
properties and the flow geometry in the mem-
brane modules. Therefore, the research on the
flux enhancement in MD can be divided into
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_815-1
two large areas, the fabrication of highly perme-
able membranes and designs of optimized mem-
brane modules.
Recently, many designs of hollow fiber mem-
brane modules have been proposed in order to
suppress the undesirable temperature and con-
centration polarization phenomena. The perfor-
mances of different polyvinylidene fluoride
(PVDF) hollow fiber membranes have been stud-
ied in different size modules (Fig. 1). The prop-
erties of the laboratory modules made, which
depend on the experiment’s requirements, can
be changed. The modules of PVDF have a stable
performance and can be used in reverse osmosis
drained wastewater treatment (Wu Chunrui
et al. 2010). The study in comparison of three
membrane distillation configurations and seawa-
ter desalination by vacuum membrane distillation
(VMD) showed that the shell-and-tube capillary
membrane module had unique advantages such
as flexible and changeable (Chen Huayan
et al. 2011).
Li et al. designed a novel membrane device
made of novel membranes. To enhance the brine
side heat transfer coefficient substantially, they
employed cross flow of hot brine over the outside
surface of hollow fiber membranes. To achieve a
compact device, they designed a hollow fiber
device built in a rectangular cross flow mode for
the hot brine to flow over the outside of the fibers
(Fig. 2) (Li and Sirkar 2005). Simplified models
have been developed to describe the observed
performance of the modules in different MD
2 Hollow Fiber Modules for Desalination

Hollow Fiber Modules

for Desalination,
Fig. 1 Modules of PVDF
hollow fiber membrane

Hollow Fiber Modules

for Desalination,
Fig. 2 Rectangular cross
flow test module without
face plates

processes (Gilron et al. 2007). The MD experi-
ment’s results have shown that the modules’ per-
formance was quite satisfactory and the design of
module enhanced the heat transfer as well as
mass transfer.
Different hollow fiber configurations with
wavy geometries (twisted and braided) for flux
enhancement in MD process have been devel-
oped by Teoh et al. in 2008 (Teoh et al. 2008).
The different module designs, such as baffles and
spacers, were incorporated during the module
Hollow Fiber Modules for Desalination
Hollow Fiber Modules for Desalination, Fig. 3 Different modules design and hollow fiber geometries
configurations
fabrication process, as illustrated in Fig. 3. A sin-
gle sieve spacer was placed about 7.5 cm away
from both ends of the module in the spacer mod-
ule designs. And the distance between each
spacer for the two or three-sieve spacers config-
urations was 5 or 3.75 cm. Similarly, the helical
baffle introduced in the central of the module
which was surrounded by hollow fibers was
placed 5 cm away from the both ends of the
membrane module. The results showed that the
application of baffles can increase the feed side
heat transfer coefficient. In addition, using
spacers among the fibers may increase the effec-
tive membrane area 18–33 %. Lastly, the appli-
cation of different hollow fiber configurations
with wavy geometries could lead to flux enhance-
ments as high as 36 % without inserting any
external turbulent promoter. In overall, the goal
of greater flux enhancements with modified hol-
low fiber membranes modules was achieved.
Five types of novel hollow fiber module con-
figurations have been designed and constructed
by Yang et al. for the direct contact membrane
distillation (DCMD) process in 2011 (Yanga
et al. 2011). The novel designs could be divided
into structured-straight fibers, curly fibers, central
tubing for feeding, spacer-wrapped fibers, and
spacer-knitted fibers. The test results showed
that the vapor permeate flux could be enhanced
from 53 % to 92 % compared with the
3
conventional module, and the spacer-knitted
module had the best performance. Experiments
reveal that improved fiber geometries or arrange-
ments can provide a better flow distribution, thus
much lower pumping energy cost and higher
thermal efficiency could be accomplished
(Fig. 4).
In 2005, Liu et al. prepared some coiled hol-
low fiber membrane modules and experimentally
examined their mass transfer performances (Liu
et al. 2005). The research results showed that,
compared with the conventional straight module,
the mass transfer in both tube and shell side of the
coiled hollow fiber module could be remarkably
enhanced. And the mass transfer coefficient of
the coiled module at either side of membrane
was more than two times higher than that of the
straight module. The configurations of the coiled
hollow fiber membrane module and the conven-
tional strait module are shown in Fig. 5. Different
geometric coiled modules were employed to
study the influences of the factors such as coiled
diameter, wind angle, and internal diameter of
fibers on mass transfer. It was found that wind
angle had an important influence on the fluid
condition of the coiled module and its mass
transfer.
Geng et al. developed a new air-gap mem-
brane distillation (AGMD) module with internal
latent heat recovery configuration (Geng
4 Hollow Fiber Modules for Desalination

Fig. 4 (continued)
Hollow Fiber Modules for Desalination 5

Hollow Fiber Modules for Desalination, Fig. 4 Novel module design and fabrication: (a) structured-straight
module; (b) curly-fiber module; (c) central-tubing module; (d) spacer-wrapped module; e spacer-knitted module
6 Hollow Fiber Modules for Desalination

Hollow Fiber Modules

for Desalination,
Fig. 5 Schematic
representation of straight
module (a) and coiled
module (b)

Th
hollow fiber membrane
polypropylene net
heat exchange
hollow fiber Hot
Feed

Cold Cold
Feed Feed

Arrangements in cross section

of hollow fiber membranes
and heat exchange hollow
fibers Tc Tc

Hollow Fiber Modules for Desalination, Fig. 6 Schematic presentation of the novel AGMD module

et al. 2014). The novel module is consisted of
parallel hollow fiber membranes and heat
exchanged hollow fibers (Fig. 6). They investi-
gated the influences of operating factors such as
feed flow rate, feed temperature, and feed initial
concentration on AGMD process. Simulta-
neously they established a theoretical model
based on the energy and mass balances of the
hot feed side in membrane. The model was used
to calculate the temperature and the vapor per-
meate flux distributions along the hollow fiber
membrane. The performance of the AGMD mod-
ule was experimentally demonstrated under dif-
ferent operating conditions, and the results
showed that the energy of AGMD process was
Hollow Fiber Modules for Desalination
recycled effectively, simultaneously, a high
gained output ratio (GOR) of 5.7 was obtained.
References
Hongxin Geng, HaoyunWu, Pingli Li, Qingfeng He
(2014) Study on a new air-gap membrane distillation
module for desalination. Desalination 334:29–38
Gilron J, Song L, Sirkar KK (2007) Design for cascade of
cross flow direct contact membrane distillation. Ind
Eng Chem Res 2007(46):2324–2334
Chen Huayan, Wu Chunrui, Jia Yue, Wang Xuan, Lu
Xiaolong (2011) Comparison of three membrane dis-
tillation configurations and seawater desalination by
vacuum membrane distillation. Desalination Water
Treat 28:321–327
7
Li B, Sirkar KK (2005) Novel membrane and device for
vacuum membrane distillation desalination process.
J Membr Sci 2005(257):60–75
Liying Liu, Lijun Li, Zhongwei Ding, Runyu Ma, Zurong
Yang (2005) Mass transfer enhancement in coiled
hollow fiber membrane modules. J Membr Sci
264:113–121.
Teoh MM, Bonyadi S, Chung T-S (2008) Investigation of
different hollow fiber module designs for flux
enhancement in the membrane distillation process.
J Membr Sci 2008(311):371–379
Wu Chunrui, Jia Yue, Chen Huayan, Wang Xuan, Lu
Xiaolong (2010) Membrane distillation and novel inte-
grated membrane process for reverse osmosis drained
wastewater treatment. Desalination Water Treat
18:1–6
Yanga X, Wanga R, Fane AG (2011) Novel designs for
improving the performance of hollow fiber membrane
distillation modules. J Membr Sci 2011(384):52–62
M

Multi-effect Membrane Distillation performance of MEMD process. Methodologies

Chunrui Wu
Institute of Biological and Chemical
Engineering, State Key Laboratory of Hollow
Fiber Membrane Materials and Membrane
Processes, Tianjin Polytechnic University,
Tianjin, China
were presented to maximize energy recovery and
show the cost of the cross-flow DCMD stages.
The results indicated that with the optimum num-
ber of cross-flow stages, the distillate cost would
be competitive with that of large-scale
seawater RO.

The MEMD Processes with DCMD

Multi-effect membrane distillation (MEMD) is a
Modules
promising technology that can avoid the disad-
vantages of single-stage MD process. Generally
In 2010, a new design was developed by integrat-
the gained output ratio (GOR) evaluating the
ing a countercurrent cascade of cross-flow
performance of the single-stage MD is less than
DCMD and a heat exchanger (Lee et al. 2010).
1. However, the GOR of the MEMD process can
The heat exchanger is filled of solid polymeric
be 20 from literatures. It is even better than
hollow fibers. A novel numerical simulator was
multiple-effect evaporation (MEE) and multi-
developed to simulate the performances of this
stage flash (MSF). The MEMD process can sig-
device. And an experiment was operated to dem-
nificantly increase the thermal energy efficiency
onstrate the numerical model. The numerical
and reduce the cost of equipment. Many
simulator predicts that the GOR can be 12 when
researchers are trying their best to study the
the brine flow rate and distillate flow rate are
MEMD technology and find out an appropriate
different.
process.
He et al. presented their research about a series
The process of a countercurrent direct contact
of countercurrent DCMD cascades of two types
membrane distillation (DCMD) module and a
(He et al. 2012). Two different configurations
heat recovery heat exchanger was developed in
(Fig. 1) with interstage heating or not were theo-
1987 (Fane et al. 1987). On this basis, different
retically analyzed. The results show that with
designs for cascade of cross-flow DCMD were
interstage heating provided at the top of each
developed by Gilron et al. (2007). They theoret-
stage, the energy recovery is about 60 % and
ically analyzed the influence of the operating
GOR may be above 20.
conditions such as brine temperature, distillate
temperature, and brine flow rate on the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_816-1
2 Multi-effect Membrane Distillation

Multi-effect Membrane Distillation, Fig. 1 Two different modes of obtaining increased recovery by operating with a
series of cascades: (a) with interstage brine heating and (b) without interstage brine heating

The MEMD Processes with VMD Modules
By replacing the flash chambers of MSF desali-
nation systems with membrane distillation mod-
ules, a small-scale and off-grid desalination
system (Fig. 2) can be built (Edward
et al. 2013). The results of model analysis showed
that the multistage vacuum membrane distillation
(MSVMD) system can achieve the performance
of MSF for the same condition. Additionally,
MSVMD has some advantages over MSF, such
as operation at lower temperature, the use of low
temperature heat sources, and the use of inexpen-
sive polymer materials.
The memsys has developed a novel vacuum
multi-effect membrane distillation (V-MEMD)
module (Zhao et al. 2013). The V-MEMD pro-
cess is achieved by many single stages
Multi-effect Membrane Distillation 3

BRINE
decreasing Pp REJECT

MD MD
@ PP TO VAC @ PP TO VAC
· ∼0
m m· ∼ 0
Qin
CONDENSER CONDENSER
FEED IN

COOLER COOLER

PERMEATE
OUT
j=1 j=n

Multi-effect Membrane Distillation, Fig. 2 Multistage vacuum MD (MSVMD) process diagram

Multi-effect Membrane Distillation, Fig. 3 Schematic diagram of the integrated system of AGMD and HEN

connecting. Every single-stage’s structure The MEMD Processes with AGMD

includes alternating membrane frames and foil
frames for evaporation and condensation. Vac-
uum enhances the membrane distillation process
and solar provides the energy. The results showed
that the heating and cooling temperatures are the
main factors among the operation conditions
affecting flux and energy recovery. Also the opti-
mization of module design shows that the
memsys module has great potential in increasing
the GOR.
Modules
A method that integrates the heat exchanger net-
work (HEN) into the MD system is presented
(Lu and Chen 2012). The schematic diagram of
the integrated system of AGMD and HEN is
showed in Fig. 3. The waste heat from HEN can
be the energy source of the MD process so as to
reduce the water cost. The method consists of two
steps: first, the stream date is calculated for the
MD design; second, HEN design is done. The
design results show the optimal multistage MD
4 Multi-effect Membrane Distillation
Multi-effect Membrane
Distillation,
Fig. 4 Schematic
presentation of hollow
fiber-based MEMD process
retentate
Th,o=29 °C
system that can keep high energy efficiency and
improve the productive rate of the system. It also
gives the optimal operating conditions and
explicit stream data. The cost difference between
HENs with and without the MD streams is con-
sidered as the partial cost of pure water resulting
from the MD process.
A heat recovery technology in AGMD process
using a two hollow-fiber-set membrane module
has been developed. In the module, the hot brine
flows through a porous hydrophobic membrane,
the vapor through the wall of the porous hydro-
phobic membrane is condensed on the wall of
dense wall fibers and warms up the cold brine
flow. The configuration of MEMD process is
presented in Fig. 4, which includes the AGMD
module described before and an external heat
exchanger. Enrichment experiment of semi-
volatile organic acids from aqueous solutions by
this MEMD process has been completed (Ban
Rui et al. 2012). The influence of operating con-
ditions for the performance of MEMD process
has been studied. The GOR of this experiment
can be 9.84 and the acid rejection rate can be
99.93 %. The results present that the MEMD
process can be potentially applied to enriching
external heater
Th,i=90 °C Tc,o=85°C
vapor
dense-Wall fiber
porous fiber
cold feed
Tc,i=25°C
distillate
Td=26 °C
organic acids from their respective dilute aqueous
solutions. Using this MEMD process, Xiaojun Li
et al. studied the concentration of aqueous sulfu-
ric acid solution (Xiaojun Li et al. 2012). The
GOR value obtained was much higher than that
in traditional and other modified membrane dis-
tillation processes. The maximum value of GOR
could reach 11.5. And in a long-term stability test
(lasting for more than 30 days), the MEMD mod-
ules were kept in good condition, which demon-
strated the stability of this MEMD process.
A conception of continuous-effect membrane
distillation (CEMD) was proposed in 2013 Yao
et al. (2013). The CEMD process based on hollow
fiber AGMD module and the MEMD process
with an AGMD module are exactly the same.
However, the research studied two kinds of
CEMD modules made from different membrane
fibers. The influences of operating conditions on
the performance of CEMD process have been
investigated. Within the studied experimental
range, the maximum GOR value could reach
13.8. The theoretical model successfully
predicted the possible ways to obtain a higher
GOR value. And the experiment data showed
agreement with theoretical conclusions.
Multi-effect Membrane Distillation
References
Fane AG, Schofield RW, Fell CJD (1987) The efficient use
of energy in membrane distillation. Desalination
1987(64):231–243
He F, Gilron J, Sirkar KK (2012) High water recovery in
direct contact membrane distillation using a series of
cascades. Desalination. Doi:10.1016/j.
desal.2012.08.006
Gilron J, Song L, Sirkar KK (2007) Design for cascade of
cross flow direct contact membrane distillation. Ind
Eng Chem Res 2007(46):2324–2334
Lee H, He F, Song L (2010) Desalination with a cascade of
cross–flow hollow fiber membrane distillation devices
integrated with a heat exchanger. AIChE J 2011
7(57):1780–1795
Summers EK, Lienhard JH V (2013) Cycle performance
of multi-stage vacuum membrane distillation
5
(MS-VMD) systems. The International Desalination
Association World Congress on Desalination and
Water Reuse 2013/Tianjin. REF: IDAWC/TIAN13-
202
Lu Y, Chen J (2012) Integration design of heat exchanger
networks into membrane distillation systems to save
energy. Ind Eng Chem Res 2012(51):6798–6810
Yao K, Qin Y, Yuan Y, Liu L, He F, Wu Y (2012)
A continuous-effect membrane distillation process
based on hollow fiber AGMD module with internal
latent-heat recovery. AIChE J 2013 4(59):1278–1297.
Zhao K, Heinzl W, Wenzel M, Butter S, Bollen F,
Lange G, Heinzl S, Sarda N (2013) Experimental
study of the memsys vacuum multi effect membrane
distillation (V–MEMD) module. Desalination
323:150–160
A
Acid Gas: Effect on Membrane
Properties
Colin A. Scholes
Department of Chemical & Biomolecular
Engineering, The University of Melbourne,
Parkville, Australia
Acidic gas removal is the largest application of
gas separation membranes and a vital process in
the natural gas processing industry. Membranes
used in this process are designed to separate H2S
and CO2, and this process is known as natural gas
sweetening. This is readily required for
low-quality natural gas reserves, which need to
be processed to achieve pipeline specifications of
CO2 <2 mol% and H2S <4 ppm (Baker 2001).
The removal of acidic gases is also required for
biogas and gasification, where H2S and CO2 are
separated from CH4, CO, and H2. For natural gas
sweetening, the membrane must exhibit high per-
meability for H2S and CO2, with a large selectiv-
ity relative to methane.
In general, nonporous polymeric membranes
are applied in acidic gas removal, taking advan-
tage of the solution-diffusion mechanism and the
high solubility of H2S and CO2, compared to
CH4. Also polymeric membranes almost always
demonstrate selectivity for H2S over CO2, again
because of the higher condensability of H2S com-
pared to CO2, as demonstrated by the difference
in critical temperature. Table 1 provides the H2S
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_817-3
permeability and H2S/CO2 selectivity for a range
of polymeric membranes. The study of porous
membranes for acidic gas removal is limited,
even though both H2S and CO2 have smaller
kinetic diameters than CH4. In the natural gas
sweetening industry, both cellulose acetate- and
polyimide-based membranes have been
commercialized.
Prolonged exposure to both H2S and CO2 can
lead to plasticization and degradation of the poly-
meric membrane over time. This is because the
acidic nature of the gases means they will readily
interact with the polymeric chains, disrupting
chain packing and lubricating polymer chain
motion, resulting in more rubbery behavior.
Membrane degradation by these gases is greatly
enhanced if water is present, because of the weak
acidic dissociation of these gases (Scholes
et al. 2009).
For inorganic and metallic membranes, H2S is
of particular concern, because of the effect sulfur
can have on the membrane material
(Lu et al. 2007). A good example of this is in H2
separation with Pd-based membranes. The pres-
ence of H2S leads to membrane brittlement and
performance degradation because of lattice
expansion on the formation of Pd-S. Hence, in
applications such as gasification, it is necessary
for the gas to have H2S removed prior to the gas
separation membrane, use sacrificial layers, or
add sulfur-resistant materials.
2 Acid Gas: Effect on Membrane Properties

Acid Gas: Effect on Membrane Properties, Table 1 H2S permeabilities (barrier) and H2S/CO2 selectivity in a range
of polymeric membranes
H2S permeability H2S/CO2
Ethyl cellulose 320 3.8
Nylon 0.34 3.86
PDMS 5,100 1.6
Polyethylene 36 2.84
PTMSP 21,400 1.2

References review and perspective. J Colloid Interface Sci

Baker R (2001) Future directions of membrane
gas-separation technology. Membr Technol 138:5–10
Lu GQ, da Costa D, Duke JC, Giessler M, Socolow R,
Williams RH, Kreutz TG (2007) Inorganic membranes
for hydrogen production and purification: a critical
314:589–603
Scholes CA, Kentish SE, Stevens GW (2009) Effect of
minor components in carbon dioxide capture using
polymeric gas separation membranes. Sep Purif Rev
38:1–44
C
Carbon Capture and Storage (CCS)
Colin A. Scholes
Department of Chemical & Biomolecular
Engineering, The University of Melbourne, VIC,
Parkville, Australia
Carbon capture and storage (CCS) is a proposed
strategy to separate carbon dioxide from indus-
trial gases and store that carbon on a geological
timescale. This is a response to the perceived
threat industrial carbon dioxide emissions have
in producing anthropogenic climate change
(IPCC 2007). CCS is divided into three distinct
stages, the capture of the carbon dioxide from the
emission source, the compression and transporta-
tion of CO2 to the storage site, and the final
storage of CO2 for long periods of time (IPCC
2005).
The capturing of CO2 is predominately asso-
ciated with large stationary point sources and in
particular coal-fired power stations. The strate-
gies to capture carbon emissions from these
sources can be classified into three distinct
approaches: post-combustion capture, oxy-fuel
combustion, and precombustion capture
(Table 1).
Post-combustion capture is the separation of
CO2 from flue gases after the combustion pro-
cess. This is primarily a separation of CO2 from
N2, as well as water and other minor components,
such as CO, SOx, and NOx. The separation
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_819-4
process occurs at lower pressures, low CO2 par-
tial pressures, and often around ambient temper-
ature. Oxy-fuel combustion is pure oxygen firing
of the combustion process. This excludes N2 from
the combustion zone and produces a flue gas
consisting of CO2 and H2O. Carbon capture is
achieved through water removal. However, the
very high flame temperature often dictates flue
gas recycling, and critically this strategy requires
the separation of high purity O2 from air, which is
commonly achieved through cryogenic methods.
Precombustion capture is the gasification of the
carbon-based fuel into synthetic gas, also called
syngas, consisting of CO and H2. This syngas is
an important industrial feed gas that is used in a
wide range of processes, such as Fischer-Tropsch
synthesis. For power generation, H2 production is
often maximized through the water gas shift reac-
tion, resulting in high-pressure gas mixtures of
CO2, CO, and H2. Separation of CO2 is achieved
before H2 undergoes combustion. This separation
strategy takes advantage of the high pressure and
CO2 partial pressure before combustion.
Carbon capture has also been applied to other
industrial applications, such as natural gas sweet-
ening, for the removal of acidic gases to meet
pipeline specifications, as well as in natural gas
reforming for ammonia production.
A range of separation technologies have been
applied to carbon capture, including solvent sep-
aration, membrane gas separation, adsorption
technology, cryogenic separation, and mineral
carbonation. The current commercial technology
2 Carbon Capture and Storage (CCS)

Carbon Capture and Storage (CCS), Table 1 Carbon capture strategy conditions and gas compositions
Post-combustion Oxy-fuel combustion Precombustion
Pressure (bar) 1 1 30
Composition (mol. frac.)
CO2 0.11 0.87 0.40
N2 0.62 – –
H2 – – 0.55
O2 0.04 0.05 –
H2O 0.23 0.08 0.02
CO – – 0.03

of choice is physical and chemical solvent tech-
nology, with membrane gas separation having
been commercial proven in natural gas
sweetening.
Transportation of captured CO2 to the storage
site is undertaken through shipping (low temper-
ature and low pressure) or pipelines (high pres-
sure and ambient temperature). The method of
transportation is dependent on distance and geog-
raphy between the source and storage sites.
Storage of carbon for extended periods of time
can be achieved through geosequestration, deep
ocean storage, or mineralization.
Geosequestration is the injection of supercritical
CO2 into geological formations, generally sedi-
mentary basin, over a kilometer underground.
Importantly, the geological formation must con-
tain a suitable reservoir rock, with high perme-
ability and porosity for CO2, as well as a seal rock
above the reservoir that forms the necessary geo-
logical trap. Possible geological sites for CO2
geosequestration include disused oil and gas
fields, saline aquifers, as well as deep coal
seams. Currently, CO2 is geosequestrated com-
mercially as part of enhanced oil recovery
procedures.
References
IPCC (2005) IPCC special report on carbon dioxide
capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
Cambridge University Press, Cambridge, UK
IPCC (2007) IPCC the physical science bases. Contribu-
tion of working group 1 to the fourth assessment report
of the Intergovernmental Panel on Climate Change.
Cambridge University Press, Cambridge, UK
D
Durability of Membrane (Lifetime of
Membrane)
Colin A. Scholes
Department of Chemical & Biomolecular
Engineering, University of Melbourne, Victoria,
Parkville, Australia
Durability (or lifetime) of membranes is a critical
factor in the commercialization potential of any
membrane material, as it must be resilient to the
process conditions over an extended period of
time. The lifetime of a membrane is also an
important factor in the economic evaluation of a
membrane process, as replacement of mem-
branes is a significant cost burden.
A range of factors influence the durability of
membrane materials. These include chemical
degradation of either the active layer or support
structure due to harsh chemical components in
the feed stream, for example, feeds with low or
high pH conditions, as well as high electrolyte
concentrations, polymeric aging, and polymer
plasticization, leading to increased probability
of the active layer rupturing. An example of this
is cellulose acetate membranes being plasticized
by exposure to hydrocarbons in petrochemical
gas separation applications; active layer compac-
tion due to the extended exposure to high-
pressure differentials across the membrane,
resulting in reduced flux because of loss in diffu-
sivity; and membrane fouling, which is the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_820-4
buildup of foreign matter on a membrane’s sur-
face resulting in decreased performance. An
example is microbial growth in water treatment.
Finally, mechanical abrasion of the active and
support layers is caused by particulate matter
being present in system. Each of these factors
influences membrane materials differently,
depending on the application.
There are a number of approaches to extend
membrane lifetimes, most of which focused on
overcoming membrane fouling. These include
feed pretreatment, chemical and mechanical
cleaning, feed stream pulsation, and pressure var-
iation, as well as chemical additives to prevent
fouling in the first place. These techniques can
extend a membrane module’s lifetime but will
not address issues such as chemical degradation,
polymeric aging, and mechanical abrasion.
Hence, all membrane modules’ separation per-
formances decrease over time in all industrial
processes and replacement is necessary.
Currently, the industry standard is for a mem-
brane module lifetime of 5 years under standard
process conditions (Li et al. 2008). For the major-
ity of reverse osmosis membrane plants currently
being commissioned or under construction, the
RO membranes are guaranteed by the manufac-
turer for 5 years. Similarly, vapor separation
membranes in the petrochemical industry have a
lifetime of 3–5 years, dependent on the condi-
tions of the feed. Seawater ultrafiltration mem-
branes last up to 7 years because of their resilient
material and the ability to avoid regular chemical
2 Durability of Membrane (Lifetime of Membrane)

cleans. Alternatively, dairy and brine processing Reference

membranes need to be replaced every year
because of biological and particulate buildup, Li NN, Fane AG, Ho WSW, Matsuura T (2008) Advanced
membrane technology and applications. Wiley,
while hemodialysis and hemofiltration mem-
Hoboken
branes are only required to function for a few
hours, as they are single-use only equipment.
N
NOx Effect on Membrane Properties
Colin A. Scholes
Department of Chemical & Biomolecular
Engineering, University of Melbourne, Parkville,
VIC, Australia
Combustion of fossil fuels at high temperature
in air results in the generation of nitrogen
oxides, commonly and collectively referred to
as NOx. This mixture is dominated by NO and
to a lesser extent NO2, but can also consist of
higher nitrogen oxides, such as N2O4, but only
rarely includes N2O. The generation of NOx is
the result of partial oxidation of N2 in combus-
tion, as well as nitrogen associated with the
fuel. Dependent on the fuel type and combus-
tion temperature, NOx can exist in the flue gas
on the order of 10–500 ppm. Their emission is
heavily regulated and must be reduced to
2–5 ppm before flue gas can be vented to the
atmosphere. This has implications in flue gas
desulfurization and CO2 postcombustion cap-
ture from flue gas.
The effect of NOx on membranes is a sparsely
studied area, with the permeability, selectivity,
and effects of NO and NO2 on polymeric mem-
branes relatively unknown. Information on per-
formance must be extrapolated from known
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_821-2
properties, such as kinetic diameter and
solubility.
NO has a smaller kinetic diameter than most
gases found in flue gas, such as N2, O2, and CO2.
Hence, molecular sieve-based membranes will show
selectivity for NO relative to these gases.
Conversely, NO2 has a larger kinetic diameter than
other gases present in flue gas and will be retained in
the retentate. For nonporous membranes where
solubility is an important factor, it is expected that
membranes show selectivity for NO2 compared to
NO, given the difference in critical temperature.
For CO2-selective membranes for carbon cap-
ture from flue gas, nonporous polymeric mem-
branes will display CO2/NO selectivity because
of strong CO2 solubility. This has been observed
for the glassy polymeric membranes of
polysulfone, and the polyimides Matrimid 5218
and 6FDA-TMPDA (Table 1; Scholes
et al. 2009). Conversely, NO2 will have a greater
permeability than CO2 in nonporous membranes
because of strong NO2 solubility, and this has
been reported for poly tetrafluoroethylene
(PTFE), with a permeability of 15.9 barrer and a
NO2/CO2 selectivity of 1.6 (Pasternak et al. 1970).
The plasticization and aging effects of NOx on
membranes has not been reported in the literature
to date. In the presence of water, NOx readily
forms nitric acid, and this will degrade membrane
materials over time. Hence, in the humid envi-
ronment of flue gas it is expected that NOx will
2 NOx Effect on Membrane Properties

NOx Effect on Membrane Properties, Table 1 NO permeability (barrer) through glassy polymeric membranes
Polysulfone Matrimid 5218 6FDA-TMPDA
NO permeability (barrer) 3.1  0.6 3.7  0.6 168  16

have similar degradation performance on mem- and nitrogen dioxide through polytetrafluoroethylene.
branes as those observed for SOx. Macromolecules 3:366–371
Scholes CA, Kentish SE, Stevens GW (2009) Effect of
minor components in carbon dioxide capture using
polymeric gas separation membranes. Sep Purif Rev
References 38:1–44

Pasternak RA, Christenson MV, Heller J (1970) Diffusion

and permeation of oxygen, nitrogen, carbon dioxide
S
SOx, Effect on Membrane Properties
Colin A. Scholes
Department of Chemical & Biomolecular
Engineering, The University of Melbourne,
Parkville, VIC, Australia
The combustion of sulfur-containing fuels, such
as coal, results in the production of SO2 and SO3,
commonly collectively referred to as SOx. The
typical coal-fired power station flue gas has SOx
concentrations between 1000 and 5000 ppm in
their untreated flue gas, dependent on the sulfur
content of the coal, of which the main component
is SO2. The contribution of SOx to acid rain has
meant that their emissions have been heavily
regulated for over 30 years. The similar chemical
properties between SOx (in particular SO2) and
CO2 also correlate into the behavior of SOx in
membrane separation processes.
The high molecular weight of SO2 and SO3
relative to other components of flue gas means
that for Knudsen diffusion-based membranes, the
SOx components will remain in the retentate.
Similarly, the large kinetic diameters of SO2
and SO3, both greater than CO2, means for
molecular sieve based membranes the SOx com-
ponents of flue gas will leave the membrane
module mainly in the retentate stream (Scholes
et al. 2009). However, SO3 and to a less extent
SO2 are strongly condensable gases, much
greater than CO2. Hence, for surface diffusion
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_822-3
and capillary condensation separation, it may be
possible for porous membranes to be selective
for SOx.
Solution diffusion-based nonporous mem-
branes have been studied for SOx separation,
because of membrane research in the 1970s on
desulfurization of flue gas. A list of polymeric
membrane SO2 permeabilities are provided in
Table 1, along with SO2/CO2 selectivity. The
majority of polymeric membranes show SO2
selectivity, because of the stronger
condensability of SO2 (Felder et al. 1975). The
relationship between SO2 permeability and SO2/
CO2 selectivity follows a typical Robeson upper
bound plot. To date no permeability data has been
reported for SO3 through a nonporous membrane.
This is probably because pure SO3 is a liquid at
room temperature and experimentally difficult to
handle. However, given the strong condensable
state of SO3 compared to SO2 and CO2, it is
reasonable that SO3 will experience a greater
permeation through glassy polymeric membranes
than either SO2 or CO2.
SO2 is a known plasticizer of polymeric mem-
branes, producing a more rubbery material and
increasing the diffusivity of penetrants. Its plas-
ticizing effect is believed to be stronger than CO2,
though this has only been confirmed for
polyvinylidene (Zavaleta and McCandless
1976). In many industrial processes where SOx
is present, there exist high levels of water vapor.
This allows for the generation of sulfuric acid,
which results in membrane degradation. For
2 SOx, Effect on Membrane Properties

SOx, Effect on Membrane Properties, Table 1 SO2 permeabilities (barrer) and SO2/CO2 selectivity in a range of
polymeric membranes
SO2 permeability SO2/CO2
Cellulose triacetate 270 48
Polyacrylate 1,700 41
Polyethylene glycol 4,100 44
Polyamide-6-b-ethylene oxide 1,000 7.6
Polytetrafluoroethylene-co-ethylene 2.6 1.32

example, cellophane-based membranes experi- References

ence a 30-fold increase in SO2 permeability
when water is present, associated with increased
free volume within the membrane because of
acidic degradation (Hanousek and Herynk
1962). The fact SO3 is a liquid at ambient tem-
perature means it is very likely to have the same
plasticization and degradation effect on poly-
meric membranes as SO2.
minx f ðxÞ
s:t: hðxÞ ¼ 0
gð x Þ  0
Felder RM, Spence RD, Ferrell JK (1975) Permeation of
sulfur dioxide through polymers. J Chem Eng Data
20:235–242
Hanousek J, Herynk L (1962) Determination of perme-
ability of foils to sulfur dioxide. Chem Listy
56:376–382
Scholes CA, Kentish SE, Stevens GW (2009) Effect of
minor components in carbon dioxide capture using
polymeric gas separation membranes. Sep Purif Rev
38:1–44
Zavaleta R, McCandless FP (1976) Selective permeation
through modified polyvinylidene fluoride membranes.
J Membr Sci 1:333–353
M
Membrane Crystallization (MCr)
Efrem Curcio
Department of Environmental and Chemical
Engineeering, University of Calabria, Rende
(CS), Italy
Membrane operation is aimed at promoting the
formation of crystals from supersaturated solu-
tions. The concept of membrane crystallization
combines the principles of mass and heat trans-
port through membranes with the theory of het-
erogeneous nucleation occurring at the interface
with polymeric films (Drioli et al. 2005).
Crystallization from solution is driven by
supersaturation S, defined as the ratio between
the actual solute concentration c and the equilib-
rium value c* (saturation):
c
S¼ 
c and Dm the chemical potential gradient between
The selective removal of solvent through appro-
priate membranes is used to increase the concen-
tration of the solute up to the required
supersaturation. Alternatively, membranes are
used to selectively feed an antisolvent to induce
a demixing effect that generates supersaturation.
Mass transport depends on the specific typol-
ogy of employed membranes: for microporous
hydrophobic membranes (mass transfer in vapor
phase under temperature and/or concentration
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_826-1
gradient) Dusty Gas Model is applied; for thin
film composite membranes (mass transfer in liq-
uid phase under pressure or concentration gradi-
ent), Solution-Diffusion Model is employed.
Morphological and physicochemical parame-
ters of the membranes, such as porosity, rough-
ness, or hydrophilic/hydrophobic character,
affect significantly the nucleation kinetics. In
fact, the formation of a critical nucleus (having
50 % probability to growth or dissolve) is an
activate process that imposes the necessity to
overcome a Gibbs energy barrier DG* that, for
homogeneous nucleation occurring in the bulk of
the solution, is given (according to the Classical
Nucleation Theory (Drioli et al. 2015)) by:


16 3 O 2
DGhomogeneous ¼ pgL (2a)
3 Dm
where gL is the surface tension of the nucleus-
(1) liquid interface, O the molar volume of the solute,
the crystalline phase and the mother solution. The
corresponding critical nucleus R* is given by:
2gL O
Rhomogeneous ¼ (2b)
Dm
Membrane surfaces act as a promoter of crystal-
lization by lowering the activation barrier to the
nucleation stage, thus allowing molecules to
aggregate in conditions of supersaturation that
would not be adequate for the spontaneous
2 Membrane Crystallization (MCr)

Membrane Crystallization (MCr), Table 1 Critical nucleus (R*) and Gibbs free energy ratio between heterogeneous
and homogeneous nucleation (DGheterogeneus/DGhomogeneous) as a function of physicochemical parameters of the
membrane
Parameter R* DGheterogeneus/DGhomogeneous
2gL O
1 3 
2  4 cos y þ 4 cos y
Contact angle (y), ideal surface 1 3
Dm
h 2
i h i3
Porosity (e) 2OgL
1  e ðð1þ cos yÞ 2 ð1þ cos yÞ2
4 ð2 þ cos yÞ ð1  cos yÞ 1  e ð1 cos yÞ2
1
Dm 1 cos yÞ2

4 Y ð cos y  3 cos y þ 2Þ
Wenzel roughness (r) 2OgL 1 3 3
Dm Y
r cos y ð1þ cos yÞ2
Y¼ cos y ð1þ cos yÞ2

nucleation; therefore, the rate of generation of crystallization was confirmed by experimental

nuclei is increased. In order to evaluate quantita-
tively this effect, a constitutive relation
expressing the mechanical equilibrium between
nucleus-solution (gL), nucleus-membrane (gi),
and solution-membrane (gs) interfaces is
required. For an ideally solid and smooth surface,
Young equation gives:
ðgS  gi Þ ¼ gL cos y
The introduction of (Eq. 3) into the energy
balance of the crystalline phase allows evaluating
the reduction of DG* for nuclei formed on a flat
sheet membrane. The values of DGheterogeneus/
DGhomogeneous for this case, as well as for porous
or rough membranes, are reported in Table 1.
Figure 1 shows that, if nucleation occurs on
polymeric membrane with y < 180 , the work
required to generate a critical nucleus on the
tests carried out on: glycine (selective crystalli-
zation of forms a and g), paracetamol (possibility
to discriminate between the monocline stable
form of polymorph I and the orthorhombic meta-
stable form of polymorph II), L-glutamic acid
(selective crystallization of forms a and b), and
L-histidine (selective crystallization of forms
A and B) (Drioli et al. 2012).
(3) When investigating nucleation kinetics, an
important parameter is the induction time,
defined as the time elapsed from the attainment
of a given supersaturation up to the formation of
critical nuclei. As a general rule, a higher
4 θ=180° (homogeneous)
θ=110°

surface is higher with respect to nucleation in θ=90°

2
the bulk of the mother solution (y = 180 ). This
ΔG (kJ/mol)

phenomenon is known as heterogeneous

nucleation.
The possibility to modulate the nucleation rate 0
as a function of morphological and physicochem-
ical properties of the membranes allows to redi-
rect the selective formation of stable or −2
metastable polymorphs. Although identical in R*
their chemical composition, different poly- 0 0.2 0.4 0.6 0.8 1
morphs often exhibit important differences in Nucleus radius (nm)
solubility, dissolution rate, stability, melting
point, density, and many other properties that Membrane Crystallization (MCr), Fig. 1 Gibbs free
significantly affect the efficacy, bioavailability, energy versus nucleus radius at three different contact
angles (y = 90 , 110 , 180 ). Curves reach a maximum
and safety of active pharmaceutical ingredients. in correspondence of the critical radius R*. Input data:
Polymorph selection by membrane c/c* = 1.5; O = 1.91028 m3; gL = 0.004 J/m2
Membrane Crystallization (MCr)
nucleation rate (lower DG*) results in a shorter
induction time. This is particularly evident in the
crystallization of proteins: macromolecules dis-
play a rather asymmetric and weak bonding con-
figuration at their surfaces and tend to aggregate
in n-mers that diversify the shape and size of
lattice units, thus making ordered attachment for
growing units less probable.
Experiments carried out on various hydro-
soluble proteins (such as lysozyme, trypsin,
b-glucosydase) showed the possibility to obtain
a crystalline product in shorted times with respect
to those measured when using conventional
vapor diffusion techniques under the same super-
saturation level (Curcio et al. 2010). Moreover,
X-ray diffraction analysis by synchrotron radia-
tion confirmed a high structural order of crystals
grown on microporous membranes (i.e., polypro-
pylene). Crystallization experiments on metals-
proteins have also resulted in a new orthorhombic
form P21212 of the complex Lysozyme-Co2+.
In order to understand the effect of the chem-
istry of surface on the heterogeneous nucleation,
Curcio et al. (2014) investigated the mechanisms
of acetaminophen (ACM) crystal formation due
to specific solute-surface interactions on
polydimethylsiloxane (PDMS) with siloxane
functional groups Si  O  Si forming the back-
bone of silicones, partially fluorinated elastomer
polyvinylidenedifluoride (PVDF), polystyrene
(PS) having weak electron-donor phenyl rings,
3
poly(n-buthyl methacrylate) (P pu BMA) show-
ing ester functionality, polyimide (PI) that
includes both hydrogen-bond acceptor imide
functionality and carbonyl groups, ethylene/
acrylic acid (EAA) copolymer with only the car-
boxyl moiety. Power X-ray Diffraction analysis
showed the occurrence of preferred orientation
(PO) depending on the strength of the
intermolecular interactions occurring at the
polymer-crystal interface during nucleation:
from nonspecific adsorption (PDMS, PnBMA,
and PS) to oriented arrangement of molecules in
the crystalline lattice (EAA, PI, and PVDF)
(Curcio et al. 2014).
References
Curcio E, Curcio V, Di Profio G, Fontananova E, Drioli
E (2010) Energetics of protein nucleation on rough
polymeric surfaces. J Phys Chem B 114:13650–13655
Curcio E, López-Mejı́as V, Di Profio G, Fontananova E,
Drioli E, Trout BL, Myerson AS (2014) Regulating
nucleation kinetics through molecular interactions at
the polymer–solute interface. Cryst Growth Des
14(2):678–686
Drioli E, Criscuoli A, Curcio E (2005) Membrane
contactors. Fundamentals, potentialities and applica-
tions. Elsevier, Amsterdam
Drioli E, Di Profio G, Curcio E (2012) Progress in mem-
brane crystallization. Curr Opin Chem Eng
1(2):178–182
Drioli E, Di Profio G, Curcio E (2015) Membrane-assisted
crystallization. Imperial College Press, London
A
Antisolvent Membrane
Crystallization
Gianluca Di Profio
Institute on Membrane Technology (ITM),
National Research Council of Italy (CNR),
Rende (CS), Italy
This is an extension of the solvent evaporation
membrane crystallization concept, where a
porous membrane is used to dose the amount of
antisolvent in the crystallizing solution, which
has been proposed very recently (Di Profio
et al. 2009). In this system, two operative config-
urations have been developed: solvent/
antisolvent demixing and antisolvent addition
membrane crystallization. In both cases, sol-
vent/antisolvent migration occurs in vapor
phase, according with the general concept of
membrane crystallization and not by forcing it
in liquid phase through the membrane. The selec-
tive and precise dosing of the antisolvent, con-
trolled by the porous membrane, allows a more
fine control of the crystallizing solution compo-
sition during the process and at the nucleation
point, with consequent advantages for the final
crystal characteristics.
In solvent/antisolvent demixing configuration,
a certain solute is dissolved in an appropriate mix
of a solvent and an antisolvent whose
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_834-1
composition is chosen in such a way that the
solute remains indefinitely in the solution in the
original conditions. When a gradient of chemical
potential is generated between the two sides of
the membranes, e.g., by a temperature difference,
the solvent, which is supposed to have a higher
vapor pressure than the antisolvent at the same
temperature, evaporates at higher flow rate thus
producing solvent/antisolvent demixing. As the
amount of solvent in the mixture decreases, the
lower solubility of the solute generates supersat-
uration and a phase separation occurs when the
antisolvent exceeds a certain volume fraction.
The requirements for this configuration are that:
(i) the antisolvent and the solvent are miscible;
(ii) the initial solvent/antisolvent balance in the
mixture guarantees that the solute is under its
solubility limit; and (iii) the solvent evaporates
at higher velocity than the antisolvent. Crystalli-
zation of a solute from an aqueous/organic
extraction mixture can be successfully carried
out by this system.
In antisolvent addition configuration, a sol-
ute is dissolved in a solvent and then an
antisolvent is gradually evaporated from the
other side of the membrane by applying a gra-
dient of chemical potential. As the antisolvent
mixes with the solvent the solute dilutes but, at
the same time, the composition of the mixture
changes. At a certain point, the excess of
antisolvent creates supersaturation and solute
2 Antisolvent Membrane Crystallization

crystallization. This configuration requires that References

the antisolvent and the solvent are miscible. In
this case, the compound to be crystallized can Di Profio G, Stabile C, Caridi A, Curcio E, Drioli E (2009)
Antisolvent membrane crystallization of pharmaceuti-
be soluble in aqueous solutions and poorly sol-
cal compounds. J Pharm Sci 98:4902
uble in organic low boiling liquids.
S
Solvent Evaporation Membrane
Crystallization
Gianluca Di Profio
Institute on Membrane Technology (ITM),
National Research Council of Italy (CNR),
Rende, CS, Italy
Solvent evaporation membrane crystallization is
a membrane-assisted crystallization configura-
tion where the substances to be crystallized are
dissolved in an undersaturated solution located at
the feed side of the membrane. In the current
general conception, a nonvolatile solute that is
likely to be crystallized (defined as the crystalliz-
ing solution or feed or retentate) is contacted, by
means of a (macro)porous membrane, with a
solution on the distillate side. The membrane
might be made by polymeric or inorganic mate-
rials or by a combination of both in a hybrid or
composite configuration. Hollow fibers as well as
flat sheet membranes can be employed
indifferently.
When the membrane is prevented to be wet
from the adjacent solutions, no mass transfer
through its porous structure is observed directly
in liquid phase but the two contacted subsystems
are subjected to mass inter-exchange in vapor
phase. Wetting of the membrane, with the conse-
quent deleterious direct passage of liquids, can be
avoided when the pressure of the solutions facing
it is lower than the entry limit (Pentry), defined by
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_835-1
Young-Laplace’s equation (Atkins 1998). This
means that hydrophobic membranes can be used
for hydrophilic (aqueous) crystallizing solutions
and hydrophilic membrane materials are suitable
for hydrophobic (or oleophilic) solutions.
For a pressure lower than Pentry, the two liq-
uids are stopped at the entrance of each pore on
both membrane sides, thus generating a curved
profile. Crystal nucleation and growth in the feed
solution are induced by generating supersatura-
tion. This can be done either by removing the
solvent from the crystallizing solution, thus
increasing solute concentration up to the over-
coming of its solubility limit. Accordingly, the
role of the membrane is not simply as a sieving
barrier to select the transport of specific compo-
nents but instead as a physical support which, by
removal of the vaporized solvent or by addition
of the antisolvent, generates and sustains a con-
trolled supersaturated environment in which
crystals can nucleate and grow.
The driving force for the mass transport of a
component from one phase to the other is given
by the difference in its electrochemical potential
in the two phases, and it is generated by changes
in temperature, pressure, activity, or electrical
potential. The hydrostatic pressure gradient
across the membrane is negligible in MCr to
avoid wetting while the electrical gradient does
not hold, so that the driving force of the process is
the partial pressure difference across the mem-
brane, established by a temperature or activity
difference between the two contacted solutions.
2 Solvent Evaporation Membrane Crystallization
In the case of a driving force generated by a
temperature gradient, the system is named ther-
mal membrane crystallizer; when the driving
force is obtained by an activity gradient, gener-
ated by a difference in ionic strength, the system
is named osmotic (or isothermal) membrane
crystallizer.
Under the action of the driving force, solvent
molecules migrate, in vapor phase through the
porous membrane structure, from the site where
their chemical potential is higher toward the
lower chemical potential subsystem, thus gener-
ating supersaturation and, hence, nucleation and
crystal growth in the crystallizing solution. The
specific mechanism for mass transport depends
on the operational configuration of the membrane
crystallizer. Two cases exist: (1) solvent evapo-
ration membrane crystallizer (thermal or isother-
mal) in which solvent is removed in vapor phase
from the crystallizing solution and (2) antisolvent
membrane crystallizer where an antisolvent is
dosed inside the crystallizing solution by means
of the membrane. Static (quiescent) and dynamic
process can be performed. In the first case, the
feed and the distillate solutions are quiescent,
while in the second case, those two solutions are
circulated in forced solution flow environment,
generally in a condition of laminar flow.
Generally, in order to avoid wetting, hydro-
phobic membrane materials are preferred for
aqueous feed solutions, while hydrophilic mem-
branes can be used for oleophilic solutions. In the
most common arrangement, the distillate side of
the membrane consists in a condensing fluid,
often the pure solvent, at a lower temperature
than the feed side in the case of thermal activation
of the driving force, or in a stripping solution
consisting in a hypertonic solution of inert salts
(NaCl, MgCl2, CaCl2, etc.) in the case of the
isothermal configuration.
While for the crystallization of inorganic sub-
stances or low molecular weight organic com-
pounds, the thermal system can be affectively
used, for the crystallization of heat-sensitive mol-
ecules, like proteins, the osmotic configuration
appears more appropriate tank to its milder oper-
ating conditions (Curcio et al. 2001).
References
Atkins PW (1998) Physical chemistry, 6th edn. Oxford
University Pres, Oxford
Curcio E, Criscuoli A, Drioli E (2001) Ind Eng Chem Res
40:2679–2684
P
Protein Crystallization by Membrane molecular surface. Hydrophobic and hydrophilic
Crystallization spots, positively and negatively charged func-
Gianluca Di Profio
Institute on Membrane Technology (ITM),
National Research Council of Italy (CNR),
Rende (CS), Italy
In a membrane crystallizer, the crystallizing solu-
tion is in direct contact with the membrane sur-
face; therefore a solute–membrane interaction
will occur in certain circumstances. In this tech-
nology, the membrane provides, in the same time,
the physical support for mass inter-exchange in
vapor phase thus generating supersaturation and
the solid support to promote heterogeneous
nucleation mechanism. This effect can be due to
both the structural and chemical properties of the
membrane surface: (1) the porous nature of the
surface might supply cavities where solute mole-
cules are physically entrapped leading, locally, to
high supersaturation values suitable for nucle-
ation, and (2) the nonspecific and reversible
chemical interaction between the membrane and
the solute molecules can allow to concentrate and
orient molecules on the surface without loss of
mobility (Kornberg and Darst 1991), thus facili-
tating effective interaction proper for crystalliza-
tion. In the case of complex molecular systems
like proteins, the different interaction mechanism
is dependent on the patches, with different chem-
ical properties, which are available on the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_836-1
tional groups, and hydrogen-bonding moieties
are known to provide affinity for almost any
kind of non-biological surface. Structural
rearrangements of adsorbed molecules develop
with solute–surface residence time and are con-
sidered as one of the driving forces of adsorption
which contributes significantly to nucleation free
energy changes (Horbett 1992). Furthermore, the
solute–membrane interaction can provide spe-
cific solute–solute interaction pathways which
would lead to the formation of specific crystal
structures (Simone et al. 2006). When inducing
heterogeneous nucleation, generally both the
induction time and solute concentration neces-
sary for the nucleation decrease, whereas the
nucleation density increases on going from a
prevalently homogeneous to a prevalently hetero-
geneous nucleation contribution.
From the classical nucleation approach, the
energetic of nucleation concerns mainly the
work to create a surface. If there is already a
solid substrate in the system, this will decrease
the work required to create critical nuclei and will
increase locally the probability of nucleation with
respect to other locations in the system. The total
change in surface free energy will be lowered by
favorable interactions between the aggregate and
the substrate and unfavorable interactions
between the crystallization medium and the sub-
strate, due to the negative value of the second
term in the equation above. Consequently,
2 Protein Crystallization by Membrane Crystallization
nucleation will be enhanced by increasing the
surface area of the substrate. The nucleation
work depends on two main parameters: the exter-
nally controlled supersaturation ratio and the
material surface/solution composition-dependent
interfacial energy. Molecules dispersed in solu-
tion are first adsorbed on the surface by means of
nonspecific attractive interactions. The irregular
structure may physically block the lateral migra-
tion of the adsorbed protein molecules into the
concaves, so that they are forced to be packed
into compact aggregates. The trapping of mole-
cules on the surface may result in a relatively
higher local supersaturation, which would
increase the possibility of nucleation compared
with that on an ideally flat surface. Here, nucle-
ation will follow with the formation of critical
clusters comprising molecules forming suitable
bond angles with their neighbors, while the mol-
ecules in a randomly packed compact structure
may form a fractal cluster, which cannot work as
a nucleus for crystal growth. Critical clusters then
grow into crystals while the fractal clusters grow
into larger clusters. This simple mechanism can
be generalized to describe heterogeneous nucle-
ation on irregular substrates such as porous sur-
faces. From a technological point of view, the
control of surface porosity in producing mem-
branes can be easily achieved, so that specific
membrane nucleants, having the desired value
of porosity which might be used to achieve the
desired heterogeneous/homogeneous activation
Gibbs energy ratio, can be produced.
References
Horbett TA (1992) In: Ahern TJ, Manning MC (eds)
Stability of protein pharmaceuticals, part 1. Plenum
Press, New York
Kornberg RD, Darst SA (1991) Curr Opin Struct Biol
1:642–646
Simone S, Curcio E, Di Profio G, Ferraroni M, Drioli EJ
(2006) Memb Sci 283:123–132
M
Membrane Crystallization
in Pharmaceuticals, Application of
Gianluca Di Profio
Institute on Membrane Technology (ITM),
National Research Council of Italy (CNR),
Rende (CS), Italy
Definition
Controlling polymorphism with membrane-
based crystallizers: application to form I and II
of paracetamol. Selective glycine polymorph
crystallization by using microporous membranes.
Effect of supersaturation control and heteroge-
neous nucleation on porous membrane surfaces
in the crystallization of L-glutamic acid
polymorphs.
Many substances can exist in solid crystalline
state as several phases, a phenomenon named
polymorphism. Each polymorph is characterized
by its specific physical properties, like solubility,
dissolution rate, thermal and mechanical stabil-
ity, optical properties, etc. Therefore, each form
represents a specific material, different to some
extent from the other phases of the same sub-
stance, and this has remarkable implications for
its specific utilization in industrial, technological,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_837-2
and scientific applications. Among the different
phases, the relative stability in a specific condi-
tion is ruled by thermodynamics, as described by
the classical nucleation theory (CNT) (Kashchiev
2001). However, the phase that will be effectively
obtained depends on kinetics (Ostwald 1987).
This is because a competition between the ther-
modynamic and kinetic control of the nucleation
phase, in combination with the relative growth
rates of the different polymorphs, will affect the
final outcome of the crystallization process.
In a membrane crystallizer, this kind of con-
trol can be achieved by controlling the composi-
tion of the crystallizing solution through the
management of the transmembrane flux. This
provides an opportunity to systematically affect
the rate of variation of the supersaturation which,
in turn, affects the polymorphic composition of
the precipitate. As this control can be produced
very precisely, by fine-tuning the operating con-
ditions and/or by choosing the opportune mem-
brane properties, selective polymorph
crystallization is an important possibility avail-
able with membrane crystallization technology
(Di Profio et al. 2007a). Namely, during a crys-
tallization process, when the least stable structure
(or a mixture of nuclei of the different poly-
morphs) forms following an Ostwald-like behav-
ior, the relative growth rates of the different
phases with respect to the supersaturation
2 Membrane Crystallization in Pharmaceuticals, Application of
generation rate will fix which form will effec-
tively be grown. When the rate of variation of
supersaturation is low, due to the low evaporation
rates through the membrane, if nuclei of the more
stable structure have time to grow at the expense
of the less stable forms via solvent-mediated
transfer of solute, a “thermodynamic control”
and the more stable polymorph will selectively
(or prevalently) be obtained. However, for higher
evaporation rates, the increase in the metastable
zone width induces nucleation at higher values of
supersaturation. In this situation, the conversion
from the metastable to the stable phase could not
be fast enough with respect to the growth of the
former, so that the growth of the kinetically
favored form (metastable), which might be also
the first to appear according with the Ostwald rule
of stages, is observed. In this case the overall
process is “kinetically controlled” (Di Profio
et al. 2007b). Accordingly, high control of the
membrane-based process provides the possibility
to induce polymorphic selection during crystalli-
zation by switching between a kinetic and a ther-
modynamic control of the nucleation stage thus
allowing the production of either a metastable or
a stable structure (Di Profio et al. 2009).
References
Di Profio G, Tucci S, Curcio E, Drioli E (2007a) Chem
Mater 19:2386–2388
Di Profio G, Tucci S, Curcio E, Drioli E (2007b) Cryst
Growth Des 7:526–530
Di Profio G, Curcio E, Ferraro S, Stabile C, Drioli
E (2009) Cryst Growth Des 9:2179–2186
Kashchiev D (2001) Nucleation, basic theory with appli-
cations. Butterworth, Oxford
Ostwald WZ (1987) Phys Chem 22:289–330
H
Hybrid Modeling of Membrane
Biofilm Reactors
Endre Nagy
Research Institute of Chemical and Process
Engineering, University of Pannonia, Veszprém,
Hungary
The immobilized whole cells in a membrane bio-
reactor are grown within the fibers and/or in the
extracapillary space-forming biofilm. The con-
ventional biofilm is increasingly used for waste-
water purification, oxidation of organic
components, nitrification, etc. as they are envi-
ronmentally friendly and less energy intensive.
Biofilm formation is a complicated dynamical
process governed by various physical and chem-
ical principles and biological protocols. Biofilms
are agglomerations of microorganisms or bacte-
ria whose structure can be homogeneous, in case
of sufficient substrate level, or heterogeneous
when the diffusion is rate limiting, due to the
change of the nutrient concentration in axial
direction (Gavin and Gillian 2012). This
circumstance can alter the value of transport
parameters (diffusion coefficient, convective
velocity) and can even alter the biochemical reac-
tion rate (the consumption rate of nutrient). The
variation of cell density is also true in the biocat-
alyst membrane layer perpendicular to the inlet
surface. Increasing distance from the surface can
mean decreasing nutrient concentration. That is
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_845-2
why the variability of the transport parameters
should also be taken into account. Assuming
simultaneous effect of two substrates, namely,
oxygen and carbon sources, the mass balance
for diffusive flow can be given for a sheet mem-
brane layer with constant parameters, as
d 2 cO 2 1 mmaxO2 cO2 cA
D
¼ 0:
dy 2 Y XO2 K MO2 þ cO2 K MA þ cA
(1)
The quasi-analytical approach of solution of
Eq. 1 is given, e.g., by Nagy (2011). Let us give
here the rate equations for limiting cases with
constant cA concentration in the biofilm. Two
important cases can be distinguished, namely,
when the outlet (at y = d) diffusive flow is zero
(dc/dy = 0, the support membrane layer is
impermeable) and dc/dy 6¼ 0 at y = d (there is
sweep phase on the permeate side of a permeable
membrane). The mass transfer rates are given for
these cases, for first-order reaction by Eqs. 2 and
4 and for zero-order reaction by Eqs. 5 and 7,
respectively. The transfer rate in the presence of
convective flows is given in entry biocatalytic
membrane reactor: mass transport (c = cO2 ,
YXO is yield coefficient):
pffiffiffiffiffiffiffiffi
J¼ k1 D tanh#co (2)
with
2 Hybrid Modeling of Membrane Biofilm Reactors

sffiffiffiffiffiffiffiffiffi
co1 coshð#Y 1 Þ
k1 d2 1 vmax ¼
W¼ ; k1 ¼ co2 coshð#½1
Y 1 Þ
D YXO kMO2
   
pffiffiffiffiffiffiffiffi  #2
cd 
D o
k1 D o J¼ c þ c2
2c1 1
½2Y 1
1 þ #
o o 2
J¼ c
(3) d 1 2
tanh# cosh#
(7)
D 2 o
J¼ # c (4) with
d
 
with #2
co1 1
½2Y 1
1
sffiffiffiffiffiffiffiffiffiffiffiffiffi 2
 
vmax d2 #2
#¼ ¼ c2 1 þ ½2Y 1
1 :
o
(8)
DY XO2 2
 
D o #2 The Y1 inflection point can be determined by
J¼ c
cd
(5)
d 2 Eq. 8 and then the mass transfer rate by Eq. 7 as
well. Detailed solution of Eq. 1 is published by
I. n order to overcome the diffusive mass transport Nagy (2011), recommended explicit expression
limitation of nutrients, especially of the sparingly for the mass transfer rate. The biofilm can involve
soluble oxygen, the substrate might be fed on several substrates with several parallel and/or
both sides of the biofilm applying oxygen perme- consecutive reactions as this is the case of aerobic
able support layer. The sum of the mass transfer wastewater treatment. System of the differential
rates for first- and zero-order reactions can be mass balance equations of the reactants should be
expressed by Eqs. 6 and 7, respectively. The solved in order to get their concentration distri-
substrate concentrations of the two sides of the butions and the mass transfer rates of the trans-
biofilm layer are co1 and co2. The substrate concen- ferring substrates.
tration curve has inflection point at Y = Y1 (Y =
y/d):
pffiffiffiffiffiffiffiffi   References
k1 D 1
J¼ 1
co
tanh# cosh2 ð#Y 1 Þ 1 Gavin L, Gillian DL (2012) Microbial biofilms: current
   research and application. Caister Academic Press,
1 Christchurch
þ 1
co (6) Nagy E (2011) Basic equations of the mass transport
cosh2 ð#½1
Y 1 Þ 2
through a membrane layer. Elsevier, Amsterdam

with
B

Biocatalytic Membrane Reactor, thickness, lumen radius, matrix structure, etc.)

Mass Transport in can considerably influence the performance of a
bioreactor, the effectiveness of the reaction. The
Endre Nagy limited transport of nutrients can cause serious
Research Institute of Chemical and Process damage in production. The introduction of con-
Engineering, University of Pannonia, Veszprem, vective transport is crucial in overcoming diffu-
Hungary sive mass transport limitation of nutrients
especially of the sparingly soluble oxygen. The
starting balance equations developed by Navier
Synonyms and Stokes (Bird et al. 1960; Seidel-Morgenstern
2010; Nagy 2011) can be essentially simplified,
Modelling of biocatalytic membrane reactor and the momentum and the mass transport
expressions can often separately be solved in the
For creating a biocatalytic membrane layer, the
case of biocatalytic processes. The principle of
biological catalyst such as whole cells (bacteria,
the mass transport of substrates/nutrients into the
yeast, mammalian and plant cells) is inoculated
immobilized enzyme/cells, through a solid,
into the porous membrane layer where they are
porous layer (membrane, biofilm) or through a
grown, or bioactive molecules such as enzymes
gel layer of enzyme/cells, is the same. The struc-
are immobilized within the membrane matrix or
ture and the thickness of this mass transport layer
in a thin layer on the membrane interface of the
can be very different; thus, the mass transport
membrane layer. A medium is flowing through
parameters, namely, diffusion coefficient, D;
the biocatalytic, mostly asymmetric, plain, or
convective velocity, u; the bioreaction rate con-
cylindrical (hollow fiber) layer, supplying the
stant; their dependency on the concentration;
cells with oxygen and nutrients or the enzyme
and/or space coordinate are characteristics of
with reactant(s) while the wastes and desired
the porous layer and the nature of the
products are removed (Drioli and Giorno 1999).
biocatalysts. Some assumptions made for expres-
The performance of a hollow fiber or sheet bio-
sion of the differential mass balance equation to
reactor is primarily determined by the momen-
the biocatalytic membrane layer are as follows:
tum and mass transport rate (Bird et al. 1960) of
reaction occurs at every position within the bio-
the key nutrients through the biocatalytic mem-
catalyst layer; mass transport through the biocat-
brane layer. Thus, the operating conditions
alyst layer occurs by diffusion and convection;
(transmembrane pressure, feed velocity) and the
mass transport parameters (diffusion coefficient,
physical properties of membrane (porosity, wall
convective velocity, bioreaction rate constant)
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_846-6
2 Biocatalytic Membrane Reactor, Mass Transport in

Biocatalytic Membrane Reactor, Mass Transport in, Table 1 Expressions of the important biocatalytic reactions
Substrate inhibition: Q ¼ KMi þcþc
rmax c
2 =K
c

Substrate inhibition and competitive product inhibition: Q¼K rmax c

Mi ð1þp=Kp Þþcþc2 =Kc
Competitive product inhibition: Q¼K rmax c
Mi ð1þp=Kp Þþc
Noncompetitive product inhibition: Q ¼ ðK rmax c
Mi þcÞ ð1þp=Kp Þ


are constant; and the process is steady state. Thus, Y
J ¼ b c0
cd
the mass balance equation can be given for a plain ePe=2 ½ðPe=2ÞsinhY þ YcoshY
membrane layer as follows, applying, e.g., the (3)
Michaelis-Menten (MM) kinetics (c denotes the
concentration): with (c = cd at y = d and c = c at y = 0;
Pe =nd/D)
d2 c dc vmax c
D
u
¼0 (1)
dy2 dy K M þ c D ð½Pe=2tanhY þ YÞ
b¼
d tanhY
The source term can be different in biocatalytic
reactions; the most often applied equations are The mass transfer rates are given by Eqs. 4 and 5
listed in Table 1. The inhibited reaction can take for cases A and B, respectively, for zero-order
place in both the enzymatic and microbial reaction as limiting case of MM kinetics (k0
reactions. denotes the reaction rate constant):
Two important cases can be discussed, namely,


when the outlet (at y = d) diffusive flow is zero D 0 W2 1
(dc/dy = 0, no sweep phase on the permeate side, J ¼ c Pe
1
Pe (4)
d Pe e
case A) and dc/dy 6¼ 0 at y = d (there is sweep
phase on the permeate side, case B). The mass and
transfer rates are given by Eqs. 2 and 3 for cases
A and B, respectively, for first-order reaction as D Pe
limiting case of MM kinetics (Nagy 2011): J¼
d 2
 

2  ePe=2 e
Pe
Pe  ð 1
TÞ c

0
cd (5)

 þ Y tanhY þ PeY
2 sinhðPe=2Þ 1
T
D 4
J¼
 c0 (2)
d Pe with
tanhY þ Y
2
sffiffiffiffiffiffiffiffiffi
W2   k0 d2
with T ¼ 2 e
Pe ½1 þ Pe
1 ; W ¼
Pe Dc0
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffi
Pe2 k1 d2 The flow through this membrane is proportional
Y¼ þ W2 ; W ¼
4 D to the transmembrane pressure drop and inversely
proportional to the fluid viscosity (Darcy law,
Eq. 6) (k is the permeability and m is the fluid
viscosity):
Biocatalytic Membrane Reactor, Mass Transport in 3

k dpM k ro pt ðzÞ
pe ðzÞ

uM ¼
(6) uM ðr, zÞ ¼ (9)
m dr em r lnð1 þ d=ro Þ

Then, one can get from Eq. 6, for capillary mem- The axial pressure distribution is given in entry
brane, as: “Hollow Fiber Enzymatic Reactor, Modelling


 of.”
1 @ @ ðruM Þ k1 @ @p
r 
r M ¼ 0 (7)
r @r @r m r @r @r
References
When Eq. 7 is integrated twice with respect to r
with boundary conditions, at r = ro then pM = pt Bird RB, Stewart E, Lightfoot EN (1960) Transport phe-
and at r = ro + d then pM = pe, one gets the nomena. Wiley, New York
radial pressure and velocity distributions (Nagy Drioli E, Giorno L (1999) Biocatalytic membrane reactor.
2011, pp. 178) within the membrane as: Taylor & Francis, London
Nagy E (2011) Basic equations of the mass transport
through a membrane layer. Elsevier, Amsterdam
pt ðzÞ
pe ðzÞ r Seidel-Morgenstern A (2010) Membrane reactors. Wiley-
pM ðr, zÞ ¼ ln þ pt ðzÞ (8)
lnð1 þ d=ro Þ ro VCH, Weinheim
B
Biocatalytic Membrane Reactor,
Modeling of
Endre Nagy
Research Institute of Chemical and Process
Engineering, University of Pannonia, Veszprém,
Hungary
There are two main types of membrane bioreac-
tors: (i) the system that consists of a traditional
stirred-tank reactor combined with membrane
separation unit and (ii) the membrane that con-
tains the immobilized biocatalysts such as
enzymes, microorganisms, and antibodies and,
thus, acts as a support and a separation unit. The
biocatalyst can be immobilized in or on the mem-
brane by entrapment, gelification, physical
adsorption, ionic binding, covalent binding, or
cross-linking (Giorno and Drioli 1999; Cabral
et al. 2001). Modeling of stirred-tank reactor,
for chemical reactions in it, is known
(Westerterp et al. 1993). This can easily be
adapted for biochemical reactions applying the
reaction kinetics given in entry “▶ Biocatalytic
Membrane Reactor: Mass Transport.” The
momentum and mass, energy transport through
membrane as a separation unit, starting with
Navier-Stokes equation (Bird et al. 1960),
strongly depend on the separation process used
(Baker 2004; Drioli et al. 2006; Nagy 2011).
Immobilizing biocatalyst in the porous mem-
brane matrix of an asymmetric membrane or
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_847-1
onto membrane interface, the membrane layer
can act as an active catalyst and a permselective
layer. The biocatalytic membrane modules (plane
and frame, hollow fiber capillary, tube as well as
spiral membrane modules) can be divided into
three sections: feed and permeate fluid phases
and the biocatalytic membrane layer itself.
Modeling of a membrane process means the
simultaneous treatment of every section starting
with Navier-Stokes equations for momentum,
mass, and energy (Bird et al. 1960) adapting
them to the real operating conditions and com-
pleting them by source or sink terms (Seidel-
Morgenstern 2010). The energy balance equation
is mostly negligible in case of biochemical reac-
tion; the process can be regarded as isotherm;
accordingly the continuity (conservation of
mass), momentum, and component balance equa-
tions (see Eqs. 1–4 in entry “▶ Modeling of Hol-
low Fiber Enzymatic Reactor”) should be
simultaneously or consecutively (mass transport
does not affect the velocities of fluids) solved
after suitable simplification of a real system.
The cylindrical effect should be taken into
account for capillary membrane when the ratio
of the membrane thickness and the internal radius
is larger than about 0.05. The second-order pres-
sure gradient can be expressed by Eq. (1)
(Nagy 2011, p. 225). From that the radial and
the axial velocity distribution in the feed
(lumen) and the shell side can easily be obtained
(see entry “▶ Biocatalytic Membrane Reactor:
2 Biocatalytic Membrane Reactor, Modeling of

Mass Transport; Hollow Fibre Enzymatic Reac- (2011) for the general Michaeli-Menten kinetics
tor: Modelling”). or bioreactions with two substrates feeding on the
two sides of the membrane reactor. This method
d2 p t 8uo mB 1 can take into account the effect of the in-space
¼ 2 fcosh½lðL  zÞ
dz 2 ro lð1 þ BÞsinhðlLÞ l2 and/or time variable or concentration dependent
parameters on the process.
 h1 þ f ð1 þ BÞicoshðlzÞg (1)

with [rk denotes the outer radius of hexagonal

References
arrangement of the hollow fibers; f is the fraction
of inlet feed directed out through the shell (Nagy Baker RW (2004) Membrane technology and applica-
2011)] tions, 2nd edn. Wiley, Chichester
Bird RB, Stewart E, Lightfoot EN (1960) Transport phe-
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  nomena. Wiley, New York
16k 1 Cabral JMS, Mota M, Tramper J (2001) Multiphase bio-
l¼ 1 þ
r3o lnð1 þ d=ro Þ B reactor design. Taylor & Francis, London
Drioli E, Giorno L (1999) Biocatalytic membrane reactor.
Taylor & Francis, London
and Drioli E, Criscuoli A, Curcio E (2006) Membrane
contactors: fundamentals, applications and potentiali-
 2  2 ties. Elsevier, Amsterdam
d rk
B¼ 1þ  Nagy E (2011) Basic equations of the mass transport
ro ro þ d through a membrane layer. Elsevier, Amsterdam
Seidel-Morgenstern A (2010) Membrane reactors. Wiley-
VCH, Weinheim
The mass transfer rates for constant parameters
Westerterp KR, Swaaij WPM, Beenackers AACM
are given in entry “▶ Biocatalytic Membrane (1993) Chemical reactor design and operation.
Reactor: Mass Transfer” for limiting cases. An Wiley, New York
analytical approach is recommended by Nagy
F
Food Packaging, Membranes for
Alberto Figoli
The Institute on Membrane Technology
(CNR-ITM), Rende, CS, Italy
Synonyms
Food packaging; Membrane operations
Food packaging is often defined as a heteroge-
neous group of boxes, envelops, papers, and coat-
ings that are employed in order to increase
foodstuffs shelf life (European Council 1994).
This means that any food packaging system
aims to avoid/slow down bacterial/fungal con-
tamination and deterioration and, at the same
time, to ensure the maintenance of properties as
firmness, color, and flavor as long as possible.
Nowadays, beside the traditional concept of
packaging as impenetrable barrier, novel systems
are required, such as modified atmosphere pack-
aging (MAP) and active packaging (AP). Poly-
meric membranes, thanks to their unique
properties of permselectivity and ability to sus-
tain controlled delivery, can be successfully used
for food packaging; indeed, their properties can
be exploited for such innovative packaging sys-
tems (Figoli et al. 2010), as also shown in Fig. 1.
Furthermore, the expertise of membranologists
could help to produce food packaging systems
from biodegradable nonpolluting sources. In
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_851-1
particular, the properties of films produced from
biopolymers can be improved by well-developed
techniques as blending, use of plasticizers, and
loading with nanoparticles.
MAP is frequently used in the case of fresh, or
minimally processed, respiring, products, like
vegetables and fruits. MAP aims at maintaining
an optimum gas balance in the package head-
space. In particular, a selected ratio between car-
bon dioxide and oxygen is often required in order
to allow living vegetal tissues respiration and
survival, at the same time preventing aging and
deterioration. The respiratory quotient
(RQ) (Cameron et al. 1995) is defined as the
optimum balance between O2 and CO2 that
should be maintained within the package; this
value is peculiar of each fruit or vegetable spec-
imen. MAP requires films having specific
permselectivity to gases, such as carbon dioxide
and oxygen, rather than impenetrable materials.
In this case, gas separation membranes can be
particularly useful, while membrane materials
can be selected, in each case, on the basis of
their permselectivity to oxygen and carbon diox-
ide. By varying the ratio between polymer and
additive concentrations, dense membranes in
modified polyether ether ketone (PEEK-WC)
and poly-alpha-pinene (PaP) were reported to
match the values required by different products,
as apple, Brussels sprouts, carrot, green pepper,
and turnip (Torchia et al. 2004).
A wide range of CO2/O2 permselectivity
values can be obtained by using packaging
2 Food Packaging, Membranes for
Food Packaging,
Membranes for,
Fig. 1 Application of
membrane in traditional
food packaging, revised
from ref. (Figoli et al. 2010)
structures based on biopolymers. These are
defined as biodegradable materials that can be
decomposed by microorganisms and enzymatic
degradation. Starch, cellulose, chitosan,
polycaprolactone (PCL), and polylactic acid
(PLA) are some examples of biopolymers suit-
able for food packaging (Mensitieri et al. 2011).
In literature, several studies already demon-
strated that biopolymers can compete with
oil-derived plastics for packaging of different
fruit and vegetable species (see for instance ref.
Conte et al. 2009; Kantola and Helen 2001;
Muratore et al. 2005; Srinivasa et al. 2002). How-
ever, hydrophilicity and poor mechanical proper-
ties are the main drawbacks for use of
biopolymers as food packaging systems. Several
strategies, already developed in the field of mem-
brane science and technology, can be useful to
improve properties and processability of biopoly-
mers for food packaging, such as use of chemical
additives (plasticizers, antioxidants, stabilizers)
(Torchia et al. 2004; Abdorreza et al. 2011),
blending (Torchia et al. 2004; John et al. 1998;
Sarazin et al. 2008), chemical cross-linking
(González et al. 2011; Yu et al. 2011), or use of
nanofillers (Belbekhouche et al. 2011; Chivrac
et al. 2009; Famá et al. 2011; Hu et al. 2011; Li
et al. 2011).
Active releasing packaging systems are used
to control the delivery of specific substances to
the packed product. Membranes loaded with spe-
cific substances, coated on the surface, or
entrapped in the polymeric matrix can be useful
in this case, similar to what already developed in
the medical field (Baker 2002). Membranes can
be used to sustain the controlled delivery of anti-
microbial substances, such as allyl isothiocyanate
(AITC) (Lee et al. 2008) or oxalic acid (Figoli
et al. 2004). Active release can be also combined
with use of biopolymers. Films based on starch,
corn zein, and PLA can be used for delivery of
lysozyme, nisin, and natural antimicrobial com-
pounds (Torchia et al. 2004); literature reports
several other interesting examples of
biopolymer-based films as active packaging sys-
tems (Atarés et al. 2011; Chana-Thaworn
et al. 2011; Gemili et al. 2009; Sánchez-González
et al. 2011). Microencapsulation is another strat-
egy for controlled delivery. It has been shown
that it can be used coupled to traditional packag-
ing materials or biopolymers for active packaging
systems releasing natural antimicrobials (Guarda
et al. 2011) or aroma compounds (Marcuzzo
et al. 2010).
References
Abdorreza MN, Cheng LH, Karim AA (2011) Effects of
plasticizers on thermal properties and heat sealability
of sago starch films. Food Hydrocoll 25:56–60
Atarés L, Pérez-Masiá R, Chiralt A (2011) The role of
some antioxidants in the HPMC film properties and
lipid protection in coated toasted almonds. J Food Eng
104:649–656
Baker RW (2002) Future directions of membrane gas
separation technology. Ind Eng Chem Res
41:1393–1411
Belbekhouche S, Bras J, Siqueira G, Chappey C,
Lebrun L, Khelifi B, Marais S, Dufresne A (2011)
Water sorption behavior and gas barrier properties of
cellulose whiskers and microfibrils films. Carbohydr
Polym 83:1740–1748
Cameron AC, Talasila PC, Joles DW (1995) Predicting
film permeability needs for modified-atmosphere
packaging of lightly processed fruits and vegetables.
Hort Sci 30:25
Chana-Thaworn J, Chanthachum S, Wittaya T (2011)
Properties and antimicrobial activity of edible films
incorporated with kiam wood (Cotyleobium
lanceotatum) extract. LWT Food Sci Technol
44:284–292
Food Packaging, Membranes for
Chivrac F, Pollet E, Averous L (2009) Progress in nano-
biocomposites based on polysaccharides and
nanoclays. Mater Sci Eng R 67:1–17
Conte A, Scrocco C, Brescia I, Del Nobile MA (2009) Dif-
ferent packaging strategies for fresh-cut ‘barattiere’
melon cultivar (cucumis melo L.). Int J Food Sci
Technol 44:1422–1428
European Council (1994) Directive 94/62/EC on packag-
ing and packaging waste. Off J Eur Union L365:10–23
Famá LM, Pettarin V, Goyanes SN, Bernal CR (2011) -
Starch/multi-walled carbon nanotubes composites
with improved mechanical properties. Carbohydr
Polym 83:1226–1231
Figoli A, Drioli E, Jansen JJM, Wessling M (2004) Film
antimicrobico per prolungare la shelf life, ISSN0033-
9687, Rassegna dell’Imballagio, Nov. 2004, N 16,
Year 25th
Figoli A, Mascheroni E, Limbo S, Drioli E (2010) Mem-
branes for food packaging. In: Peinemann K-V,
Pereira Nunes S, Giorno L (eds) Membrane technol-
ogy, vol 3. WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim
Gemili S, Yemenicioglu A, Altinkaya SA (2009) Devel-
opment of cellulose acetate based antimicrobial food
packaging materials for controlled release of lyso-
zyme. J Food Eng 90:453–462
González A, Strumia MC, Alvarez Igarzabal CI
(2011) Cross-linked soy protein as material for biode-
gradable films: synthesis, characterization and biodeg-
radation. J Food Eng 106:331–338
Guarda A, Rubilar JF, Miltz J, Galotto MJ (2011) The
antimicrobial activity of microencapsulated thymol
and carvacrol. Int J Food Microbiol 146:144–150
Hu Q, Fang Y, Yang Y, Ma N, Zhao L (2011) Effect of
nanocomposite-based packaging on postharvest
quality of ethylene-treated kiwifruit (Actinidia
deliciosa) during cold storage. Food Res Int
44:1589–1596
John J, Tang J, Bhattacharya M (1998) Processing of
biodegradable blends of wheat gluten and modified
polycaprolactone. Polymer 39:2883–2895
3
Kantola M, Helen H (2001) Quality changes in organic
tomatoes packaged in biodegradable plastic films.
J Food Qual 24:167–176
Lee DS, Yam K, Piergiovanni L (2008) Overview of food
packaging system, Ch. 1’, In: Food Pack. Sci. Tech.,
CRC Press, p 5–7
Li X, Li X, Ke B, Shi X, Du Y (2011) Cooperative
performance of chitin whisker and rectorite fillers on
chitosan films. Carbohydr Polym 85:747–752
Marcuzzo E, Sensidoni A, Debeaufort F, Voilley A (2010)
Encapsulation of aroma compounds in biopolymeric
emulsion based edible films to control flavour release.
Carbohydr Polym 80:984–988
Mensitieri G, Di Maio E, Buonocore GG, Nedi I,
Oliviero M, Sansone L, Iannace S (2011) Processing
and shelf life issues of food packaging materials and
structures from renewable resources. Trends Food Sci
Technol 22:72–80
Muratore G, Del Nobile MA, Buonocore GG, Lanza CM,
Nicolosi AC (2005) The influence of using biodegrad-
able packaging films on the quality decay kinetic of
plum tomato (PomodorinoDatterino ®). J Food Eng
67:393–399
Sánchez-González L, Cháfer M, González-Martínez C,
Chiralt A, Desobry S (2011) Study of the release of
limonene present in chitosan films enriched with ber-
gamot oil in food simulants. J Food Eng 105:138–143
Sarazin P, Li G, Orts WJ, Favis BD (2008) Binary and
ternary blends of polylactide, polycaprolactone and
thermoplastic starch. Polymer 49:599–609
Srinivasa PC, Baskaran R, Ramesh MN, Harish Prashanth
KV, Tharanathan RN (2002) Storage studies of mango
packed using biodegradable chitosan film. Eur Food
Res Technol 215:504–508
Torchia AM, Clarizia G, Figoli A, Drioli E (2004) Poten-
tiality of PEEKWC as new material in food packaging.
Ital J Food Sci XV:173–184
Yu Q, Song Y, Shi X, Xu C, Bin Y (2011) Preparation and
properties of chitosan derivative/poly(vinyl alcohol)
blend film crosslinked with glutaraldehyde. Carbohydr
Polym 84:465–470
P
Pervaporation in Natural Aroma
Processing
Alberto Figoli
The Institute on Membrane Technology
(CNR-ITM), Rende (CS), Italy
Natural aromas are extremely volatile organic
compounds. The aromatic fraction reveals infor-
mation on the quality of the food and it is directly
related to its odor, texture, and taste. Aroma com-
pounds are generally present in very low concen-
trations (1–20 ppm) even if the complex of the
single aromatic compounds in a fruit is very high.
Studies of different types of fruits, in fact, indi-
cate that more than 6,000 compounds are respon-
sible of their aroma (Aroujalian and Raisi 2007)
belonging to different chemical classes such as
alcohols, ketones, aldehydes, esters, carboxylic
acids, and phenols. Aroma recovery for food
and cosmetic industries continues to be a great
challenge for economic and quality reasons
(Sampranpiboon et al. 2000). In the fruit juice
industry, for instance, where a concentration
step is needed, a loss and a degradation of
aroma compounds, due to the thermal treatment,
can occur. For this reason, in order to restore the
original flavor quality of the final product, it is
necessary to recover and add these aromatic com-
pounds back to the concentrated juice (Pereira
et al. 2006). In this context, pervaporation
(PV) is a novel method that can be applied for
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_855-2
aroma recovery from diluted aqueous solutions.
Pervaporation, in fact, is based on the chemical-
physical interaction between membrane material
and the components present in the feed. Hydro-
phobic pervaporation, in particular, is applied to
aroma recovery by using hydrophobic membrane
materials such as polydimethylsiloxane (PDMS)
and polyoctylmethyl siloxane (POMS) (Lipnizki
et al. 2002). Compared to other traditional tech-
niques, such as distillation, adsorption, air strip-
ping, and solvent extraction, pervaporation offers
numerous advantages: high selectivity, low
energy requirement, no chemical addition, and
low-operating temperature. Pervaporation per-
formances are evaluated by taking in consider-
ation the permeate flux and selectivity. Up to now
most studies focused on the separation of model
binary or multicomponent solutions and just a
few of them were based on real feed obtained
from fresh fruits (Figoli et al. 2010). Aromas
have been isolated by pervaporation from several
fruits such as pineapples, grapes, kiwis, straw-
berries, oranges, and pomegranates. During the
last few years, most of the research on aroma
recovery has been carried out on laboratory
scale. Pervaporation scale-up, in fact, is still
underdeveloped due to several limitations mainly
due to the membranes and modules, which are not
sufficient selective and economic.
2 Pervaporation in Natural Aroma Processing
References
Aroujalian A, Raisi A (2007) Recovery of volatile aroma
components from orange juice by pervaporation.
J Membr Sci 303:154–161
Figoli A, Tagarelli A, Cavaliere B, Voci C, Sindona G,
Sikdar SK, Drioli E (2010) Evaluation of
pervaporation process of kiwifruit juice by SPME-
GC/Ion trap mass spectrometry. Desalination
250:1113–1117
Lipnizki F, Olsson J, Tragardh G (2002) Scale-up of
pervaporation for the recovery of natural aroma
compounds in the food industry. Part 1. Simulation
and performance. J Food Eng 54:183–195
Pereira CC, Ribeiro CP Jr, Nobrega R, Borges CP
(2006) Pervaporative recovery of volatile aroma com-
pounds from fruit juices. J Membr Sci 274:1–23
Sampranpiboon P, Jiraratananon R, Uttapap D, Feng X,
Huang RYM (2000) Separation of aroma compounds
from aqueous solutions by pervaporation using
polyoctylmethyl siloxane (POMS) and polydimethyl
siloxane (PDMS) membranes. J Membr Sci 174:55–65
S
Separation of Organic from Organic
Components (Pervaporation
Application)
Alberto Figoli
The Institute on Membrane Technology
(CNR-ITM), Rende (CS), Italy
Separation of organic-organic compounds is one
of main areas in which pervaporation (PV) is
employed together with solvent dehydration and
removal of volatile organic compounds (VOCs)
from aqueous solutions. Many organic com-
pounds either have a close boiling point or they
form azeotropic mixtures that cannot be effi-
ciently separated by common techniques such as
distillation. In this framework, pervaporation can
be used to separate these mixtures alone or, most
of the times, combined with distillation in a
hybrid process in order to improve the separation
efficiency.
Pervaporative organic-organic separation is
the least developed field of application of
pervaporation, and it is still very challenging
principally due to the lack of membranes able to
resist to the harsh conditions of solvents and the
high temperatures required by the process (Baker
2004. In order to overcome the swelling effect
and the degradation phenomenon caused by
organic solvents, cross-linked membranes and
blended polymeric materials have been devel-
oped and employed. On the other hand, inorganic
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_856-1
and inorganic-polymer hybrid membranes gained
a great acceptance, thanks to their high mechan-
ical, thermal, and chemical stability.
The choice of using hydrophilic or hydropho-
bic membranes is based on the solubility of the
target organic compound in a particular material.
With the installation of the first plant for the
separation of methanol/methyl tert-butyl ether
mixture in 1991, the commercial interest in the
separation of organic mixtures trough
pervaporation started to rise. Over the last
50 years, organic pervaporation has been exten-
sively investigated by the chemical and petro-
chemical industries in which refinery streams
contain a large number of organic components
such as benzene, styrene, and toluene.
Pervaporative organic-organic separations can
be classified as:
(i) Separation of polar/nonpolar solvent mix-
tures such as methanol/methyl tert-butyl
ether and ethanol/ethyl tert-butyl ether
(ii) Separation of aromatic/aliphatic and aro-
matic/alicyclic mixtures such as benzene/
cyclohexane
(iii) Separation of aliphatic hydrocarbons such
as toluene/isooctane
(iv) Separation of isomers such as m-/p-xylene
and n-/t- butanol (Smitha et al. 2004)
2 Separation of Organic from Organic Components (Pervaporation Application)

References Smitha B, Suhanya D, Sridhar S, Ramakrishna M (2004)

Separation of organic-organic mixtures by
Baker RW (2004) Membrane technology and applica- pervaporation-a review. J Mem Sci 241:1–21
tions, 2nd edn. Wiley, Chichester, West Sussex PO19
8SQ, England pp 355–392, Chapter 9
V
Vacuum-Driven Pervaporation
Alberto Figoli
The Institute on Membrane Technology
(CNR-ITM), Rende, CS, Italy
Pervaporation is a concentration-driven mem-
brane process in which a feed liquid mixture is
directly in contact with the “active selective
layer” of the membrane, while the permeate in a
vapor phase is constantly removed from the other
side. The driving force is represented by a gradi-
ent in the partial vapor pressure that creates a
chemical potential gradient in the liquid phase,
which is responsible for the selective sorption of
one feed component into the membrane matrix,
its subsequent diffusion through the membrane,
and its final desorption into the permeate side. In
pervaporation, in order to maintain a vapor pres-
sure difference, any of the following, i.e., a
sweeping carrier gas, a vacuum downstream
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_857-1
pressure, or a temperature difference, can be
used. By applying vacuum to the downstream
side, for instance, a decrease in the chemical
potential gradient is obtained and a selective
mass transfer can be induced (Vallieres and
Favre 2004).
At small scale a vacuum pump is often used in
order to get a low vapor pressure. At industrial
scale, on the contrary, the dimensions required
for a vacuum pump would be prohibitive to reach.
An alternative is represented by the condensation
of the permeate vapor that spontaneously creates
a vacuum in the permeate side (Baker 2004)
(Fig. 1).
Vacuum, as opposed to sweeping gas, does not
require any further separation from the sweeping
gas; moreover, the vapors can be recovered by
condensation, and in many cases, its use can
simplify the overall process.
2 Vacuum-Driven Pervaporation

Vallieres C, Favre E (2004) Vacuum versus sweeping gas

operation for binary mixtures separation by dense
membrane processes. J Membr Sci 244:17–23

Vacuum-Driven Pervaporation, Fig. 1 Vacuum-

driven pervaporation

References

Baker RW (2004) Membrane technology and applica-

tions, 2nd edn. Wiley, Chichester,West Sussex PO19
8SQ, England, pp 355–392, Chapter 9
H
Heterogenization or Immobilization
of a Catalyst
Enrica Fontananova
Institute on Membrane Technology (ITM-CNR),
Rende, Italy
The heterogenization or immobilization of a cat-
alyst in/on a membrane consists in the incorpora-
tion of a catalyst in/on a membrane by chemical
bonds or physical entrapment.
In the case of a homogeneous catalyst, the
incorporation constitutes a way to
heterogenize it.
When a catalyst is incorporated within or on
the surface of a membrane, the membrane com-
position (characteristics of the membrane mate-
rial, hydrophobic or hydrophilic, presence of
chemical groups with specific functionality,
etc.) and the membrane structure (dense or
porous, symmetric or asymmetric) can positively
influence the catalyst performance, not only by
the selective absorption and transport of reagents
and/or products but also influencing the catalyst
activity by electronic and conformational effect.
The main requirements that must be consid-
ered to produce an “ideal catalyst” are: low costs,
high selectivity, high stability under reaction con-
ditions, nontoxicity, “green properties,” and first
of all recoverability, i.e., the possibility to
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_859-1
recover and reuse the catalyst (Gladysz 2001;
Hill 1999).
In this perspective, the heterogenization of
catalysts has interesting implications because it
allows the reuse several times of the same cata-
lyst. Among the different heterogenization
methods, the entrapping of a catalyst in/on a
membrane offers new possibility for the design
of new catalytic processes.
In addition to the fundamental criteria that
have to be considered in the selection of a mem-
brane for a specific separation process, i.e.:
– Stability (mechanical, thermal, and chemical)
– Permeability and selectivity
– Fouling tendency
– Cost (capital and operating)
Extra technical complexities need to be con-
sidered in the design and realization of catalytic
membranes:
– Catalyst stability during the immobilization
procedure
– Influence of the catalyst particles on the mem-
brane properties (mechanical, transport, etc.)
– Effect of the catalyst loading, dimensions, and
distribution, on the catalytic efficiency
– Leaching out from the membrane of the
catalyst
2 Heterogenization or Immobilization of a Catalyst
However, catalytic membranes deserve spe-
cial advantages that in many cases justify these
additional efforts.
In the design of a catalytic membrane, major
issues in the polymer selection are the mechani-
cal, thermal, and chemical stability under reac-
tion conditions.
What is fundamental is to realize a stable
catalyst immobilization in order to avoid its
leaching out from the membrane. Different
immobilization strategies can be used in order
to achieve these goals: covalent bonds, electro-
static and weak interactions (van der Waals or
hydrogen bonds) of the catalyst with the mem-
brane, or catalyst encapsulation.
A good affinity for the catalyst is desirable in
order to avoid catalyst leaching and to have a
good adhesion between the polymer and the cat-
alyst, with an optimal dispersion of the
second one.
The affinity between a compound and a poly-
meric material can be often anticipated by the
calculation of the affinity parameters (Van
Krevelen 1990; Barton 1990). These parameters
reflect the ability to form hydrogen bond, polar,
and van der Waals interactions in condensed
phase.
The polymer/catalyst affinity can be also
improved by an appropriate chemical functiona-
lization of one or both components.
In the case of application in liquid phase,
ideally, the solvent used for the reaction needs
to be a non-solvent for the catalyst, and the mem-
brane has not to have an excessive swelling in it.
It is also possible in some cases to improve the
catalyst retention in the membrane by the catalyst
enlargement as: dendrimers, hyperbranched
polymers, and catalyst bound to a soluble poly-
mer (Dioos et al. 2006).
Mass transfer of the reagents to the catalytic
sites, and of the products away from them, should
be fast enough in order to not limit the reaction,
but, at the same time, the contact time catalyst/
reagent should be also appropriate.
For a porous membrane, the choice of the
polymer material is of less importance for trans-
port properties in comparison with a dense
membrane, because permeation does not take
place through the polymer matrix, but through
the membrane pores (Vankelecom 2002).
However, the membrane material is relevant
for the membrane stability and surface properties,
such as wettability and fouling tendency.
The membrane preparation conditions
depend on the membrane material and the
desired structure and morphology. In the case
of a catalytic membrane, the incorporation of
the catalyst complicates the process because
the catalyst should be firmly entrapped in the
membrane and the catalyst structure and activity
has to be preserved during the membrane prep-
aration procedure.
Moreover, the properties (including transport
properties) of the catalytic membrane are usually
different than those of the reference membrane
prepared in the same conditions but without the
catalyst.
Different techniques for membrane prepara-
tion are today available and can be opportunely
employed also to prepare catalytic membranes:
phase separation, coating, interfacial polymeriza-
tion, sintering, stretching, and track etching are
some examples (Strathmann et al. 2006).
In some cases, the catalyst is entrapped in/on
the membrane already formed, by covalent
bonds, electrostatic interactions, absorption by
weak interactions, or physical entrapment. In
alternative, the catalyst immobilization can be
carried out in the same time of the membrane
formation, for example, by dispersing the cata-
lyst in the polymer casting solution and succes-
sive phase separation (Drioli and Fontananova
2010).
References
Barton AFM (1990) Handbook of polymer-liquid interac-
tion parameters and solubility parameters. CRC Press,
Boca Raton
Dioos BML, Vankelecom IFJ, Jacobs PA (2006) Aspects
of immobilisation of catalysts on polymeric supports.
Adv Synth Catal 348:1413–1446
Drioli E, Fontananova E (2010) Catalytic membranes
embedding selective catalysts: preparation and
Heterogenization or Immobilization of a Catalyst
applications. In: P. Barbaro and F. Liguori (eds.),
Heterogenized homogeneous catalysts for fine
Chemicals Production, Catalysis by Metal Complexes
33, Springer, Berlin
Gladysz JA (2001) Recoverable catalysts. Ultimate goals,
criteria of evaluation, and the green chemistry inter-
face. Pure Appl Chem 73:1319–1324
Hill CL (1999) Homogeneous catalysis. Controlled green
oxidation. Nature 401:436–437
3
Strathmann H, Giorno L, Drioli E (2006) An introduction
to membrane science and technology. Publisher CNR,
Roma. ISBN 88-8080-063-9
Van Krevelen DW (1990) Properties of polymers, 3rd edn.
Elsevier Science, Amsterdam
Vankelecom IFJ (2002) Polymeric membranes in catalytic
reactors. Chem Rev 102:3779–3810
H
Heteropolyacid Composite
Membranes
Enrica Fontananova
Institute on Membrane Technology (ITM-CNR),
Rende, Italy
Heteropolyacid composite membranes are
membranes functionalized with heteropolyacids
(HPAs).
Acid catalysis and catalytic oxidation are two
of the main application areas of HPAs composite
membranes. Moreover, interesting examples of
HPAs immobilized in membranes are present in
the field of the polymer electrolyte membrane
fuel cells (PEMFCs) (Norby 1999).
There are many different structural types of
HPAs, but the Keggin type (Mioč et al. 2005) is
the most common for the majority of the applica-
tions as catalysts or solid state proton conductors.
The HPAs discussed in the following text are
molybdophosphoric acid (H3PMo12O40),
phosphotungstic acid (H3PW12O40), and
silicotungstic acid (H4SiW12O40).
Catalysis by heteropoly acids has well-
established industrial applications including het-
erogeneous catalyzed selective oxidations
(oxidation of methacrolein to methacrylic acid
and ethylene to acetic acid) and acid-catalyzed
reactions (homogeneous liquid-phase hydration
of olefins, biphasic polymerization of THF to
poly(tetramethylene glycol) and the gas-phase
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_860-1
synthesis of ethyl acetate from ethylene and
acetic) (Kozhevnikov 2007).
Nevertheless, in many processes using HPA
catalysts, there are relevant difficulties
concerning catalyst separation and recovery and
reaction selectivity. In this perspective, the
heterogenization of HPAs in membranes can
offer important advantages in catalysis by the
integration of the catalytic activity with the selec-
tive transport through the membranes.
Hydration of a-pinene to a-terpineol over
molybdophosphoric acid entrapped in polyvinyl
alcohol (PVA) membranes cross-linked with
succinic acid, and molybdophosphoric acid
encaged in zeolites and dispersed in
polydimethylsiloxane (PDMS) membranes,
have been reported in literature (Castanheiro
et al. 2003). In both cases, the catalytic activity
of the membranes is quite good in successive runs
although a partial catalyst leaching was observed.
Catalytic membranes have been prepared by
linking phosphotungstic acid on the surface of
plasma-modified membranes made of
polyvinylidene fluoride (PVDF). The PVDF
membranes was modified by plasma treatments
on the surface, in order to graft N-containing
polar groups able to act as binding sites with
phosphotungstic acid. The catalytic activity of
the membranes has been evaluated in the aerobic
degradation reaction of phenol in water
(Fontananova et al. 2006). Higher phenol degra-
dation rate was observed for the HPA
heterogenized on PVDF membrane compared to
2 Heteropolyacid Composite Membranes

Heteropolyacid
Composite Membranes, O
Fig. 1 Schematic view of
the interactions by S O –
hydrogen bonds between a O S
heteropoly acid (the Keggin –
O H2O H3O+ O
structure is represented) H3O+ O
with the sulfonic group of a
cation exchange H2O
membrane, the water H3O+ H2O
hydration molecules, and
dioxonium ions O H3O+
O–
S H2O
O
H3O+
H3O+ –O

H2O H3O+ S
O
H2O H2O
O

homogeneous catalyst dissolved in solution.
Moreover, the catalytic membranes have given
proof of their complete stability under photooxi-
dation condition and their good recycle.
In numerous literature studies, it has been
reported that the HPAs can reduce the resistance
to the proton transport in PEMFCs.
The reduction of the HPAs particles sizes and
their good dispersion inside the polymeric matrix
resulted to be key factors in order to have a
positive effect on the proton conductivity because
of the increase of the surface to volume ratio of
the additives and the possibility to have a more
efficient proton hopping (Ramani et al. 2005).
HPAs typically exist in hydrated phase with
the degree of hydration varying from 6 to 30 mol-
ecules of water, depending on the temperature
and the relative humidity (e.g., six molecules of
water are present in the H3PW12O40 structure up
to 175–230  C) (Mioč et al. 2005). In Keggin-
type HPAs, hydrogen bonds exist between each
acid proton and two water molecules, are also
present between water molecules and the termi-
nal oxygen atoms of the HPAs, and moreover,
involving different Keggin units (Moffat 1986).
If the HPA sizes are in the order of a few
nanometers and uniformly distributed in the pro-
ton exchange membrane, the water hydration
molecules and/or dioxonium ions of the additive
can be used to better interconnect the ionic cluster
of the polymeric matrix providing a better path-
way for proton hopping (Ramani et al. 2005).
Composite membranes with higher glass tran-
sition temperature (Tg) and higher stability of the
proton conductivity at high temperature have
been obtained by incorporation of 60 wt.% of
three different HPAs (H3PW12O40,
H3PMo12O40, Na2HPW12O40) in SPEEK mem-
branes with 70 %, 74 %, and 80 % degree of
sulfonation (Zaidi et al. 2000).
Hybrid membranes prepared from sulfonated
polyetherketone (SPEK), heteropoly acids, and
an inorganic network of ZrO2 or RSiO3/2 have
been also prepared obtaining a higher proton
conductivity of the membranes (Ponce
et al. 2003).
The HPAs have been also used to stabilize the
proton conductivity of the Nafion membranes at
elevated temperature and low relative humidity.
For example, H3PW12O40, also exchanged with
larger cations such as Cs+, NH4+, Rb+, and Tl+,
has been heterogenized in Nafion membranes
observing better proton conductivity (Ramani
et al. 2005).
Tungstophosphoric acid, silicotungstic acid,
and phosphomolybdic acid have been used as
functional additives in composite membranes
made of the sulfonated derivative of an
amorphous-modified polyetheretherketone,
called SPEEK-WC (Fontananova et al. 2010).
Heteropolyacid Composite Membranes
The embedding of the inorganic HPAs, in
particular the H4SiW12O40, in SPEEK-WC mem-
branes, enhanced the proton conductivity
because the HPAs improved the interconnection
of the ionic clusters in the polymeric matrix pro-
viding a preferential pathway for proton hopping
(Fig. 1).
References
Castanheiro JE, Ramos AM, Fonseca I, Vital J (2003) The
acid-catalysed reaction of a-pinene over
molybdophosphoric acid immobilised in dense poly-
meric membranes. Catal Today 82:187–193
Fontananova E, Donato L, Drioli E, Lopez L, Favia P,
d’Agostino R (2006) Heterogenization of
polyoxometalates on the surface of plasma modified
polymeric membranes. Chem Mater 18:1561–1568
Fontananova E, Trotta F, Jansen JC, Drioli E (2010) Prep-
aration and characterization of new non-fluorinated
polymeric and composite membranes for PEMFCs.
J Membr Sci 348:326–336
3
Kozhevnikov IV (2007) Sustainable heterogeneous acid
catalysis by heteropoly acids. J Mol Catal A Chem
262:86–92
Mioč UC, Todorović MR, Davidović M, Colomban P,
Holclajtner-Antunović I (2005) Heteropoly
compounds – from proton conductors to biomedical
agents. Solid State Ionics 176:3005–3017
Moffat JB (1986) Cation-anion effects in heteropoly com-
pounds with Keggin structures. Polyhedron 5:261–269
Norby T (1999) Solid-state protonic conductors: princi-
ples, properties, progress and prospects. Solid State
Ionics 125:1–11
Ponce ML, Prado L, Richau K, Mohr R, Nunes SP
(2003) Reduction of methanol permeability in
polyetherketone-heteropolyacid membranes.
J Membr Sci 217:5–15
Ramani V, Kunz HR, Fenton JM (2005) Effect of particle
size reduction on the conductivity of Nafion ®/
phosphotungstic acid composite membranes.
J Membr Sci 266:110–114
Zaidi SMJ, Mikhailenko SD, Robertson GP, Guiver MD,
Kaliaguine S (2000) Proton conducting composite
membranes from polyether ether ketone and
heteropolyacids for fuel cell applications. J Membr
Sci 173:17–34
P
Polymer Electrolyte Membrane Fuel
Cell (PEMFC)
Enrica Fontananova
Institute on Membrane Technology (ITM-CNR),
Rende, Italy
Fuel cells (FCs) are electrochemical devices for
the direct conversion of chemical energy into
electrical energy.
Unlike the classical battery, FCs do not store
the energy within the chemicals internally, but
they use a continuous supply of the fuel from an
external storage tank. Moreover, while the elec-
trodes in a battery react and change as a battery is
charged or discharged, in a fuel cell the electrodes
are catalytic.
Because FCs do not include the conversion of
thermal to mechanical energy, they are not sub-
ject to the Carnot efficiency limit typical of a heat
engine (e.g., steam and gas turbine) and are char-
acterized by a high energy efficiency (Song
2002).
The primary components of a FC are: the
anode, the cathode, and the ion conducting elec-
trolyte. In a FC, the selective transport of ions
through an electrolyte occurs in combination with
a redox reaction.
In a Polymer Electrolyte Membrane Fuel Cell
(PEMFC), the electrolyte is a polymer electrolyte
membrane (PEM) which allows the transport of
the protons from the anode, where they are
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_861-1
produced in the oxidation of a fuel (usually H2
or methanol), to the cathode, where the protons
react with O2 to produce water (Table 1).
The PEM is a cation exchange membrane and
the flow of ionic charges (ideally only cations)
through the membrane is balanced by the flow of
electronic charge through the external circuit pro-
ducing an electrical power. The only secondary
products in the overall reaction are: water, heat
(eventually recoverable), and CO2, if the fuel
contains carbon (e.g., methanol as fuel in direct
methanol PEMFC).
The reaction at the anode is exothermic; how-
ever, it requires to overcome an activation energy
barrier. Three strategies are used in FCs technol-
ogy in order to improve the kinetic reaction:
raising the temperature, increasing the surface
electrode area, and using catalysts (usually Pt or
Pt alloys).
The ion-exchange membrane is pressed with a
porous electrode layer on each side and the cata-
lyst is present at the interfaces membrane/elec-
trode forming the so-called membrane electrode
assembly (MEA).
A single PEMFC typically gives a voltage
from 0.6 to 0.7 V, as a consequence, to produce
a useful voltage, many cells are connected in
series. Such a design is called fuel cell stack.
Bipolar plates, generally made of graphite, inter-
connect the cathode of one cell with the anode of
the next cell, serving in parallel the following
functions: conducting electricity, feeding oxygen
to the cathode and fuel to the anode, and
2 Polymer Electrolyte Membrane Fuel Cell (PEMFC)
Polymer Electrolyte Membrane Fuel Cell (PEMFC), Table 1 Reactions occurring in hydrogen and direct methanol
polymer electrolyte membrane fuel cell (PEMFC)
H2-PEMFC
Anode H2 ! 2 H+ + 2 e
Cathode 1
/2 O2 + 2 H+ + 2 e ! H2O
Overall reaction 1
/2 O2 + H2 ! H2O
channeling away wastewater and heat from the
reaction sites.
Currently, the most commonly used PEMs for
applications in PEMFCs are made of perfluoro-
sulfonic acid polymers, such as Nafion
membranes.
In the last decades, the development of new
PEMs with improved properties for long-term
fuel cells operations has received relevant atten-
tion. Not only perfluoropolymers but also par-
tially fluorinated and nonfluorinated
hydrocarbon, nonfluorinated aromatic, mixed
matrix, and acid–base blend membranes, have
been investigated. Various reviews are available
which give an overview of the progress made in
the development of proton-conducting polymer
materials for PEMFCs (Roziere and Jones 2003;
Hickner et al. 2004; Smitha et al. 2005; Tripathi
and Shahi 2011; Thiam et al. 2011; Drioli and
Fontananova 2012).
The properties required to the PEMs are: high
proton conductivity; no electronic conductivity;
low permeability to the reagent species; appro-
priate chemical, thermal, and mechanical stabil-
ity; and acceptable costs.
The low operating temperatures (50–130
C)
and the high power density (400–1000 W/Kg) of
the PEMFCs make them ideal for automotive
applications, distributed power generation, and
portable electronic devices (Larmine and
Andrews 2000).
Although PEMFCs have recently passed the
demonstration phases and have reached a partial
Methanol-PEMFC
CH3OH + H2O ! CO2 + 6H+ + 6e
3
/2O2 + 6H+ + 6e ! 3H2O
CH3OH + 3/2O2 ! CO2 + 2H2O
commercialization stage (Wee 2007), there are
still many issues to be addressed before large
scale diffusion, including the high cost and lim-
ited durability of PEMs, the appropriate fuel pro-
duction and storage.
References
Drioli E, Fontananova E (2012) Membrane materials for
addressing energy and environmental challenges.
Annu Rev Chem Biomol Eng 3:395–420
Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath
JE (2004) Alternative polymer systems for proton
exchange membranes (PEMs). Chem Rev
104:4587–4612
Larmine J, Andrews D (2000) Fuel cell systems explained.
Wiley, Chichester
Roziere J, Jones DJ (2003) Non-fluorinated polymer mate-
rials for proton exchange membrane fuel cells. Annu
Rev Mater Res 33:503–555
Smitha S, Sridhar S, Khan A (2005) Solid polymer elec-
trolyte membranes for fuel cell applications – a review.
J Membr Sci 259:10–26
Song C (2002) Fuel processing for low-temperature and
high-temperature fuel cells: challenges, and opportu-
nities for sustainable development in the 21st century.
Catal Today 77:17–49
Thiam HS, Daud WRW, Kamarudin SK, Mohammad AB,
Kadhum AAH, Loh KS, Majlan EH (2011) Overview
on nanostructured membrane in fuel cell applications.
Int J Hydrog Energy 36:3187–3205
Tripathi BP, Shahi VK (2011) Organic–inorganic
nanocomposite polymer electrolyte membranes for
fuel cell applications. Prog Polym Sci 36:945–979
Wee JH (2007) Applications of proton exchange mem-
brane fuel cell systems. Renew Sust Energ Rev
11:1720–1738
S
Sulfonated PEEK-WC (SPEEK-WC)
Enrica Fontananova
Institute on Membrane Technology (ITM-CNR),
Rende, Italy
The sulfonated PEEK-WC (SPEEK-WC) is
the sulfonated derivative of an amorphous
polyetheretherketone called PEEK-WC or poly
(oxa-p-phenylene-3,3-phthalido-p-phenylene-oxa-
p-phenylene-oxy-phenylene) (Zhang et al. 1987)
(Fig. 1).
PEEK-WC has a lactonic group, called cardo
group (WC in the polymer name means with
cardo), which prevents the crystalline organiza-
tion of the polymer chains; as a consequence,
PEEK-WC is amorphous, and it is suitable for
the preparation of membranes by solubilization in
solvents with medium polarity (e.g., chloroform,
dichloromethane, dimethyl sulfoxide, dimethyla-
cetamide, dimethylformamide, 1-methyl-2-
pyrrolidinone, etc.) and casting. On the contrary,
the “classical” PEEK (Fig. 1) is semicrystalline
and insoluble in organic solvents. PEEK-WC has
a high glass transition temperature (Tg = 222  C)
and very good chemical, thermal, and mechanical
stability.
Moreover, PEEK-WC properties can be mod-
ified by introducing specific chemical groups on
the polymer chain. The reaction with
chlorosulfonic acid or concentrated sulfuric acid
already at room temperature introduces a sulfonic
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_862-1
group on the aromatic ring giving a polymeric
material (SPEEK-WC) with ion exchange capac-
ity (Fig. 1) (Trotta et al. 1998). The degree of
sulfonation (DS) of the SPEEK-WC can be mod-
ulated by changing the reaction time and/or
temperature.
The reaction is carried out in homogenous
phase and in shorter times compared to that of
the traditional PEEK. For example, the reaction
of PEEK with concentrated sulfuric acid at room
temperature for 192 h gives a polymer with
DS = 0.85 (Nunes et al. 2002), while for
PEEK-WC the same DS can be obtained by reac-
tion in 4 h (Drioli et al. 2004).
Sulfonated PEEK-WC is a promising
non-fluorinated material for application in poly-
mer electrolyte membrane fuel cells (PEMFCs),
suitable for the preparation of membranes by
casting and solvent evaporation. The sulfonation
level of the polymer influences the membrane
properties, in particular the ion exchange capac-
ity and the proton conductivity, which both
improve with increasing DS.
Moreover, polymeric SPEEK-WC mem-
branes with high performance in terms of proton
conductivity were recently obtained by optimiz-
ing the membrane preparation conditions (type of
solvent, temperature, and post-treatment) which
strongly influence the membrane microstructure
and, as a consequence, the membrane transport
properties and thermal behavior (Fontananova
et al. 2012).
2 Sulfonated PEEK-WC (SPEEK-WC)

PEEK PEEK-WC

O O
O
O

O O
O O

SPEEK-WC

O O
O O
O O SO3H

O O O O

1-DS DS

Sulfonated PEEK-WC (SPEEK-WC), Fig. 1 Repetitive unit of the PEEK, PEEK-WC, and the SPEEK-WC (DS is the
degree of sulfonation)

SPEEK-WC membranes have been also mod-
ified by thermal annealing and chemical cross-
linking with a diamine in order to improve their
long-term durability (Fontananova et al 2013).
Various ex situ characterizations were carried
out on the modified and pristine SPEEK-WC
membranes, including ion exchange capacity,
proton conductivity, liquid water uptake,
counter-elastic index, chemical resistance in oxi-
dative conditions, and gas permeability. The
results indicated that the proposed methodologies
are able to increase hydrolytic and oxidative sta-
bility of the SPEEK-WC membranes.
SPEEK-WC membranes offer a higher resis-
tance to water and methanol vapor transport than
commercial Nafion membranes (which until
today are the most commonly used membranes
for PEMFCs). Also, the H2 and O2 permeabilities
of the SPEEK-WC membranes are lower in com-
parison with Nafion (Fontananova et al. 2010).
These results justify the conclusion that less
crossover problems may occur in the PEMFCs
operating with SPEEK-WC membranes com-
pared to PEMFCs operating with Nafion.
The lower permeability of the SPEEK-WC-
based membranes was due to their lower diffu-
sion coefficients, caused by the higher stiffness of
the aromatic polymer chains of SPEEK-WC with
respect to Nafion.
Functional additives were also heterogenized
in SPEEK-WC membranes, in order to improve
their properties for applications in PEMFCs.
Mixed matrix membranes were prepared
dispersing amorphous zirconium phosphate
sulfophenylenphosphonate (Zr(HPO4)
(O3PC6H4SO3H)), in the SPEEK-WC matrix
(Regina et al. 2006). The membranes obtained
were characterized by a homogeneous distribu-
tion of the inorganic filler. The membranes
exhibited a significantly lower swelling degree
in water and methanol compared to the polymeric
membranes without the filler.
Heteropoly acids (HPAs) have been also dis-
persed into the membrane dope solutions to
Sulfonated PEEK-WC (SPEEK-WC)
prepare mixed matrix membranes (Fontananova
et al. 2010, 2012). The embedding of the inor-
ganic HPAs, in particular the silicotungstic acid
(H4SiW12O40•n H2O), in SPEEK-WC membranes,
enhanced the proton conductivity because the
HPAs, uniformly distributed on a nanometric
scale, interconnected better the ionic cluster of the
polymer providing a favored pathway for protons
hopping.
References
Drioli E, Regina A, Casciola M, Oliveti A, Trotta F,
Massari T (2004) Sulfonated PEEK-WC membranes
for possible fuel cell applications. J Membr Sci
228:139–148
Fontananova E, Trotta F, Jansen JC, Drioli E (2010) Prep-
aration and characterization of new non-fluorinated
polymeric and composite membranes for PEMFCs.
J Membr Sci 348:326–336
3
Fontananova E, Cucunato V, Curcio E, Trotta T,
Biasizzo M, Drioli E, Barbieri G (2012) Influence of
the preparation conditions on the properties of poly-
meric and hybrid cation exchange membranes.
Electrochim Acta 66:164–172
Fontananova E, Brunetti A, Trotta F, Biasizzo M, Drioli E,
Barbieri G (2013) Stabilization of sulfonated aromatic
polymer (SAP) membranes based on SPEEK-WC for
PEMFCs. Fuel Cell 13:86–97
Nunes SP, Ruffmann B, Rikowski E, Vetter S, Richau K
(2002) Inorganic modification of proton conductive
polymer membranes for direct methanol fuel cells.
J Membr Sci 203:215–225
Regina A, Fontananova E, Drioli E, Casciola M,
Sganappa M, Trotta F (2006) Preparation and charac-
terization of sulfonated PEEK-WC membranes for
fuel cell applications. A comparison between poly-
meric and composite membranes. J Power Sources
160:139–147
Trotta F, Drioli E, Moraglio G, Poma EB (1998) Sulfona-
tion of polyetheretherketone by chlorosulfuric acid.
J Appl Polym Sci 70:477–482
Zhang HC, Chen TL, Yuan YG (1987) CN Patent No. CN
85(1987)751
I

Impedance Spectroscopy, the first case, the configuration is indicated as a

Membrane Characterization by two-probe (or two electrodes) type (Fig. 1a). If
two additional electrodes are used to collect the
Enrica Fontananova response of the system, the configuration is indi-
Institute on Membrane Technology (ITM-CNR), cated as four-probe (or four electrodes) type
Rende, Italy (Fig. 1b). Another possible configuration uses
three electrodes, but it is usually employed to
characterize only one half of an electrochemical
Synonyms cell, or phenomena occurring on an electrode and
it will not be discussed here. The two-probe con-
Electrochemical impedance spectroscopy; figuration is usually applied when the membrane
Impedance spectroscopy is pressed between two solid conductive elec-
trodes, like in the case of the membrane electrode
The impedance spectroscopy (IS), or electro-
assembly (MEA) for fuel cells (Fontananova
chemical impedance spectroscopy (EIS), is a
et al. 2012).
powerful technique for characterizing electrical
On the contrary, if the membrane is in contact
behavior of systems in which coupled electrical
with a liquid electrolyte, the four-probe configu-
processes occur at different rates (Barsoukov and
ration is the most convenient and commonly used
Macdonald 2005). The IS technique is able to
(Antony et al. 2013). This second configuration
measure quantitatively the electrical resistance
has the advantage to eliminate the contribution of
in the bulk and interfacial regions of solid and
the electrode injecting stimulus/electrolyte
liquid electrolyte materials, including
charge transfer resistance, from the impedance
membranes.
spectra, focusing the probing on the membrane
IS technique is widely used in the in situ non-
and its interfaces.
destructive characterization of membranes, as
The sinusoidal electrical stimulus is injected
well as to investigate concentration polarization
through two planar electrodes (working and
and fouling phenomena (Fontananova et al. 2012;
counter electrode), and the response of the system
Antony et al. 2013).
to the sine wave perturbation is measured by two
In EIS experiments, a sinusoidal electrical
reference electrodes (indicated as sense and ref-
stimulus (voltage or current) is applied over a
erence) using an impedance analyzer (usually a
frequency range to a pair of electrodes, and the
potentiostat/galvanostat combined with a fre-
response of the system under investigation is
quency response analyzer) which measures volt-
observed by the same or different electrodes. In
age, current, and phase shift (Fig. 1).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_863-1
2 Impedance Spectroscopy, Membrane Characterization by

Impedance Spectroscopy, Membrane Characterization by, Fig. 1 Schematic view of the experimental setup used
for membrane characterization by impedance spectroscopy using two-probes (a) and four-probes configuration (b)

In analogy to Ohm’s law, the impedance is Z00 ¼ jZj sin ’ (6)

defined as (Barsoukov and Macdonald 2005):
U ðoÞ
ZðoÞ ¼ (1)
I ðoÞ
where Z(o) [Ω] is the impedance, U(o) [V] is the
voltage drop, I(o) [A] is the current, and they
depend on the circular velocity or circular fre-
quency o [rad/sec] as follows:
U ðoÞ ¼ Uo sin ot
I ðoÞ ¼ I o sin ðot þ ’Þ
where o = 2pu and u [sec1] is the frequency,
t [sec] is the time, ’ [ ] is the phase shift between
voltage and current, and the subscript  refers to
the amplitude of voltage and current in phase; j is
pffiffiffiffiffiffi
ffi
the imaginary number j ¼ 1.
The impedance can be also rearranged as
follows:
ZðoÞ ¼ jZj cos ’ þ jjZ j sin ’
The Eq. 4 indicates that the impedance is com-
posed of two parts, i.e., the real part:
Z0 ¼ jZ j cos ’
and the imaginary part:
The real part of the impedance is the resistance
(Z0 ); the imaginary part is called reactance (Z00 ).
On the contrary of the measurement in direct
current (DC), using an alternate current
(AC) over a frequency range, it is possible to
distinguish phenomena proceeding at different
rates, like bipolar concentration polarization of
an ion exchange membrane (IEM) in contact with
an electrolyte solution, which induces the forma-
(2) tion of an electrical double layer (EDL) and a
diffusion boundary layer (DBL) (Sang
(3) et al. 2008).
As a consequence, the total electrical resis-
tance is the sum of the contribution for the trans-
port through the membrane and the interfaces.
The bipolar concentration polarization during
an AC cycle, caused by the buildup and depletion
of ions at the interfaces, is time dependent. The
contribution of the interfacial ionic charge trans-
fer through the interfaces layers at low frequen-
cies is greater than at high frequencies, because at
(4) high frequencies there is insufficient time for
their formation.
The experimental impedance data can be fitted
with equivalent electrical circuit models able to
represent the physical system and phenomena
(5) under investigation (Zhang and Spichiger 2000).
The typical shape of the impedance spectra
(Z00 vs. Z0 ) in the case of an IEM pressed between
two solid electrodes exhibits a distinct arc
Impedance Spectroscopy, Membrane Characterization by
a b
Rct
Rm
C C
Cct
Z’’ (Ω)
ω
Rm Rm+Rct
Z’ (Ω)
Impedance Spectroscopy, Membrane Characteriza-
tion by, Fig. 2 Impedance spectra reported as imaginary
(Z00 ) versus real part of the impedance (Z0 ) for an ion
exchange membrane: pressed between two solid elec-
trodes (a) and separating two electrolyte solutions (b).
The spectra are registered respectively with the two- and
four-probe configuration, and the corresponding
(Fig. 2a). In the case of an IEM separating two
liquid electrolyte solutions, additional semicir-
cles appear in the spectra (Fig. 2b). The
corresponding equivalent circuits are also
shown in Fig. 2.
At high frequencies (o!1) the intercept on
the real axis gives the membrane (Rm) or mem-
brane plus solution resistance (Rm+s). Of course,
the solution resistance can be obtained by blank
experiments (without the membrane) and its con-
tribution can be subtracted to obtain the pure
membrane resistance.
At low frequencies (o!0), the intercept on
the real axis gives the sum of membrane (plus
solution, if present) and the interface resistances.
3
Rm+s Redl Rdbl
Cedl CPEdbl
Z’’ (Ω)
ω
Rm+s Rm+s+Redl Rm+s+Redl+Rdbl
Z’ (Ω)
equivalent circuit models are also shown. The resistor is
indicated as R, the capacitor as C, and the constant phase
element (a nonideal capacitor) as CPE. The subscript “m”
is referring to the membrane, “ct” to the charge transfer
between electrode and membrane, “m+s” to membrane
plus solution, “edl” to the electrical double layer, and
“dbl” to the diffusion boundary layer
References
Antony A, Chilcott T, Coster H, Leslie G (2013) In situ
structural and functional characterization of reverse
osmosis membranes using impedance spectroscopy.
J Membr Sci 425–426:89–97
Barsoukov E, Macdonald JR (2005) Impedance spectros-
copy. Theory, experiment, and applications, 2nd edn.
Wiley, New Jersey
Fontananova E, Cucunato V, Curcio E, Trotta F,
Biasizzo M, Drioli E, Barbieri G (2012) Influence of
the preparation conditions on the properties of poly-
meric and hybrid cation exchange membranes.
Electrochim Acta 66:164–172
Sang S, Wu Q, Huang K (2008) A discussion on ion
conductivity at cation exchange membrane/solution
interface. Colloids Surf A 320:43–48
Zhang Z, Spichiger UE (2000) An impedance study on
Mg2+ selective membrane. Electrochim Acta
45:2259–2266
P
Polymeric Catalytic Membranes
Enrica Fontananova
Institute on Membrane Technology (ITM-CNR),
Rende, Italy
A polymeric catalytic membrane is a polymeric
membrane with catalytic properties. The base
material used to prepare the membrane is a poly-
mer, and a catalyst is immobilized within the
membrane or on its surface, conferring catalytic
activity to the system.
Moreover, some polymeric membranes can
have intrinsic catalytic properties towards some
reactions because of the presence of specific
functional chemical groups in the polymer mate-
rial. This is the case of acid polymeric mem-
branes, like Nafion (a perfluorosulfonic acid
polymer), which can work as solid acid catalysts.
Polymeric catalytic membranes are usually
employed when the reaction temperatures are
low (<200  C), such as in the field of fine
chemicals or when a biocatalyst is present
(Vankelecom 2002).
The use of polymeric catalytic membranes has
a lot of interest in the field of membrane reactors
because: a much wider choice of polymeric mate-
rials is available (Ulbricht 2006), the cost of the
polymer membranes is generally lower, and the
preparation protocols are more reproducible in
comparison with inorganic membranes.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_864-1
Polymeric membranes are generally less resis-
tant to high temperatures and aggressive
chemicals than inorganic ones; however, some
polymeric materials resistant under rather harsh
conditions are available like: polydimethyl-
siloxane (PDMS), polyvinylidene fluoride
(PVDF), Hyflon (a perfluoro amorphous poly-
mer), Nafion, and polyimides (PI) (Drioli and
Fontananova 2010).
Some selected examples of polymeric cata-
lytic membranes used in membrane reactors are
listed in Table 1.
In classical heterogeneous catalysis (catalyst
absorbed or linked in porous polymeric or inor-
ganic solids), the conversion and selectivity of
the catalytic process is often limited by the diffu-
sion of the reagents to the catalytic sites and the
products removal from them.
On the contrary, the convective or diffusive
flux in a catalytic membrane can be easily con-
trolled and adjusted to the reaction kinetic mod-
ulating the driving force and/or the membrane
structure and/or membrane material
(Westermann and Melin 2009).
Moreover, in a catalytic membrane, especially
if polymeric, the catalyst entrapment in the func-
tional microstructured environment of the mem-
brane can have a positive influence on the
transition states and reaction kinetics by elec-
tronic and weak interactions, as well as by spatial
restriction and transport dynamics (Fontananova
and Drioli 2010).
2 Polymeric Catalytic Membranes

Polymeric Catalytic Membranes, Table 1 Selected examples of polymeric catalytic membranes used in membrane
reactors
Catalyst and membrane type Applications References
Metal or bimetal nanoparticles in porous membranes: Selective hydrogenation in gasa and a
Groschel
Pd in PAAa,b liquid phaseb et al. 2005
Au-Pd/PVP in PIc Oxidation of alcoholsc b
Schmidt
et al. 2005
c
Mertens 2008
Catalyst in dense membranes: Cyclohexane oxidationd d
Vankelecom
FePcY in PDMSd Enantioselective hydrogenation of et al. 1996
Transition metal complexes with bisphosphine ligands in methyl 2-acetamidoacrylatee e
Wolfson
PDMSe et al. 2002
Enzymes immobilized in UF membranes: (S)-Naproxen esters hydrolysisf f
Giorno
Lipase from Candida rugosa in PA capillary membranesf (-)MPGM resolution by Sepracor et al. 2007
g
Lipase from Serratia marcescens in hollow fibers reactor (industrial application) Shibatani
hydrophilic membranesg et al.2000
Acid membranes and/or membranes functionalized with Transesterification of soybean oilh h
Guerreiro
solid acid catalysts: Esterification reactioni et al. 2006
PVA/sulfosuccinic acidh; Nafionh; supported acid catalysts Dimerisation of isobutenei,j i
Bagnell
mixed with a polymeric binder on PAN/PDMSi,j et al. 1993
j
Fritsch
et al. 2004
k
Polyoxometalates immobilized in/on porous or dense Photooxidation of alcohols in Bonchio
membranes: waterk et al. 2003
Porous PVDFk,l; dense Hyflonm Phenol photodegradationl,n l
Drioli
Surface functionalized PVDFn membranes Photooxygenation of hydrocarbons m et al. 2008
m
Carraro
et al. 2006
n
Fontananova
et al. 2006
PAA polyacrylic acid, FePcY iron phthalocyanine in zeolite Y, PA polyamide, PVA polyvinyl alcohol, MPGM
(3-(4-methoxyphenyl)glycidic acid methyl ester), PVP polyvinylpyrrolidone, PAN polyacrylonitrile, PVDF
polyvinylidene fluoride

References fine chemicals production: materials and processes.

Bagnell L, Cavell K, Hodges AM, Mau AW-H, Seen AJ
(1993) The use of catalytically active pervaporation
membranes in esterification reactions to simulta-
neously increase product yield, membrane
permselectivity and flux. J Membr Sci 85:1291–1299
Bonchio M, Carraro M, Scorrano G, Fontananova E,
Drioli E (2003) Heterogeneous photooxidation of
alchols in water by Photocatalytic Membranes Incor-
porating Decatungstate. Adv Synth Catal
345:1119–1126
Carraro M, Gardan M, Scorrano G, Drioli E,
Fontananova E, Bonchio M (2006) Solvent-free, het-
erogeneous photooxygenation of hydrocarbons by
Hyflon ® membranes embedding a fluorous-tagged
decatungstate: the importance of being fluorous.
Chem Commun 43:4533–4535
Drioli E, Fontananova E (2010) Catalytic membranes
embedding selective catalysts: preparation and appli-
cations. In: Heterogenized homogeneous catalysts for
Springer, Berlin
Drioli E, Fontananova E, Bonchio M, Carraro M,
Gardan M, Scorrano G (2008) Catalytic membranes
and membrane reactors: an integrated approach to
catalytic process with a high efficiency and a low
environmental impact. Chin J Catal 29(11):1152
Fontananova E, Drioli E (2010) Catalytic membranes and
membrane reactors. In: Drioli E (ed) Comprehensive
membrane science and engineering, vol 3. Elsevier,
Oxford, pp 109–133
Fontananova E, Donato L, Drioli E, Lopez L, Favia P,
d’Agostino R (2006) Heterogenization of
polyoxometalates on the surface of plasma modified
polymeric membranes. Chem Mater 18:1561–1568
Fritsch D, Randjelovic I, Keil F (2004) Application of a
forced-flow catalytic membrane reactor for the
dimerisation of isobutene. Catal Today 98:295–308
Giorno L, D’Amore E, Mazzei R, Piacentini E, Zhang J,
Drioli E, Cassano R, Picci R (2007) An innovative
approach to improve the performance of a two separate
Polymeric Catalytic Membranes
phase enzyme membrane reactor by immobilizing
lipase in presence of emulsion. J Membr Sci
295:95–101
Gröschel L, Haidar R, Beyer A, Cölfen H, Frank B,
Schomäcker R (2005) Hydrogenation of propyne in
palladium-containing polyacrylic acid membranes
and its characterization. Ind Eng Chem Res
44:9064–9070
Guerreiro L, Castanheiro JE, Fonseca IM, Martin-Aranda
RM, Ramos AM, Vital J (2006) Transesterification of
soybean oil over sulfonic acid functionalised poly-
meric membranes. Catal Today 118:166–171
Mertens PGN (2008) Membrane-occluded gold-
palladium nanoclusters as heterogeneous catalysts for
the selective oxidation of alcohols to carbonyl com-
pounds. Adv Synth Catal 350:1241–1247
Schmidt A, Haidar R, Schomäcker R (2005) Selectivity of
partial hydrogenation reactions performed in a pore-
through-flow catalytic membrane reactor. Catal Today
104:305–312
3
Shibatani T, Omori K, Akatsuka H, Kawai E, Matsumae
H (2000) Enzymatic resolution of diltiazem interme-
diate by Serratia marcescens lipase: molecular mech-
anism of lipase secretion and its industrial application.
J Mol Catal B: Enzym 10:141–149
Ulbricht M (2006) Advanced functional polymer mem-
branes. Polymer 47:2217–2262
Vankelecom IFJ (2002) Polymeric membranes in catalytic
reactors. Chem Rev 102:3779–3810
Vankelecom IFJ, Parton RF, Casselman MJA,
Uytterhoeven JB, Jacobset PA (1996) Oxidation of
cyclohexane using FePcY-Zeozymes occluded in
polydimethylsiloxane membranes. J Catal
163:457–464
Westermann T, Melin T (2009) Flow-through catalytic
membrane reactors – principles and applications.
Chem Eng Process 48:17–28
Wolfson A, Geresh S, Gottlieb M, Herskowitz M (2002)
Asymmetric hydrogenation of methyl
2-acetamidoacrylate with Rh-DuPHOS occluded in
PDMS. Chem Commun 4:388–390
E
Encapsulation Application
Goran Vladisavljevic
Chemical Engineering Department,
Loughborough University, Leicestershire, UK
Synonyms
Microencapsulation synonym: Microentrapment;
Bichromal particles synonym: Two-colored
particles
Definitions
Carbonless Copy Paper - Paper coated on the
back side with colorless dye or ink capsules,
that burst under the pressure of writing or typing
and react with colorless clay particles coated on
the upper surface of the second sheet.; Phase
Change Material - A substance with a high heat
of fusion that absorb or release a high amount of
energy during melting of freezing, thus acting as
a thermal energy storage; Electrophoretic display -
a display that forms images by rearranging
charged pigment particles with an applied elec-
tric field.
Microencapsulation can be done:
1. To protect the encapsulated material against
oxidation or deactivation due to reactions with
reactive species from the environment.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_879-5
2. To mask the organoleptic properties like color,
taste, and odor of the actives.
3. To achieve controlled/triggered/targeted
release.
4. For safe handling of toxic materials.
5. To achieve in vitro compartmentalization or
immobilization of biological materials and
catalysts.
Microencapsulated materials are utilized in
agriculture, pharmaceuticals, foods, cosmetics
and fragrances, textiles, paper, paints, coatings
and adhesives, toner applications, and many
other industries.
Carbonless copy paper developed by Green
and Schleicher in the 1950s was the first com-
mercial product to employ microcapsules.
A coating of microencapsulated colorless ink is
applied to the top sheet of the paper, and a devel-
oper is applied to the subsequent sheet. When
pressure is applied by writing, the capsules
break and the ink reacts with the developer to
produce the dark color of the copy. Paper-like
displays with low power consumption such as
rotating bichromal microspheres system and
microencapsulated electrophoretic system are
other examples of commercial applications of
microencapsulated ink (Yoshizawa 2004). In the
rotating bichromal system (Gyricon), bichromal
capsules with oppositely charged hemispheres
are free to rotate within oil-filled cavities. In the
microencapsulated electrophoretic display sys-
tem (E ink), oppositely charged black and white
2 Encapsulation Application
particles move under an applied electric field in a
clear liquid encapsulated within a transparent
capsule.
Today’s textile industry makes use of
microencapsulated materials to enhance the prop-
erties of finished goods. One application increas-
ingly utilized is the incorporation of
microencapsulated phase change materials
(PCMs), such as paraffin wax. Phase change
materials absorb and release heat in response to
changes in environmental temperatures. When
temperatures rise, the phase change material
melts, absorbing excess heat, and feels cool. Con-
versely, as temperatures fall, the PCM releases
heat as it solidifies, and feels warm. Microencap-
sulation is also used in thermochromic and pho-
tochromic fabrics, which change color with
changes in temperature or light, insect-repellent
fabrics, which ward off mosquitoes, and scented
fabrics, which release fragrance (Nelson 2002).
Pesticides are encapsulated to be released over
time, allowing farmers to apply the pesticides less
often rather than requiring very highly concen-
trated and perhaps toxic initial applications
followed by repeated applications to combat the
loss of efficacy due to leaching, evaporation, and
degradation.
Ingredients in foods are encapsulated for sev-
eral reasons (Gouin 2004). Most flavorings are
volatile; therefore, encapsulation of these com-
ponents extends the shelf life of products by
retaining the food flavors within that would oth-
erwise evaporate out and be lost. Some ingredi-
ents are encapsulated to mask taste, such as
nutrients added to fortify a product without
compromising the product’s intended taste.
Alternatively, flavors are sometimes
encapsulated to last longer, as in chewing gum.
Some food ingredients must be encapsulated to
be protected from oxidation or other degradation
reactions caused by exposure to light, moisture,
or oxygen. Microencapsulation preserves lactic
acid bacteria, both starters and probiotics, in food
and during the passage through the gastrointesti-
nal tract, and may contribute to the development
of new functional foods.
Many drug formulations for oral, intravenous,
ocular, and subcutaneous administration are
microencapsulated to achieve controlled,
targeted, or triggered release of active ingredi-
ents. Aspirin, for example, can cause peptic
ulcers and bleeding if doses are introduced all
at once.
Microencapsulation of cells and enzymes is
used to improve efficiency of bioreactors since
very high volumetric productivity can be
achieved; encapsulated biocatalysts typically
have greater thermal and operational stability
and downstream processing is simplified, since
the encapsulated biocatalyst can easily be recov-
ered and reused. In molecular biology, single-cell
encapsulation is used to achieve high-throughput
screening in directed evolution experiments.
References
Gouin S (2004) Microencapsulation: industrial appraisal
of existing technologies and trends. Trends Food Sci
Technol 15:330–347
Nelson G (2002) Application of microencapsulation in
textiles. Int J Pharm 242:55–62
Yoshizawa H (2004) Trends in microencapsulation
research. KONA 22:23–31
B

Buffer Displacement in Diafiltration If constant volume diafiltration is used and

B has an apparent rejection coefficient of zero,
Greg Foley the concentration of B declines according to the
School of Biotechnology, Dublin City expression (Cheryan 1998)
University, Dublin, Ireland
cB ¼ cB0 expðV b =V s Þ

Buffer displacement involves the use of
diafiltration to replace the solvent (non-product)
fraction of a macromolecular solution, with a
buffer. The basis of the operation is that the
solvent, including low molecular weight impuri-
ties, passes through the membrane, while the
solute (product) is retained. Suppose the solution
can be viewed as a mixture containing a macro-
molecular product, A, and a micromolecular
impurity, B. Now suppose that the buffer contains
a desired component, C – a salt perhaps. Then,
buffer displacement involves the reduction in the
concentration of B while keeping the concentra-
tion of A constant and raising the concentration
of C to the desired level. This can be done using
constant volume (continuous) diafiltration, dis-
continuous diafiltration by dilution, or discontin-
uous diafiltration by volume reduction.
where Vb is the volume of buffer added while Vs
is the (constant) volume of solution. Assuming
that component, C, also has a rejection coefficient
of zero, its concentration in the retentate solution
increases according to the expression
cc ¼ cc0 ð1  expðV b =V s ÞÞ
where cc0 is the concentration of C in the buffer
tank. If the product, A, has a rejection coefficient
of 1.0, its concentration will remain unchanged.
References
Cheryan M (1998) Ultrafiltration and microfiltration,
2nd edn. CRC Press, Boca Raton

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_881-4
B

Buffer Flush in Diafiltration
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
A buffer flush is simply the replacement of an
impure, product-containing solution with buffer
by subjecting it to ▶ diafiltration.
The most common way of performing a buffer
flush, at least in a membrane context, is to use
constant volume (continuous) diafiltration in
which a certain volume of buffer is added to a
given volume of impure solution while that solu-
tion undergoes batch ▶ ultrafiltration, all the
while keeping the solution volume constant.
The greater the ratio of buffer volume (Vb) to
solution volume (Vs) (▶ Diafiltration Factor), the
greater will be the reduction in undesired impu-
rities. For example, if an impurity has a rejection
coefficient of 0.2 and the diafiltration factor is
5
, the reduction in impurity concentration is
given by (Foley 2013)
c=c0 ¼ eð1sÞV b =V s ¼ e5ð10:2Þ ¼ 0:018
References
Foley G (2013) Membrane filtration – a problem solving
approach with MATLAB. Cambridge University
Press, Cambridge, UK

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_882-4
C
Cascade Diafiltration
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
Cascade systems may be used when the product is
in the permeate of a microfiltration or ultrafiltra-
tion system.
Consider a two-stage cascade. Constant vol-
ume diafiltration is performed in the first stage to
maximize the recovery of the product which
passes through the membrane. The product-
containing permeate enters the second stage
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_883-4
where it undergoes batch ultrafiltration using a
membrane which retains the product.
Cascades can be operated in open-loop or
closed-loop configurations (Charcosset 2012). In
the open-loop configuration, the permeate from
the second stage goes to drain. In the closed-loop
configuration, the permeate from the second
stage is used as the diluant for the first stage,
thus reducing substantially the volume of fresh
diluant required.
References
Charcosset C (2012) Membrane processes in biotechnol-
ogy and pharmaceutics, 1st edn. Elsevier, Boston
C
Closed-Loop Cascade Diafiltration
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
Closed-loop cascade diafiltration (Charcosset
2012) is used when the product to be recovered
appears in the permeate of the first stage of a
two-stage process. It is similar to ▶ open-loop
cascade diafiltration but differs in that the perme-
ate from the second stage is recycled and used as
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_884-4
the diluant of the first stage. A schematic is shown
below (Fig. 1).
The obvious advantage of this approach over
the open-loop configuration is the reduced
requirement for a fresh diluant. In principle, the
product should have a low rejection coefficient in
the first stage and a high rejection coefficient in
the second stage.
References
Charcosset C (2012) Membrane processes in biotechnol-
ogy and pharmaceutics, 1st edn. Elsevier, Boston
2 Closed-Loop Cascade Diafiltration

Closed-Loop Cascade
Diafiltration,
Fig. 1 Closed-Loop
Cascade Diafiltration

Permeate Permeate

Diafiltration Ultrafiltration
D
Diafiltration Factor
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
One of the most commonly used methods of
diafiltration is constant volume diafiltration
(CVD) also known as continuous diafiltration.
In this process, diluant is added to the retentate
solution which is undergoing batch ultrafiltration.
The process is set up so that the rate of addition of
the diluant exactly balances the permeate flow
rate – hence the retentate volume is constant.
For any given solute with apparent rejection coef-
ficient, s, the solute concentration declines dur-
ing a CVD process according to the equation
(Cheryan 1998)
c ¼ c0 eð1sÞV b =V s
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_885-4
where Vb is the volume of diluant (buffer) added
while Vs is the solution (i.e., retentate) volume.
The ratio Vb/Vs is termed the diafiltration factor,
sometimes referred to as the number of
diavolumes. Once the rejection coefficient is
known, this quantity completely specifies the
reduction in solute concentration that will be
achieved during CVD.
In discontinuous diafiltration processes,
including both dilution and volume reduction
methods, one must specify both the level of vol-
ume reduction/dilution in each stage and also the
number of stages so the diafiltration factor is not
so easily, or meaningfully, defined in those
instances.
References
Cheryan M (1998) Ultrafiltration and microfiltration hand-
book, 2nd edn. CRC Press, Boca Raton
D
Diluant
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
Any diafiltration process involves the replace-
ment of solvent (including undesired impurities)
with a liquid of desired composition. This liquid
is known as the diluant. For example, in constant
volume diafiltration (CVD), also known as con-
tinuous diafiltration, diluant is added to a tank of
unpurified solution while it undergoes batch
ultrafiltration. The rate of diluant addition is set
equal to the permeate flow rate, and thus the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_886-3
solution (retentate) volume remains constant.
The effect of this process is the gradual replace-
ment of the solvent and any solutes with low
rejection coefficients with the diluant. Mathemat-
ically, the reduction in concentration of any sol-
ute, with rejection coefficient, s, is given by
c ¼ c0 eð1sÞV d =V s
where Vd is the volume of diluant added and Vs is
the solution (retentate) volume. The ratio Vd/Vs is
known as the diafiltration factor.
The diluant may be purified water or, more
likely, a buffer.
D
Discontinuous Diafiltration by
Sequential Dilution (Sequential
Dilution Diafiltration)
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
Discontinuous diafiltration by the sequential dilu-
tion method can be summarized in terms of the
three steps shown below. The apparent rejection
coefficients are assumed to be 1.0 and 0 for
macrosolute and microsolute, respectively.
Step 1: Add buffer to increase solution volume
from V0 to Vf. Macrosolute (A) and
microsolute (B) concentrations decrease.
Step 2: Use batch ultrafiltration to reduce solution
volume back from Vf back to V0. Macrosolute
concentration returns to its initial value,
microsolute concentration remains
unchanged. (This follows from the rejection
coefficients of both solutes.)
Step 3: Repeat steps 1 and 2 as required.
# Springer-Verlag Berlin Heidelberg 2015
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DOI 10.1007/978-3-642-40872-4_887-4
A microsolute balance on the first step gives
b ¼ cB0 =cBf ¼ V f =V 0
Extending this analysis to n stages (i.e., repeating
steps 1 and 2 above n times) gives
V f =V 0 ¼ b1=n
For example, if the microsolute concentration is
to be reduced by a factor of 10 (= b) and then if a
single stage is used, Vf/V0 = 10, while if three
stages are used, Vf/V0 = 101/3 = 2.15.
The total volume of buffer used in this case is
given by



V b =V 0 ¼ n V f  V 0 =V 0 ¼ n V f =V 0  1
 
¼ n b1=n  1
For a single stage system, this ratio works out as
9, while for a three-stage system, it works out as
3.46. Thus, the more stages that are used, the
smaller the buffer consumption.
D
Discontinuous Diafiltration by
Volume Reduction (Intermittent
Feed Diafiltration)
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
The steps involved in a discontinuous
diafiltration by volume reduction (▶ intermittent
feed diafiltration) are outlined below. The appar-
ent rejection coefficient of the macrosolute is 1.0,
while that of the microsolute is zero.
Step 1: Batch ultrafiltration from volume V0 to Vf.
Macrosolute concentration increases,
microsolute concentration remains the same
because it has a rejection coefficient of zero.
Step 2: Replace lost permeate with diluant (pure
water or buffer). Macrosolute concentration
returns to initial concentration, microsolute
concentration reduced.
Step 3: Repeat steps 1 and 2 as required.
Consider a single “stage,” i.e., steps 1 and
2 above. The concentration of the macrosolute
remains unchanged. A mass balance on the
microsolute gives the following expression for
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_888-4
its concentration at the end of the two-step
process.
b ¼ cB0 =cBf ¼ V f =V 0
If this is repeated n times, one gets
V 0 =V f ¼ b1=n
The buffer consumption is given by



V b =V 0 ¼ n V 0  V f =V 0 ¼ n 1  V f =V 0
 
¼ n 1  b1=n
Thus, for a tenfold reduction in microsolute
concentration and a three-stage process, one
gets V0/Vf = 101/3 = 2.15 in each
step, while the buffer consumption works out as
Vb/V0=3(1101/3) = 1.607.
If one stage had been used, one would have
had V0/Vf = 10 and Vb/V0 = 1.0(1101) = 0.9.
Thus, increasing the number of stages increases
the amount of buffer required.
The single-stage approach is not always pos-
sible as too large a ▶ volume concentration factor
(V0/Vf) might lead to unsustainably high solution
viscosities.
O

Open-Loop Cascade Diafiltration
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
The configuration for open-loop cascade
diafiltration is shown below. The product recov-
ery is maximized in the first stage using constant
volume diafiltration and concentrated in the sec-
ond stage by ultrafiltration. Ideally, the rejection
coefficient of the product is zero in the first stage
and 1.0 in the second stage. In the closed-loop
configuration, the permeate from the second
stage is used as diluant for the first stage (Fig. 1).

Open-Loop Cascade
Diafiltration,
Fig. 1 Open-Loop
Cascade Diafiltration
Diluant

Permeate Permeate

Diafitration Ultrafitration

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_889-4
S

Sequential Dilution Diafiltration In the subsequent ultrafiltration step, in which

the ▶ retentate volume is reduced to its original
Greg Foley value, the macrosolute, which is assumed to have
School of Biotechnology, Dublin City a rejection coefficient of 1.0, is increased in con-
University, Dublin, Ireland centration to its original value, while the concen-
tration of microsolute, whose rejection
coefficient is zero, remains at its value
Sequential dilution diafiltration is simply another post-dilution.
name for discontinuous diafiltration by sequential Sequential dilution diafiltration can be
dilution. performed as a multistage process, leading to a
It involves repeated dilution of a solution reduction in buffer consumption for a given
followed by batch ultrafiltration. In the dilution reduction in microsolute concentration.
step, both the macrosolute product and the
microsolute impurity are reduced in
concentration.

# Springer-Verlag Berlin Heidelberg 2012

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_890-2
V

Volume Concentration Factor For a solute or particle that has a rejection

coefficient of 1.0, the increase in concentration
Greg Foley during batch operation is given by
School of Biotechnology, Dublin City
University, Dublin, Ireland cf =c0 ¼ V 0 =V f

Therefore,
The aim of any batch membrane filtration process
is to reduce the retentate volume, thus increasing cf ¼ c0 VCF
the concentration of a key molecular or particu-
late species. If the solute has an arbitrary and constant appar-
The volume concentration factor is simply the ent rejection coefficient of s, one gets
ratio of the initial solution volume to the final
solution volume, i.e., V0/Vf. It is usually denoted cf ¼ c0 VCFs
by the abbreviation VCF.

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_891-3
W
Wash Water in Diafiltration
Greg Foley
School of Biotechnology, Dublin City
University, Dublin, Ireland
In the context of ▶ diafiltration, wash water is
simply another term for diluent.
This is the water used to replace impure sol-
vent while retaining the desired product.
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_892-2
A typical example might be the washing of a
cell suspension prior to cell disruption to release
an intracellular product.
The typical way of doing this would be to
subject the cell suspension to batch crossflow
microfiltration while adding wash water at a rate
that exactly balances the filtrate (▶ permeate)
flow rate. Thus, the cells are retained, but the
impure liquid in which the cells are suspended
is gradually displaced by wash water.
B
Blending Modification
of Membranes
Annarosa Gugliuzza
Institute on Membrane Technology - Research
National Council, ITM-CNR, Rende (CS), Italy
When using the word “blend,” we mean a mixture
of two or more components with low or high
molecular weight, organic or inorganic nature,
and solid or liquid state. Physical or chemical
blends with various degree of complexity can be
produced depending on the nature of the mixed
materials. Generally, in a blend we distinguish
between a continuous film (hosting matrix) and a
dispersed phase (filler) consisting of polymers,
oligomers, nanoparticles, nanotubes, nanowires,
zeolites, and so many others (Fig. 1).
The blending is used for making new formu-
lations with superior performance, when compo-
nents with complementary functions are well
interlaced and uniformly distributed. Major con-
cerns are compatibility, uniformity, adhesion,
and minimum loading for maximum surface
area (Gugliuzza 2013; Gugliuzza et al. 2006).
Segregation, nano-confinement, phase separa-
tion, and discontinuity are frequent phenomena,
which take place in solution or during fabrication
of the composite (Gugliuzza et al. 2007; De
Lorenzo et al. 2012). These events occur mainly
when the mixed compounds do not exhibit com-
patibility and/or miscibility at all. In this respect,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_893-2
the glass transition temperature (Tg) could be a
powerful tool for examining the degree of misci-
bility of binary blends, e.g., mixed polymers.
When one Tg is obtained, the blend is considered
fully miscible. If two Tg values are measured and
a dependence on the composition is estimated,
the blend is partially miscible. Finally, immisci-
ble blends show distinct and independent Tg
values, as illustrated by Fig. 2.
A set of equations can be useful to predict the
x-dependence of Tg, where x is the composition.
The Fox equation (1956) is the simplest one and
is traditionally used for binary systems, thereby
giving indication based on the properties of pure
components:
1 x1 x2
¼ þ (1)
T g T g1 T g2
where Tg is related to the blend, whereas Tgi and xi
are glass transition temperature and composition
of the i-esimo pure component, respectively.
The Gordon and Taylor equation (1952)
includes an additional experimental parameter
(kGT) that considers unequal contributions of the
components:
x1 T g1 þ kGT x2 T g2
Tg ¼ (2)
x1 þ kGT x2
Two other more complex relations are the Kwei
(1984) and Brostow (2008), Eqs. 3 and 4, which
take in account additional parameters such as
2 Blending Modification of Membranes

Blending Modification of Membranes, Fig. 1 Examples of miscible and immiscible blends

Blending Modification
of Membranes, Fig. 2 A
schematic representation of
the dependence of Tg on
composition in binary
polymer blends


KKW, q, and ai upon complexity of the polymer
blend and/or copolymers: T g ¼ x1 T g1 þ x2 T g2 þ x1 x2 : a0 þ a1 ð2x1  1Þ

x1 T g1 þ kKW x2 T g2 þa2 ð2x1  1Þ2 þ a3 ð2x1  1Þ3
Tg ¼ qx1 x2 (3)
x1 þ kKW x2 (4)
Blending Modification of Membranes
In all equations the index 2 is referred to the
component with the highest Tg, whereas x2 is
1-x1.
A good blend depends on the degree of inter-
action between the hosting matrix and the exter-
nal surface area of the dispersed phase and can be
regarded as the result of the buoyancy of van der
Waals forces and/or hydrogen bonds established
at their interface (De Luca et al. 2009). Chemical
functionalization and/or compatibilizing agents
are two viable routes for strengthening these
reciprocal interactions and dispersing the phases
in continuous volumetric spaces. This needs to
promote desired events in every region of the
blend.
In membranes, the blend is a common practice
to reinforce or produce specific properties,
including transport, wetting, pores and mechan-
ics, and so many others. Transport properties can
be modified depending on the phase behavior and
related morphology. Permeability, selectivity, or
conductivity can be varied with respect to the
upper bound relationship as a function of the
orientation of the dispersed phase and/or the
nature of the interface generated between the
various components (Robeson 2010). Indeed,
the molecular separation can be addressed via
diffusion or sorption events dependently on free
volume distribution and/or binding sites density.
Similarly, the blending can give new solutions
to dry-wet membranes; changes in supramolecu-
lar chemistry can modulate the wettability, mak-
ing the membrane usable for numerous times
without damages and/or special treatments.
This approach is also preferred when pores
must be generated through polymer networks.
Pore-forming agents are often blended with poly-
mers and, then, removed by washing treatments.
This takes the advantage of generating empty
spaces inside dense polymer networks, but the
major difficulty is often the complete removal
of the filler from the matrix. In this respect, a
good compatibility between pore-forming agent
and polymer matrix is necessary to produce a
3
large number of uniform and regular pores
through the network.
Finally, the blend is often preferred to provide
composites with mechanical, chemical, and ther-
mal properties beyond those observable for the
single elements. Enhanced tensile properties
along with reinforced resistance to high temper-
atures and harsh environments can be obtained by
blending organic and inorganic materials in dif-
ferent ratios.
References
Brostow W, Chiu R, Kalogeras IM, Vassilikou-Dova
A (2008) Prediction of glass transition temperatures:
binary blends and copolymers. Mater Lett
62:3152–3155
De Lorenzo L, Tocci E, Gugliuzza A, Drioli E (2012) Pure
and modified co-poly (amide-12-b-ethylene oxide)
membranes for gas separation studied by molecular
investigations. Membranes 2(3):346–366
De Luca G, Gugliuzza A, Drioli E (2009) Competitive
hydrogen-bonding interactions in modified polymer
membranes: a density functional theory investigation.
J Phys Chem B 113(16):5473–5477
Fox TG (1956) Influence of diluent and of copolymer
composition on the glass temperature of a polymer
system. Bull Am Phys Soc 1:123–125
Gordon M, Taylor JS (1952) Ideal copolymers and the
second-order transitions of synthetic rubbers.
1. non-crystalline copolymers. J Appl Chem
2(9):493–500
Gugliuzza A (2013) Nanocomposite membranes for mem-
brane reactors. In: Basile A (ed) Handbook of mem-
brane reactors volume I: fundamental materials
science, design and optimisation. Woodhead Publish-
ing, Cambridge
Gugliuzza A, Fabiano R, Garavaglia MG, Spisso A, Drioli
E (2006) Study of the surface character as responsible
for controlling interfacial forces at membrane–feed
interface. J Coll Interf Sci 303(2):388–403
Gugliuzza A, De Luca G, Tocci E, De Lorenzo L, Drioli
E (2007) Intermolecular interactions as controlling
factor for water sorption into polymer membranes.
J Phys Chem B 111(30):8868–8878
Kwei TK (1984) The effect of hydrogen bonding on the
glass transition temperatures of polymer mixtures.
J Polym Sci Lett 22(6):307–313
Robeson LM (2010) Polymer blends in membrane trans-
port processes. Ind Eng Chem Res 49:11859–11865
D
Differential Scanning Calorimetry
in Membrane Characterization
Annarosa Gugliuzza
Institute on Membrane Technology - Research
National Council, ITM-CNR, Rende (CS), Italy
The differential scanning calorimetry (DSC) is a
thermodynamic technique that measures the dif-
ference in heat flow between sample and related
reference against time or temperature, while pro-
gramming the sample temperature under specific
atmosphere conditions (Haines 1995). The sam-
ple is contained in a pan and the reference is the
related empty pan. There are two kinds of calori-
metric techniques, including:
• Heat flux DSC, where sample and reference
are heated in the same furnace and a difference
of temperature (DT) is measured. Succes-
sively, the signal is converted to a power dif-
ference by the calorimetric sensitivity.
• Power-compensated DSC, where both the
sample and reference are heated in two inde-
pendent heaters, while the electrical power
ðDP ¼ dðDQ=dtÞ, requested to maintain
close to zero the difference of temperature
between sample and reference, is measured
in real time.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_894-2
The energy flux is associated with a transition
or reaction and is graphed as a heat flow along the
ordinate, while the temperature or time is the
abscissa. In DSC curve, the endothermic peak is
associated with absorption of power, while the
exothermic peak implies release of power from
the sample. The verse of the peaks depends on the
sign of the heat flow.
DSC allows studying different events, includ-
ing phase transitions, glass transition, and chem-
ical reactions. For each thermal event,
thermodynamic magnitudes such as latent heat
(l), specific heat (Cp), and/or a variation of
enthalpy (DH) can be calculated (Table 1).
The transitions studied for polymers and com-
pounds at low molecular weight can also be
examined for related membranes (Gugliuzza
and Drioli 2003). DSC plays a relevant role in
materials science and membrane technology,
because it permits to identify the best-performing
materials through the identification of structure-
transport relationships that form the base of the
membrane performance (Gugliuzza and Drioli
2004). History, molecular rearrangements, and
interactions are some critical issues to be taken
in account when a membrane is processed (Yang
et al. 2000). In this respect, DSC analysis can
provide useful indication about structural fea-
tures of the samples enabling the design of new
interfaces with superior performance in prospect.
Figure 1 shows typical transitions studied on
polymeric membranes, including the glass tran-
sition (Tg) that is displayed as a change in the
2 Differential Scanning Calorimetry in Membrane Characterization

Differential Scanning Calorimetry in Membrane Characterization, Table 1 Thermal transitions and related
parameters measurable by DSC
Event Phase transition Energy sign Parameter
Fusion sol!liq Endothermic l, DH
Crystallization liq!sol Exothermic l, DH
Evaporation liq!gas Endothermic l, DH
Condensation gas!liq Exothermic l, DH
Sublimation sol!gas Endothermic l, DH
Deposition gas!sol Exothermic l, DH
Glass transition Change of the baseline Cp
Chemical reactions Exothermic/endothermic DH

Differential Scanning
Calorimetry
in Membrane
Characterization,
Fig. 1 Main endothermic
and exothermic transitions
observable by DSC

baseline due to a variation of Cp of the polymer
forming the membrane.
All amorphous polymers exhibit a Tg; below
this temperature value, the membrane becomes
glassy owing to the inability of the polymer seg-
ments to rotate and rearrange themselves. When
the membrane temperature is increased over its
Tg, an increase in energy and free volume is
observed due to a broader mobility of the chains,
which enters the polymer in the rubbery region.
Heating and cooling rates as well as chain relax-
ation can affect Tg value and shape, respectively.
The fusion is another endothermic event
involving crystalline domains distributed through
the membranes. The amount and extent of these
ordered regions depends on the chemistry,
molecular weight, and thermal history of the
samples. Polymorphism and crystalline features
of the membranes can be examined in relation to
transport properties and mechanical stability as
well. If the polymer forming the membrane is
available to crystallize, a release of energy is
associated with a decrease in heat flow. The
study of crystallization is often more useful than
fusion, because it allows distinguishing peaks
that normally cannot be well visible in melting.
Phase separation, miscibility, and compatibil-
ity of polymer binary blends, copolymers, and,
more generally, composites are among the most
interesting events to examine by DSC
(De Lorenzo et al. 2012). In this case, the ability
of the materials to interact and distribute them-
selves in continuous and uniformly interlaced
spaces can be evaluated under different experi-
mental conditions. Other interesting indication
about the membranes solidity can be achieved
from the study of curing, aging, as well as degra-
dation and oxygen stability. All these parameters
can significantly affect the membrane transport
properties.
Differential Scanning Calorimetry in Membrane Characterization
References
De Lorenzo L, Tocci E, Gugliuzza A, Drioli E (2012)
Assembly of nanocomposite PEBAX membranes: a
complementary study of affinity and clusterization
phenomena. J Membr Sci 421–422:75–84
Gugliuzza A, Drioli E (2003) New performance of a
modified poly (amide-12-b-ethyleneoxide). Polymer
44(7):2149–2157
3
Gugliuzza A, Drioli E (2004) Role of additives in the
water vapor transport through block co-poly (amide/
ether) membranes: effects on surface and bulk polymer
properties. Eur Pol J 40/10:2381–2389
Haines PJ (1995) Thermal methods of analysis, principles,
applications and problems. Blackie A&P, Oxford
Yang H, Nguyen QT, Ding YD, Long YC, Ping Z (2000)
Investigation of poly(dimethyl siloxane)
(PDMS)–solvent interactions by DSC. J Membr Sci
164(1–2):37–43
H
Honeycomb Membrane Structure
Annarosa Gugliuzza
Institute on Membrane Technology - Research
National Council, ITM-CNR, Rende (CS), Italy
Synonyms
Breath figure membranes; air bubble geometry;
high-defined porous films
Honeycomb membrane structures are a competi-
tive and concrete example of highly ordered
polymeric patterns, which can work as perm-
selective interfaces in advanced membrane pro-
cesses (Gugliuzza et al. 2008). They are prepared
by using a bioinspired nanotechnology, which
exploits the ability of water to condense from
fog to cooled surfaces and self-assemble in semi-
crystalline lattices under dragging Marangoni
convection and capillary forces (Gugliuzza
et al. 2009). When the solvent evaporates, a dif-
ference of temperature is established between the
cooled liquid film and nearby humid atmosphere,
causing droplets to condense and rearrange in
honeycomb-packed geometries. The droplet lat-
tice works as a real pore builder through the
polymeric solution, leading to the formation of
air bubble arrays. Each single cavity can be
regarded as the result of the imprinting action of
the droplets. No coalescence is observed when a
stable polymeric protective layer is formed
# Springer-Verlag Berlin Heidelberg 2015
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DOI 10.1007/978-3-642-40872-4_895-4
around each single droplet during sinking
(Fig. 1).
Under suitable experimental conditions, drop-
let dynamics can be directed towards the forma-
tion of membranes with modulated spherical pore
size, monodisperse pore distribution, long-range
order, and high interconnectivity (Speranza
et al. 2010). The typical hexagonally packed
geometry, resembling natural structures, pro-
duces very high interfacial area necessary to pro-
mote large mass transfer through the membranes.
Also, the complete propagation of the porous
structure along the entire membrane thickness
reduces significantly any resistance to transport,
yielding performance higher than that observed
for commercial tubular modules when worked in
membrane distillation plants (Gugliuzza
et al. 2008).
The singular topography of honeycomb mem-
branes has significant consequences on wettabil-
ity as well. The hexagonally packed geometry
increases the surface roughness according to zig-
zag geometrical model (Thomas 1999),
preventing wetted pores owing to air pockets
uniformly distributed through the surface.
Indeed, the air is easily entrapped inside the big
cavities according to the Cassie–Baxter model,
thereby minimizing the spreading of the liquid
and improving significantly the water resistance
of the membrane.
Chemical and structural features make the
honeycomb membranes ideal interfaces for
some membrane contactors operations, including
2 Honeycomb Membrane Structure
Honeycomb Membrane Structure, Fig. 1 Representative mechanism for the formation of honeycomb membranes
membrane distillation, membrane crystallization,
and membrane emulsification (in particular pre-
mix membrane emulsification), where large mass
transfer along with the establishment of durable
interfaces at the entrance of each single pore are
in great demand. Moreover, the extraordinary
regularity and stability of 3D polymeric architec-
ture make these membranes suitable for working
as molecular reservoirs, scaffolds for tissue engi-
neering, and platforms for sensors.
Compared with traditional manufacturing pro-
cedures, the one-pot fabrication of micro- and
nanostructured membranes, based on the self-
assembly of sacrificial natural building blocks,
is regarded as a novel, flexible, and eco-friendly
technology. This approach is expected to open
new routes to fabricate a large variety of ordered
functional membranes for industrial applications,
but also for handling the miniaturization of light-
weight systems perceptively.
References
Gugliuzza A, Aceto MC, Macedonio F, Drioli E (2008)
Water droplets as template for next generation self-
assembled poly-(etheretherketone) with Cardo mem-
branes. J Phys Chem B 112(34):10483–10496
Gugliuzza A, Speranza V, Trotta F, Drioli E (2009)
Bio-inspired membranes with well-defined channels.
Chem Eng Trans 17:1537–1542
Speranza V, Trotta F, Drioli E, Gugliuzza A (2010) High-
definition polymeric membranes: construction of 3D
lithographed channel arrays through controlling natu-
ral building blocks dynamics. ACS Appl Mater Inter-
faces 2(2):459–466
Thomas JR (1999) Rough surfaces. Imperial College
Press, London
T

The Principle of Reverse Osmosis describing the transport in reverse osmosis mem-
(RO) branes two approaches are described in the liter-
ature. One is the so-called solution-diffusion
Lidietta Giorno1, Enrico Drioli1 and model which neglects kinetic coupling of differ-
Heiner Strathmann2 ent fluxes (Merten 1966). The second is based on
1
Institute on Membrane Technology, National the phenomenological equation of the thermody-
Research Council of Italy, ITM-CNR, National namic of irreversible processes (Katchalsky and
Research Council of Italy, Rende(CS), Calabria, Curran 1967). This model does consider kinetic
Italy coupling between different fluxes. Both models
2
Universität Stuttgart, Institute of Chemical describe the transport in reverse osmosis mem-
Process Engineering Stuttgart, branes quite accurately indicating that kinetic
Baden-W€ urttemberg, Germany coupling is not of great importance in reverse
osmosis.

Synonyms
Reverse Osmosis Mass Transport
Mass transfer in Reverse Osmosis RO
Described by the Solution-Diffusion
Model
In reverse osmosis the driving force is also a
hydrostatic pressure difference. The principle of
In the solution-diffusion model, the flux of dif-
the process is illustrated in Fig. 1, which shows a
ferent components through a membrane is
solution containing a low molecular weight com-
assumed to be by diffusion only and can be
ponent separated by a membrane from the solvent
described by the product of its concentration
and a hydrostatic pressure difference applied
and mobility in the membrane matrix and the
across the membrane resulting in a flux of solvent
chemical potential gradient of the component in
from the solution into the pure solvent
the membrane. Furthermore, it is assumed that
(Strathmann et al. 2006).
there is no kinetic coupling between fluxes, that
The membrane used in reverse osmosis has an
the volume flux is approximately identical to the
asymmetric structure with a dense barrier layer at
flux of the solvent, and that the solute flux due to
the side facing the feed solution. It is assumed
the pressure gradient is negligibly small com-
that in this layer the individual components are
pared to the solute flux due to the activity
transported by diffusion and that viscous flow
gradient.
through pores or pinholes can be neglected. For
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_908-1
2 The Principle of Reverse Osmosis (RO)

asymmetric membrane The concentration of the different components in

with dense skin layer the membrane is proportional to the concentra-
* * * * * permeate
tion in the outside solutions and it is given by:
feed * *
* (filtrate)
* *
**
*
*
* *
*
m
Ci ¼ k i Ci (4)
* * * *
* * **
** *
* * Here, ki is the partition coefficient of the compo-
* * *
* *
*
*
* * *
* nent i between the membrane and the adjacent
* *
* ** solution, Ci and mCi are the concentrations in the
* *
* * ** * outside solution and in the membrane.
flux Introducing Eq. 4 into Eqs. 2 and 3 gives the
Δp volume flux, i.e., the filtration rate, and the flux of
the solute as function of the applied hydrostatic
The Principle of Reverse Osmosis (RO), pressure, the osmotic pressure, the diffusion coef-
Fig. 1 Schematic drawing illustrating the principle of
reverse osmosis ficient of a component in the membrane, its con-
centration in the feed and permeate solution, and
its partition coefficient between the membrane
Thus, the flux of a component in the mem-
and the feed solution:
brane can be described by:

 k w Dw Cw V w
2
J i ¼ Li dmi ¼ Li V i dp þ RTdlnai Jv ¼ ðDp  DpÞ
RT
Di m Ci

¼ V i dp þ RTdlnai (1) k w Dw V w
RT ¼ ðDp  DpÞ (5)
RT
Here, J is the flux, L is phenomenological coeffi-
cient, m is the chemical potential, p is the hydro- and
static pressure, a is the activity, V is the partial

molar volume, D is the diffusion coefficient, and J s ¼ ks Ds Cfs  Cps (6)
m
Ci is the concentration in the membrane; the
subscript i refers to a component. Here, Jv is the volume flux, Js is the solute flux,
For the solvent, i.e., i ¼ w it is assumed that D is the diffusion coefficient, k is the partition
J v ffi J w and Cw V w ¼ 1. For the solute, i.e., i ¼ s it coefficient of the components between the mem-
is assumed that: dms ffi RTDln as and p ffi RTln aw
. brane and the adjacent solutions, C is the concen-
Here the subscripts v, w, and s refer to volume,
Vw
tration, p the hydrostatic pressure, and p the
solvent, and solute. osmotic pressure of the solutions, the subscripts
Integrating over the cross section of the mem- s and w refer to solute and water, respectively,
brane and expressing the activity of the solvent and the superscripts m, f, and p refer to the mem-
by the osmotic pressure and that of the solute by brane, the feed, and the permeate. Furthermore is
its concentration gives the volume flux to: V w Cw ¼ 1.
To determine the rejection, the Eqs. 5 and 6
 
2
 Cp
J v ¼ Lw V w Dp  Dp ; (2) are introduced into Equation Ri ¼ 1  Cif .
i

Thus is:
and the solute flux to:

J s ¼ Ds m Cs dlnm Cs ¼ Ds dm Cs (3)
The Principle of Reverse Osmosis (RO)
Cps Js
Rs ¼ 1  f
¼1
Cs J v Cfs


ks m Ds Cfs  Cps RT
¼1
kw m Dw V w ðDp  DpÞCfs
Equation 7 shows that rejection of a component
in reverse osmosis is not only a function of the
membrane and feed solution properties it is also a
function of the applied hydrostatic pressure. The
rejection will increase with increasing applied
hydrostatic pressure and approaches asymptoti-
cally a maximum value.
Reverse Osmosis Transport Described
by the Phenomenological Equations
In deriving Eqs. 5, 6, and 7 on the solution diffu-
sion model, a number of assumptions have been
made including the neglecting of all kinetic cou-
pling between transported components and any
viscous flow. A more comprehensive treatment of
the mass transport in reverse osmosis mem-
branes, where kinetic coupling and convective
flow are taken into account, is based on phenom-
enological equations applied to the laws of the
thermodynamic of irreversible processes. In a
reverse osmosis system, which consists of a
membrane and a two component feed solution,
i.e., a solvent and a solute, two independent fluxes
will be obtained when the membrane is used as
frame of reference. These fluxes can be described
by:
X
Ji Lik Xk ði, k ¼ 1, 2, 3 . . . , nÞ
k C ¼ J w dmw þ J s dms
Here, J is the flux of the different components,
L is the phenomenological coefficient, and X is
the driving force, the subscripts i and k refer to
different components.
Assuming a system without viscous flow com-
posed of a solute, a solvent, and a membrane as
frame of reference there are two independent
fluxes:
3
J w ¼ Lw dmw þ Lws dms (9)
and
(7)
J s ¼ Lsw dmw þ Ls dms (10)
Here, J is the flux, m is the chemical potential, L is
the phenomenological coefficient, the subscripts
w and s refer to the solvent which is assumed to be
water and the solute which is assumed to be salt,
the subscripts ws and sw refer to the coupling
between the fluxes of water and salt and salt and
water.
The diagonal coefficients Lw and Ls are always
positive while coupling coefficients Lsw and Lws
can be positive or negative as can be seen from
the dissipation function which describes the
entropy production in a process. The total number
of coefficient in the phenomenological equations
is reduced by the Onsager relation, which postu-
lates that the coupling coefficients Lsw and Lws are
identical (Onsager 1931a, b). However, Eqs. 9
and 10 are not very useful to describe the trans-
port properties of a reverse osmosis membrane
because the coupling coefficients are difficult to
determine in an independent measurement and
generally in reverse osmosis the total filtration
rate, i.e., the volume flux is of interest. However,
the coupling coefficient can be converted to more
easily measurable constants when the phenome-
nological equations are slightly modified by
introducing the volume flux and a diffusive flux
(Kedem and Katchalsky 1961).
The dissipation function for the Eqs. 9 and 10
is given by:
(8)


¼ J w d V w p þ RT ln aw


þ J s d V s p þ RT ln as (11)
Here, c is the dissipation function, J is the flux, a,
m, and V are the activity, the chemical potential,
and the partial molar volume, and p is the hydro-
static pressure, the subscripts w and s refer to
solvent and solute.
Assuming a linear relation for the chemical
potential gradients and introducing the osmotic
4 The Principle of Reverse Osmosis (RO)

pressure for the activities of the water and solute ðJ v ÞDp¼0 ¼ LpD Dp (19)
integration of Eq. 11 lead to:

 Assuming that there is no osmotic pressure dif-
C ¼ J w V w þ J s V s Dp ference, i.e., Dp = 0, then the diffusive flux is
  given by:
Js
þ  J w V w Dp
Cs
ðJ D ÞDp¼0 ¼ LDp Dp (20)
¼ J v Dp þ J D Dp (12)
and the volume flux is given by:
Introducing a volume and a diffusion flux given
by: ðJ v ÞDp¼0 ¼ Lp Dp (21)

Jv ¼ JwVw þ JsVs (13) The hydrostatic pressure difference at zero vol-

ume flux, i.e., the osmotic equilibrium is given
and by:

Js LpD
JD ¼  VwJw (14) ðDpÞjv ¼0 ¼  Dp¼sDp (22)
Cs Lp

into the dissipation function results in: Here, s is the so-called Staverman reflection
coefficient which is a measure for the
C ¼ J v Dp þ J D Dp (15) permselectivity of a membrane.
Equation 22 shows that in osmotic equilibrium
The first term in Eq. 15 describes the total volume the hydrostatic pressure difference between two
flux Jv as function of the applied pressure, and the solutions separated by a membrane is equal to the
second term describes the diffusion flux of the osmotic difference Lp = LpD and therefore s =1.
salt JD. This is only the case for a strictly semipermeable
The new set of phenomenological equations membrane. Usually, the Staverman reflection
is: coefficient has values between 0 and 1.
If the volume flux is 0, the ratio of salt flux to
J v ¼ Lp Dp þ LpD Dp (16) osmotic pressure difference is given by:

and  
Js Cs Lp LD  L2pD
¼ ¼o (23)
Dp J v ¼0 Lp
J D ¼ LD p Dp þ LD Dp þ LD Dp (17)

By applying different experimental conditions to Here, o is the permeability of the salt.

the Eqs. 16 and 17, the phenomenological coeffi- Combing Eqs. 13, 14, 18, 22, and 23 leads to:
cients can be determined from experimental
measurements. J v ¼ Lp ðDp  sDpÞ (24)
Assuming no pressure difference is applied,
i.e., Dp = 0, then the diffusive flux is given by: and

ðJ D ÞDp¼0 ¼ L D Dp (18) J s ¼ Cs ð1  sÞJ v þ oDp (25)

Based on the phenomenological equations, the

and the volume flux is given by:
mass transport in reverse osmosis of a solution
of a single salt solution can be described by three
The Principle of Reverse Osmosis (RO)
coefficients, i.e., Lp the hydrodynamic permeabil-
ity of the membrane, o the salt permeability, and
s the reflection coefficient. All three coefficients
can be experimentally determined.
Comparing Eqs. 24 and 25 with Eqs. 5 and 6
which are based on the solution-diffusion model
that for membrane with high salt rejection, i.e.,
s  1 and when kinetic coupling between the
water and the salt flow is low which can be
assumed in most reverse osmosis membranes
the transport in reverse osmosis can adequately
be described by the solution-diffusion model.
5
References
Katchalsky A, Curran PF (1967) Nonequilibrium thermo-
dynamics in biophysics. Harvard University Press,
Cambridge, MA
Kedem O, Katchalsky A (1961) A physical interpretation
of the phenomenological coefficients of membrane
permeability. J Gen Physiol 45:143
Merten U (1966) Transport properties of osmotic mem-
branes. In: Merten U (ed) Desalination by reverse
osmosis. M.I.T. Press, Cambridge, MA, pp 15–54
Strathmann H, Giorno L, Drioli E (2006) An introduction
to membrane science and technology, chapter 2. CNR
Publisher, Roma. ISBN 88-8080-063-9
Onsager L (1931a) Reciprocal relations in irreversible
processes I, Phys. Rev. 37, 405
Onsager L (1931b) Reciprocal relations in irreversible
processes II, Phys. Rev. 38, 2265
A
Aged Carbon Membrane
Miki Yoshimune
Research Institute for Chemical Process
Technology, National Institute of Advanced
Industrial Science and Technology (AIST),
Tsukuba, Japan
If the use of high-performance carbon mem-
branes in gas separations is to be commercial-
ized, the aging characteristics of such
membranes will become important. Little work
has been done on studying this aspect of carbon
membranes, but some researchers have pointed
out that there are significant problems related to
the performance stability of carbon membranes
(Jones and Koros 1995a; Lagorsse et al. 2004,
2005; Saufi and Ismail 2004). Although they are
chemically and thermally resistant, carbon
membranes generally suffer deterioration in per-
formance upon exposure to substances that
become strongly adsorbed, such as water vapor
or oxygen. As carbon membranes have a sharp
pore-size distribution with a critical size ranging
from 0.3 to 0.7 nm, small changes in the effec-
tive size of the pore structures can markedly
affect their permeability toward adsorbing gas
molecules. In addition, constrictions in the pore
system can occur as a result of chemisorption of
oxygen or by strong adsorption of species having
very low diffusivity because of their
organophilic nature. Such species will block
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_909-1
the pores in the membrane and attenuate the
permeation of other species.
In a study of the effects of air oxidation and
humidity at room temperature on the aging of
carbon membranes, Menendez and Fuertes
(2001) found the membrane stored in dry or
humid air underwent a rapid loss of permeability,
whereas membranes stored under propene or
nitrogen were protected from damage. The
researchers suggested that chemisorption of oxy-
gen rather than physisorption of water is princi-
pally responsible for the loss of permeability that
occurs when a fresh carbon membrane is exposed
to air.
Jones and Koros (1994) found that carbon
membranes are highly vulnerable to adverse
effects of exposure to organic contaminants,
even at concentrations as low as 0.1 ppm.
Attempts to regenerate membranes after expo-
sure to hydrocarbons by high-temperature
(363 K) treatment in a vacuum were unsuccess-
ful. Jones and Koros (1995a) also studied the
effects of humidity on the O2/N2 selectivity and
permeability of a carbon membrane by using
feeds with relative humidities of 23–85 %.
Some losses in performance occurred at all
humidity levels, but this problem could be alle-
viated by rendering the surface of the membranes
hydrophobic by coating them with thin layers of
Teflon AF1600 or AF2400 (Jones and Koros
1995b). The resulting composite carbon mem-
branes were significantly protected from the
adverse effects of humidity.
2 Aged Carbon Membrane
Lagorsse et al. (2008) made a thorough inves-
tigation on the effects of exposure to air and
humidity on the performance of commercialized
carbon hollow fiber membranes, supplied by Car-
bon Membranes Ltd. (Israel). The production of
these membranes involved pyrolysis followed by
chemical vapor deposition and an activation step
(Lagorsse et al. 2004). The researchers found that
the membrane underwent a loss of permeability
with time when exposed to pure oxygen or to air;
however, the performance of the membrane ulti-
mately stabilized after prolonged exposure.
Attempts to regenerate the membranes by expo-
sure to flowing nitrogen at 343 K or by treatment
with propene and propyne as cleaning agents
resulted in no significant recovery of permeabil-
ity. However, no deterioration in permeability of
these membranes was observed when they were
stored under nitrogen. The researchers therefore
concluded that aging of carbon membranes is
caused exclusively by chemisorption of oxygen
from air. On the other hand, humidity adversely
affects the performance of membranes in
multicomponent separation processes because
water is strongly adsorbed, but diffuses relatively
easily through the membranes. Heating under an
atmosphere of hydrogen at 893 K to remove
surface oxygen groups had some effect on stable
surfaces protected from chemisorption of oxy-
gen. This treatment can be used to restore the
permeation properties to those of fresh
membranes.
These studies demonstrated that the effects of
aging are more pronounced when membranes are
stored under a high-humidity atmosphere and are
exposed to air. The chemisorption of oxygen
leads to the formation of C–O surface groups,
thereby creating a more hydrophilic interface
that favors increased adsorption of water.
Adsorbed species can reduce the pore size of the
carbon over time, leading to decreases in the
permeability and selectivity of the membrane.
Therefore, studies on the stability of carbon
membranes will be an important aspect on
research on such membranes in the future.
References
Jones CW, Koros WJ (1994) Carbon molecular sieve gas
separation membranes. II. Regeneration following
organic exposure. Carbon 32:1427–1432
Jones CW, Koros WJ (1995a) Characterization of
ultramicroporous carbon membranes with humidified
feed. Ind Eng Chem Res 34:158–163
Jones CW, Koros WJ (1995b) Carbon composite mem-
branes: a solution to adverse humidity effects. Ind Eng
Chem Res 34:164–167
Lagorsse S, Magalhães FS, Mendes A (2004) Carbon
molecular sieve membranes: sorption, kinetic and
structural characterization. J Membr Sci 241:275–287
Lagorsse S, Campo MC, Magalhães FD, Mendes A (2005)
Water adsorption on carbon molecular sieve mem-
branes. Experimental data and Isotherm model. Car-
bon 43:2769–2779
Lagorsse S, Magalhães FD, Mendes A (2008) Aging study
of carbon molecular sieve membranes. J Membr Sci
310:494–502
Menendez I, Fuertes AB (2001) Aging of carbon mem-
branes under different environments. Carbon
39:733–740
Saufi SM, Ismail AF (2004) Fabrication of carbon mem-
branes for gas separation—a review. Carbon
42:241–259
P
Pectins, Recovery of
Katalin Belafi-Bako
Research Institute of Bioengineering, Membrane
Technology and Energetics, University of
Pannonia, Veszprem, Hungary
Pectins occur in the plant tissues; its recovery
means a combined process involving extraction
and separation (clarification, purification, and
concentration). In the separation steps, mem-
brane processes (mainly ultrafiltration) can be
widely applied.
In the commercial pectin extraction process,
citrus peels and apple pomace are used as raw
materials. However pectin recovery from agro-
wastes would be more beneficial, since it is not
only important from the environmental protec-
tion point of view (waste minimalization), but it
may contribute to the more economical produc-
tion. The potential pectin-rich agro-wastes are,
e.g. cocoa husks, sunflower head, peach pomace,
peels of mango, etc. Recently wastes of berry
fruit (red and black current, blackberry, elder-
berry, etc.) processing have been studied
(Belafi-Bako et al. 2012).
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_926-2
Extraction of pectic substances can be carried
out by hot aqueous (acidic or neutral) solution in
high temperature. It takes quite long (appr.
10–12 h). To improve the process, microwave
technique can be applied (Fishmann et al. 2006).
As a result of the extraction (from, e.g., the
berry press cakes by boiling water), majority of
the pectic polysaccharides can be obtained in the
aqueous phase. Ultrafiltration can be used then to
clarify the extracted solution, and the diluted
aqueous pectin solution may be concentrated
partly by membranes (e.g., ultrafiltration, or
nanofiltration, or reverse osmosis) up to 5 %
total solid substance (TSS), partly by evaporation
up to 30 % TSS. Then pectin in powder form can
be obtained from the concentrated pectic solution
after precipitation with ethyl alcohol.
References
Belafi-Bako K, Cserjesi P, Beszedes S, Csanadi Z, Hodur
C (2012) Berry pectins: microwave-assisted extraction
and rheological properties. Food Bioprocess Technol
5:1100–1105
Fishmann ML, Chau HK, Hoagland PD, Hotchkiss AT
(2006) Microwave-assisted extraction of lime pectin.
Food Hydrocoll 20:1170–1177
www.encyclopedia.com/topic/pectin.aspx
P
Pectin Hydrolysis and Membrane
Operations
Katalin Belafi-Bako
Research Institute of Bioengineering, Membrane
Technology and Energetics, University of
Pannonia, Veszprem, Hungary
Hydrolysis of pectin can be carried out by
pectinase enzymes that are classified into three
main groups (Pilnik and Voragen 1993):
• Pectinesterases – catalyzing de-esterification
of the methoxyl group of pectin
• Depolymerizing hydrolytic enzymes
(including polymethyl-galacturonases and
polygalacturonases) – catalyzing the hydro-
lytic cleavage of 1,4-glycosidic bonds
• Lyases – catalyzing the cleavage of glycosidic
bond by transelimination
Among the pectin hydrolyzing enzymes,
(endo)polygalacturonases (PG, E.C. 3.2.1.15.)
play a key role in the process. Regarding the
kinetics it was found that PG enzyme from Asper-
gillus niger was inhibited by its monomeric prod-
uct, galacturonic acid. The Michaelis-Menten
model completed with competitive product inhi-
bition describes properly the process.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_928-4
To avoid product inhibition in hydrolysis of
pectin, the inhibiting product should be removed
by, e.g., a membrane separation. Ultrafiltration
membranes provide proper separation since the
small inhibitory product molecule (galacturonic
acid) can easily pass through the membrane and
be removed continuously from the system, while
the large molecules (substrate and enzyme) are
retained by the membrane. The enzymatic reac-
tion and the membrane separation can be carried
out simultaneously in the same setup, which is
called membrane bioreactor (Belafi-Bako
et al. 2007; Kiss et al. 2009). In this way higher
yields and efficiency can be achieved.
Pectolytic enzymes have been used for long in
the fruit processing industry to increase yields, to
improve liquefaction and clarification (Pilnik and
Voragen 1993), and moreover to produce
D-galacturonic acid (monomer of pectin), which
is an important compound, raw material in the
food, pharmaceutical, and cosmetic industry to
manufacture, e.g., vitamin C or acidifying,
tensioactive agents.
References
Belafi-Bako K, Eszterle M, Kiss K, Nemestothy N,
Gubicza L (2007) Hydrolysis of pectin by Aspergillus
niger polygalacturonase in a membrane bioreactor.
J Food Eng 78:438–442
2 Pectin Hydrolysis and Membrane Operations

Kiss K, Nemestothy N, Gubicza L, Belafi-Bako K (2009) Pilnik W, Voragen AGJ (1993) Pectic enzymes in fruit
Vacuum assisted membrane bioreactor for enzymatic juice and vegetable juice manufacture. In: Reeds G -
hydrolysis of pectin from various sources. Desalina- (ed) Food and science technology, enzymes in food
tion 241:29–33 processing. Academic, New York, pp 363–399
P
Pectins
Katalin Belafi-Bako
Research Institute on Bioengineering, Membrane
Technology and Energetics, University of
Pannonia, Veszprem, Hungary
Pectin is a general term for various polysaccha-
rides. According to a standard nomenclature
(Nelson et al. 1977), pectic substances are a
group of complex, colloid carbohydrate polymers
which are present and recovered from plant tis-
sues and consist of mainly galacturonic acid as
monomer (Walter 1991). Regarding structure,
three different pectic polysaccharides can be dis-
tinguished: homogalacturonan (HGA) and
rhamnogalacturonans I and II (RGs I and II).
HGA is a linear polymer consisting of
D-galacturonic acid monomers. The backbone
of RG I is built from rhamnose and galacturonic
acid alternately, while the main bone of RG II is
composed of linear oligogalacturonic acid
sequences (eight to ten monomers), where vari-
ous monosaccharides are coupled to, resulting in
a complex, branching polymer. The galacturonic
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_929-4
acid units may occur in a free acid form, esterified
by methanol, or as a salt formed with Na+, K+,
and NH4+; moreover it may contain acetyl groups
coupled to the OH groups. The composition of
pectins (galacturonic acid content, molecular
weight, methylation, acylation degree, etc.)
depends on the source, i.e., pectins from citrus
fruits have low esterification degree.
Pectin is widely used as thickening, gelling,
and emulsifying additive in food, cosmetic, and
pharmaceutical industries (Walter 1991).
Cross-References
▶ Pectin Hydrolysis and Membrane Operations
▶ Pectins
References
Nelson DB, Smit CJB, Wiles RR (1977) Commercially
important pectic substances. In: Graham HD (ed) Food
colloids. AVI, Westport, pp 418–437
Walter RH (1991) The chemistry and technology of pec-
tin. Academic, New York
C
Cellulase in Membrane Bioreactors
Katalin Belafi-Bako
Research Institute of Bioengineering, Membrane
Technology and Energetics, University of
Pannonia, Veszprem, Hungary
Membrane reactors have been developed mainly
for catalytic reactions, using various membrane
modules (e.g., flat sheet, hollow fibers). If
biocatalysts (enzymes or cells) are applied, the
equipments can be operated as membrane bio-
reactors (Drioli and Giorno 1999). One of the
main advantages of the membrane bioreactors is
that they make recovery and reuse of biocatalysts
possible.
Usage of membrane bioreactors is especially
beneficial for polymer degradation processes,
where the small size product may have inhibitory
effect, but can be separated easily by a proper
porous membrane. This is the case of enzymatic
hydrolysis of polysaccharides, like cellulose or
starch. The long polysaccharide chain as well as
the biocatalyst (enzyme or cell) are rejected by
the membrane, while the product (glucose)
passes through the membrane into the other
phase. In such a system, continuous uptake of
substrate and release of product without loss of
biocatalysts can be achieved.
The huge amount of biomass produced annu-
ally worldwide is mainly composed of cellulose;
its application for various purposes (industrial
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_930-3
raw material, bioethanol, etc.) is extremely
important nowadays. In these cases cellulose
should be degraded by hydrolysis, resulting in
glucose (monomer of cellulose). Enzymatic cel-
lulose hydrolysis is carried out by various
cellulases.
In general, hydrolysis of cellulose is more
difficult to achieve than that of the other poly-
saccharides. The process is influenced by three
main factors: the nature of the enzymes; the
structure of the substrate; and the enzyme-
substrate interactions (Mansfield et al. 1999).
The action of the cellulase enzyme system
includes three main groups: endoglucanases,
cellobiohydrolases, and cellobiases (ß-glucosidase).
These enzymes work in a synergistic mode to
degrade cellulose, therefore it would be more
effective to apply the whole complex enzyme
system. One of the most effective cellulase
systems can be obtained from the fungus
Trichoderma reesei.
The main difficulty in cellulose hydrolysis is
attributed to the dual nature of the substrate. The
accessibility of the crystalline and amorphous
regions is different; moreover, the solubility of
the substrate is limited.
Finally in the enzyme-substrate interactions, it
should be considered that hydrolysis of cellulose
is a surface phenomenon. Before the reaction
itself, the enzyme has to be bound to the sub-
strate, i.e., the process requires the adsorption of
the biocatalyst onto the insoluble substrate prior
to the hydrolysis.
2 Cellulase in Membrane Bioreactors
In a recent work, a membrane bioreactor was
used with a hairy membrane layer (Bélafi-Bakó
et al. 2006) that offered a special surface area for
simultaneous adsorption of the substrate and
enzyme. In this way the cellulose-cellulase layer
formed provided a further advantage: diffusion
resistance between the substrate and enzyme was
reduced. Since solid particles present might cause
troubles (fouling), it required special conditions
for the construction of the membrane reactor. To
avoid blockage, tubular type membrane module
was used in the experiments. The simultaneous,
reversible immobilization of the biocatalyst and
the substrate onto the membrane surface was
found to improve the efficiency of the process.
References
Bélafi-Bakó K, Koutinas A, Nemestóthy N, Gubicza L,
Webb C (2006) Continuous enzymatic cellulose
hydrolysis in a tubular membrane bioreactor. Enzyme
Microb Technol 38:155–161
Drioli E, Giorno L (1999) Biocatalytic membrane reac-
tors. Taylor and Francis Group, London
Mansfield SD, Mooney C, Saddler JN (1999) Substrate
and enzyme characteristics that limit cellulose hydro-
lysis. Biotechnol Prog 15:804–816
D
Dealcoholization by Pervaporation
Shota Ando, Shuichi Sato and Kazukiyo Nagai
Department of Applied Chemistry, Meiji
University, Tama-ku, Kawasaki, Japan
Dealcoholization by pervaporation (PV) is one of
the most innovative processes for the selective
separation and condensation of ethanol from a
dilute aqueous solution of ethanol obtained from
biomass fermentation (about 10 wt%) using PV
method. The energy for bioethanol that is pro-
duced using distillation requires approximately
1.5 times than that obtained from ethanol fuel.
Among them, about 70 % is estimated to be
consumed in distillation. Thus, dealcoholization
by PV is efficient because of energy conservation
and separation of an azeotropic mixture, which
cannot be separated by distillation. In PV, a liquid
mixture is supplied to a membrane on one side.
The permeated components are evaporated from
the other side (Fig. 1). Thus, the driving force of
this process is a gradient of partial pressure or
chemical potential located across a membrane.
To enhance the flux or the total amount of the
product, the permeated side is always maintained
at a pressure below the saturated pressure of a
given component, either under a vacuum or by
sweeping the vapor using a carrier gas. The vapor
at the permeated side is then condensed and
recovered as liquid (Nagai 2010). The features
of this method are: (1) increased separation
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_934-1
performance from solution, diffusion, and vapor-
ization; (2) the driving force of permeation does
not depend on the pressure and is applicable to
the organic liquid solution with high osmotic
pressure; (3) PV does not need pressurization;
(4) this method can be applied to separate the
mixture solution, which cannot be done by distil-
lation, for example, the separation of the thermal
denaturation/thermally decomposable mixture,
azeotropic mixture, near-boiling point mixture,
and structural/optical isomers can be concen-
trated; (5) the reaction can be promoted because
of the movement of the equilibrium reaction; and
(6) the method does not pressurize, and no con-
solidation of the membrane occurs. The term PV
is a compound word of Permeation and Evapora-
tion. Moreover, it has been originated from the
article of Kober (1917). There are two kinds of
method for alcohol concentration by PV. The
alcohol-selective method removes alcohol from
the dilute alcohol aqueous solution of concen-
trated alcohol, whereas the water-selective
method removes water at a high-concentrated
alcohol solution. The materials differ according
to their use. The alcohol-selective method uses
silicone gum and poly(1-trimethylsilyl-1-
propyne). By contrast, the water-selective
method uses cellulose acetate and poly
(phenylene oxide), which yield good results.
Generally, the alcohol-selective method is called
dealcoholization by PV. Researches on alcohol-
selective permeable membranes are fewer than
those on water-selective permeable membranes.
2 Dealcoholization by Pervaporation
Dealcoholization by
Pervaporation,
Fig. 1 Dealcoholyzation
by a pervaporation process
In addition, membranes with performance that
can be set in bench-scale plants have not been
developed. Thus, the developments of alcohol-
selective permeable membranes are delayed
compared with that of water-selective mem-
branes. The cause is due to the larger molecular
size of alcohol molecules, which are permeated
preferentially, compared with that of water mol-
ecules. When alcohol from alcohol aqueous solu-
tion is permeated preferentially, separation on the
diffusion process cannot be expected in PV
method based on a solution-diffusion mecha-
nism. Thus, separation can be performed using
the difference in the only solution process of both
components of the membrane. However, the
membrane is excessively swelled by very high
affinity to alcohol because it is in direct contact
with the mixture solution to be separated in PV
method. Thus, permeability increases. However,
the small molecular size of water enters the
membrane by the plasticizing effect because of
membrane swelling, which significantly reduces
the selectivity to alcohol. To solve this problem,
the balance of hydrophobicity and affinity of the
membrane is examined by graft, copolymers,
multiblock, blend, and three dimensional struc-
tures by cross-link. In each case, there is a limit to
improvement in separation performance by pre-
vious method because there is a discrepancy
between affinity and swelling.
References
Kober PA (1917) Pervaporation, perstillation and
percrystallization. J Am Chem Soc 39:944–948
Nagai K (2010) Fundamentals and perspectives for
pervaporation. In: Enrico D, Lidietta G (eds) Compre-
hensive membrane science and engineering, 1st edn.
Elsevier, Amsterdam, pp 243–271
A
Antioxidant Recovery by
Membranes
Laurent Bazinet
Department of Food Sciences, Université Laval,
Quebec, QC, Canada
Antioxidants and Membrane Processes
Antioxidants are natural or synthesized sub-
stances that inhibit or retard the oxidation of
other molecules (fat, oil, food, petroleum
product. . .) (Focke et al. 2012; Rozoy
et al. 2012; Roblet et al. 2012). However, for
natural antioxidants, which are present in com-
plex matrices, their separation and purification
are required. Indeed, they must be separated
from the feedstock in order to increase their
purity and antioxidant capacity.
Membrane processes are the main processes
used for the separation of antioxidant molecules.
Membranes are selective barriers that allow for
the transmission of certain feed components
while retaining other components. Membrane
technology can be used to concentrate and/or
selectively fractionate bioactive compounds
with antioxidant activity from aqueous and alco-
holic processing streams of products,
by-products, and wastes from agro-food industry
(Diaz-Reinoso et al. 2011). It is important to note
that, when compared with other concentration
methods (evaporation, spray drying. . .), during
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_938-3
membrane processes the product is not subjected
to high temperatures and there is no change in the
physical state of the solvent, meaning that the
functional properties of the compounds of inter-
est are preserved and the process as a whole is
energy saving (Negrao Murakami et al. 2011).
Membrane Processes and Applications
to Antioxidant Recovery
On a large production scale, pressure-driven
membrane technologies and electrically driven
membrane technologies have been developed to
improve the efficiency of antioxidant production
(Table 1).
Pressure-Driven Membrane Processes
Pressure-driven membrane technologies are
often used in the food industry to isolate antiox-
idant molecules such as specific peptides or pep-
tide fractions (Bazinet and Firdaous 2012;
Pouliot et al. 2000; Tessier et al. 2006a, b;
Vandanjon et al. 2009) and phenolic compounds
(Nawaz et al. 2006; Kalbasi and Cisneros-
Zevallos 2007; Mello et al. 2010; Tylkowski
et al. 2010). Pressure is the main driving force
for these processes. The pressure used depends on
the pore size of the filtration membrane and has to
be adjusted as a function of the concentration rate
desired. Pressure-driven membrane processes
comprise microfiltration (MF), ultrafiltration
(UF), nanofiltration (NF), and reverse osmosis
2 Antioxidant Recovery by Membranes

Antioxidant Recovery by Membranes, Table 1 Membrane processes for separation/concentration of different types
of antioxidants
Driving force Membrane process Antioxidants References
Pressure-driven Microfiltration Tocopherols (de Souza et al. 2008)
membrane and
processes tocotrienols
Phenols (Russo 2007; Laorko et al. 2010)
Organic (Laorko et al. 2010)
acids
Ultrafiltration Phenols (Russo 2007; Laorko et al. 2010; El-Abbassi 2012;
Borneman et al. 2001; Cassano et al. 2008; Cissé
et al. 2011; Conidi et al. 2011; Nawaz et al. 2006; Li
et al. 2005)
Organic (Cassano et al. 2006)
acids
Peptides (Bouhallab and Touzé 1995; Lajoie et al. 2001;
Vandanjon et al. 2007)
Nanofiltration Tocopherols (Subramanian et al. 1998a, b, 2003)
Phenols (Cissé et al. 2011; Negrao Murakami et al. 2011; Mello
et al. 2010; Conidi et al. 2011)
Peptides (Vandanjon et al. 2007; Fenton-May et al. 1971;
Tessier et al. 2006b)
Electrically Electrodialysis Phenols (Bazinet et al. 2005)
driven membrane Organic (Vera Calle et al. 2003)
processes acids
Electrodialysis Organic (Vera Calle et al. 2002)
with bipolar acids
membranes
Electrodialysis Phenols (Labbé et al. 2005; Bazinet et al. 2009, 2012)
with filtration Organic (Bazinet et al. 2012)
membranes acids
Peptides (Langevin et al. 2012)

(RO). The solution properties, charges of ionic
species and the type of membrane used, affect the
behavior and the efficiency of the separation
method (Martin-Orue et al. 1998). Working at
low concentration is preferable to avoid the for-
mation of a polarization layer which could affect
selectivity of the membrane (Shahidi 2004).
For the separation of tocopherols and
tocotrienols, only MF (de Souza et al. 2008)
and NF (Subramanian et al. 1998a, b, 2003)
were reported. For phenols recovery, MF was
used on vegetation waters (VW) (Russo 2007)
and pineapple juice (Laorko et al. (2010). The
authors showed that MF did not affect signifi-
cantly the pH, reducing sugar and acidity of clar-
ified juice whereas the suspended solids and
microorganism were completely removed. UF
was studied on different sources such as olive
mill wastewater (Russo 2007; El-Abbassi 2012),
fruit juices (Borneman et al. 2001; Cassano
et al. 2008; Laorko et al. 2010; Cissé
et al. 2011; Conidi et al. 2011), grape seeds
(Nawaz et al. 2006), and green tea
(Li et al. 2005). NF was tested on roselle extract
(Cissé et al. 2011), on mate (Negrao Murakami
et al. 2011), on aqueous propolis extract (Mello
et al. 2010), and on bergamot juice (Conidi
et al. 2011). Organic acids such as Ascorbic,
isoascorbic, folic, and citric acids can also be
recovered by filtration process. Hence, MF was
used for the recovery of ascorbic acid (Laorko
et al. 2010), while UF was tested on kiwifruit
Antioxidant Recovery by Membranes
juice to recover folic, ascorbic, and citric acids
(Cassano et al. 2006). Concerning antioxidant
peptides, they are separated into fractions using
membranes in the range 1–10 kDa (Je et al. 2005;
Jeon et al. 1999; Rajapakse et al. 2005). NF can
be used to concentrate hydrolysates (Vandanjon
et al. 2007; Fenton-May et al. 1971; Tessier
et al. 2006b) whereas UF membranes with high
MWCO (20–100 kDa) are adapted to the separa-
tion of peptides and nonhydrolyzed proteins or
proteolytic enzymes (Bouhallab and Touzé 1995;
Lajoie et al. 2001). On the other hand, UF mem-
branes with intermediate molecular weight cut-
offs (about 4000–8000 Da) allow hydrolysates to
be fractionated with the result of enrichment in
some ranges of molecular weight (Vandanjon
et al. 2007). The use of integrated membrane
system (UF/MF/RO, MF/NF, . . .) is becoming
another real alternative to recover, purify, or con-
centrate antioxidants as it is established in some
recent works (Paraskeva et al. 2007; Russo 2007;
Garcia-Castello et al. 2010; Conidi et al. 2011;
Diaz-Reinoso et al. 2011).
Electrically Driven Membrane Processes
Electrically driven processes, like electrodialysis
(ED) and hybrid processes (ED with bipolar
membranes (EDBM) and ED with filtration
membranes (EDFM)), use ion-exchange mem-
branes and/or filtration membrane to separate
molecules (Bazinet 2005). The electric field is
the main driving force involved in these pro-
cesses. Molecular transfer is mainly due to the
charge of the molecule and the flux depends on
the strength of the electric field (Poulin
et al. 2007; Doyen et al. 2012).
Conventional electrodialysis has been tested
as a mean of selectively extracting polyphenols
from aqueous tobacco extracts (Bazinet
et al. 2005). High polyphenol migration rates
around 31.1–90.8 % were reported. EDFM a
new electrically driven technology has been
recently tested for the recovery of polyphenols.
EDFM was used on green tea to perform selec-
tive extraction of catechins (Labbé et al. 2005)
and on cranberry juice to enrich cranberry juice in
its own natural phenolic antioxidant compounds
(Bazinet et al. 2009, 2012). For organic acids
3
having antioxidant properties,Vera Calle
et al. (2003) were indirectly precursor in the use
of ED for the recovery of citric acid. In all the
deacidified juices, a decrease in the citrate and
malate concentrations was obtained. Vera Calle
et al. (2002) also tested the deacidification of
clarified passion fruit juice, by electrodialysis
with bipolar membrane (EDBM). Citric acid
was formed in the concentrate compartment by
citrate ions extracted from juice and protons pro-
vided by the BM separating the concentrate and
electrode compartments. This configuration
allowed the production of citric acid with 89 %
purity. During EDFM of cranberry juice, Bazinet
et al. (2012) observed that enriched juice concen-
trations in citric and malic acids decreased
respectively of 7.3 % and 4.7 % resulting in a
significant decrease of its sour taste intensity, a
major problem for cranberry juice producer.
However, the concentration in the raw juice was
not significant due to the high ratio of raw juice/
enriched juice. Very recently, a combination of
UF membrane stacked in an electrodialysis cell
was tested successfully for the selective separa-
tion of anionic and cationic antioxidant peptides
(Langevin et al. 2012). The results showed only a
significant increase in the antioxidant capacity
for anionic peptide fractions recovered at pH 3
and pH 6 compared to the feed hydrolysate
(Langevin et al. 2012). In the comparative study
of Langevin et al. (2012), it was demonstrated
that NF was more efficient in terms of mass flux
than EDFM when compared on a same basis
(membrane area, process duration), but EDFM
recovered larger range of peptide molecular
weights and amount of polar amino acids.
References
Bazinet L (2005) Electrodialytic phenomena and their
applications in the dairy industry: a review. Crit Rev
Food Sci Nutr 44:525–544
Bazinet L, Firdaous L (2013) Separation of bioactive
peptides by membrane processes: technologies and
devices. Recent Pat Biotechnol 7 (1): 9–27
Bazinet L, DeGrandpré Y, Porter A (2005)
Electromigration of tobacco polyphenols. Sep Purif
Technol 41:101–107
4 Antioxidant Recovery by Membranes
Bazinet L, Cossec C, Gaudreau H, Desjardins Y (2009)
Production of a phenolic antioxidant enriched cran-
berry juice by electrodialysis with filtration mem-
brane. J Agric Food Chem 57:10245–10251
Bazinet L, Brianceau S, Dubé P, Desjardins Y (2012)
Evolution of cranberry juice physico-chemical param-
eters during phenolic antioxidant enrichment by elec-
trodialysis with filtration membrane. Sep Purif
Technol 87:31–39
Borneman Z, Gökmen V, Nijhuis HH (2001) Selective
removal of polyphenols and brown colour in apple
juices using PES/PVP membranes in a single ultrafil-
tration process. Sep Purif Technol 22–23:53–61
Bouhallab S, Touzé C (1995) Continuous hydrolysis of
caseinomacropeptide in a membrane reactor: kinetic
study and gram-scale production of antithrombotic
peptides. Lait 75:251–258
Cassano A, Figoli A, Tagarelli A, Sindona G, Drioli E
(2006) Integrated membrane process for the produc-
tion of highly nutritional kiwifruit juice. Desalination
189:21–30
Cassano A, Donato L, Conidi C, Drioli E (2008) Recovery
of bioactive compounds in kiwifruit juice by ultrafil-
tration. Innov Food Sci Emerg Technol 9:556–562
Cissé M, Vaillant F, Pallet D, Dornier M (2011) Selecting
ultrafiltration and nanofiltration membranes to concen-
trate anthocyanins from roselle extract (Hibiscus
sabdariffa L.). Food Res Int 44:2607–2614
Conidi C, Cassano A, Drioli E (2011) A membrane-based
study for the recovery of polyphenols from bergamot
juice. J Membr Sci 375:182–190
de Souza MP, Cunha Petrus JC, Guaraldo Gonçalves LA,
Viotto LA (2008) Degumming of corn oil/hexane
miscella using a ceramic membrane. J Food Eng
86:557–564
Dı́az-Reinoso B, Moure A, Domı́nguez H, Parajó JC
(2011) Membrane concentration of antioxidants from
Castanea sativa leaves aqueous extracts. Chem Eng
J 175:95–102
Doyen A, Saucier L, Beaulieu L, Pouliot Y, Bazinet L
(2012) Electroseparation of an antibacterial peptide
fraction from snow crab by-products hydrolysate by
electrodialysis with ultrafiltration membranes. Food
Chem 132:1177–1184
El-Abbassi A, Kiai H, Hafidi A (2012) Phenolic profile
and antioxidant activities of olive mill wastewater.
Food Chem 132:406–412
Fenton-May RI, Hill CG, Amundson CH (1971) Use of
ultrafiltration and reverse osmosis systems for the con-
centration and fractionation of whey. J Food Sci
36:14–21
Focke WW, van der Westhuizen I, Lofté Grobler AB,
Nshoane KT, Reddy JK, Luyt AS (2012) The effect
of synthetic antioxidants on the oxidative stability of
biodiesel. Fuel 94:227–233
Garcia-Castello E, Cassano A, Criscuoli A, Conidi C,
Drioli E (2010) Recovery and concentration of poly-
phenols from olive mill wastewaters by integrated
membrane system. Water Res 44:3883–3892
Je J-Y, Kim S-Y, Kim S-K (2005) Preparation and
antioxidative activity of hoki frame protein hydroly-
sate using ultrafiltration membranes. Eur Food Res
Technol 221:157–162
Jeon Y-J, Byun H-G, Kim S-K (1999) Improvement of
functional properties of cod frame protein hydroly-
sates using ultrafiltration membranes. Process
Biochem 35:471–478
Kalbasi A, Cisneros-Zevallos L (2007) Fractionation of
monomeric and polymeric anthocyanins from concord
grape (Vitis labrusca L.) juice by membrane ultrafil-
tration. J Agric Food Chem 55:7036–7042
Labbé D, Araya-Farias M, Tremblay A, Bazinet L (2005)
Electromigration feasibility of green tea catechins.
J Membr Sci 254:101–109
Lajoie N, Gauthier SF, Pouliot Y (2001) Improved storage
stability of model infant formula by whey peptides
fractions. J Agric Food Chem 49:1999–2007
Langevin M-E, Roblet C, Moresoli C, Ramassamy C,
Bazinet L (2012) Comparative application of pressure-
and electrically-driven membrane processes for isola-
tion of bioactive peptides from soy protein hydroly-
sate. J Membr Sci 403–404:15–24
Laorko A, Li Z, Tongchitpakdee S, Chantachum S,
Youravong W (2010) Effect of membrane property
and operating conditions on phytochemical properties
and permeate flux during clarification of pineapple
juice. J Food Eng 100:514–521
Li P, Wang Y, Ma R, Zhang X (2005) Separation of tea
polyphenol from green tea leaves by a combined
CATUFM-adsorption resin process. J Food Eng
67:253–260
Martin-Orue C, Bouhallab S, Garem A (1998)
Nanofiltration of amino acid and peptide solutions:
mechanisms of separation. J Membr Sci 142:225–233
Mello BCBS, Petrus JCC, Hubinger MD (2010) Concen-
tration of flavonoids and phenolic compounds in aque-
ous and ethanolic propolis extracts through
nanofiltration. J Food Eng 96:533–539
Nawaz H, Shi J, Mittal GS, Kakuda Y (2006) Extraction of
polyphenols from grape seeds and concentration by
ultrafiltration. Sep Purif Technol 48:176–181
Negrão Murakami AN, de Mello Castanho Amboni RD,
Prudêncio ES, Amante ER, de Moraes Zanotta L,
Maraschin M, Cunha Petrus JC, Teófilo RF
(2011) Concentration of phenolic compounds in aque-
ous mate (Ilex paraguariensis A. St. Hil) extract
through nanofiltration. LWT Food Sci Technol
44:2211–2216
Paraskeva CA, Papadakis VG, Tsarouchi E,
Kanellopoulou DG, Koutsoukos PG (2007) Membrane
processing for olive mill wastewater fractionation.
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Poulin J-F, Amiot J, Bazinet L (2007) Improved peptide
fractionation by electrodialysis with ultrafiltration
membrane: influence of ultrafiltration membrane
stacking and electrical field strength. J Membr Sci
299:83–90
Antioxidant Recovery by Membranes
Pouliot Y, Gauthier SF, L’Heureux J (2000) Effect of
peptide distribution on the fractionation of whey pro-
tein hydrolysates by nanofiltration membranes. Lait
80:113–120
Rajapakse N, Mendis E, Jung W-K, Je J-Y, Kim S-K
(2005) Purification of a radical scavenging peptide
from fermented mussel sauce and its antioxidant prop-
erties. Food Res Int 38:175–182
Roblet C, Amiot J, Lavigne C, Marette A, Lessard M,
Jean J, Ramassamy C, Moresoli C, Bazinet L (2012)
Screening of in vitro bioactivities of a soy protein
hydrolysate separated by hollow fiber and spiral-
wound ultrafiltration membranes. Food Res Int
46:237–249
Rozoy E, Simard S, Liu Y, Kitts D, Lessard J, Bazinet L
(2012) The use of cyclic voltammetry to study the
oxidation of l-5-methyltetrahydrofolate and its preser-
vation by ascorbic acid. Food Chem 132:1429–1435
Russo C (2007) A new membrane process for the selective
fractionation and total recovery of polyphenols, water
and organic substances from vegetation waters (VW).
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Shahidi F (2004) Functional foods: their role in health
promotion and disease prevention. J Food Sci
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Subramanian R, Nakajima M, Kawakatsu T (1998a)
Processing of vegetable oils using polymeric compos-
ite membranes. J Food Eng 38:41–56
Subramanian R, Nakajima M, Kimura T, Maekawa T
(1998b) Membrane process for premium quality
expeller-pressed vegetable oils. Food Res Int
31:587–593
5
Subramanian R, Raghavarao KSMS, Nakajima M,
Nabetani H, Yamaguchi T, Kimura T (2003) Applica-
tion of dense membrane theory for differential perme-
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Tessier B, Harscoat-Schiavo C, Marc I (2006a) Contribu-
tion of electrostatic interactions during fractionation of
small peptides complex mixtures by UF/NF mem-
branes. Desalination 200:333–334
Tessier B, Harscoat-Schiavo C, Marc I (2006b) Selective
separation of peptides contained in a rapeseed
(Brassica campestris L.) protein hydrolysate using
UF/NF membranes. J Agric Food Chem 54:3578–3584
Tylkowski B, Trusheva B, Bankova V, Giamberini M,
Peev G, Nikolova A (2010) Extraction of biologically
active compounds from propolis and concentration of
extract by nanofiltration. J Membr Sci 348:124–130
Vandanjon L, Johannsson R, Derouiniot M, Bourseau P,
Jaouen P (2007) Concentration and purification of blue
whiting peptide hydrolysates by membrane processes.
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Vandanjon L, Grignon M, Courois E, Bourseau P, Jaouen P
(2009) Fractionating white fish fillet hydrolysates by
ultrafiltration and nanofiltration. J Food Eng 95:36–44
Vera Calle E, Ruales J, Dornier M, Sandeaux J,
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C
Ceramic Membranes
Bo Wang
Department of Chemical Engineering, Imperial
College London, London, UK
Ceramic membranes are made of ceramic mate-
rials, and to be specific, they must undergo a high-
temperature sintering process to fall into the
“ceramic membranes” category. Ceramic mem-
branes belong to “inorganic membranes” category
and need to be distinguished with other types such
as metallic membranes or other hybrid inorganic
membranes.
Membrane Types
Ceramic membranes can be divided to two types:
porous and dense. Porous ceramic membranes
have found their industrial usages in various fil-
tration processes, while dense membranes are still
at stages not more than pilot plants.
Porous ceramic membranes separate sub-
stances based on size exclusion; therefore, they
can be further categorized as microfiltration, ultra-
filtration, and nanofiltration membranes
according to the pore size. Dense ceramic mem-
branes separate one or two particular species
(usually oxygen or hydrogen) based on the ionic
conductivity of membrane materials, and they
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_940-1
often need to be used at high temperatures to
increase their ionic conductivity.
Membrane Materials
Porous ceramic membranes are usually used in
liquid filtration processes and mostly in aqueous
environments; therefore, the membrane material
must be compatible with water aside from proper
mechanical strength. Most commonly used mem-
brane materials are alumina, titanium oxide, zir-
conia, and silicon carbide. Alumina is
predominant among all ceramic membrane mate-
rials because of its availability and relatively low
cost, and it also provides strong mechanical prop-
erties, inert chemical nature, good thermal stabil-
ity, and good surface hydrophilicity to the
membranes. Zirconia or stabilized zirconia gives
similar membrane characteristics as alumina
membranes but much better mechanical proper-
ties; however, their price is also higher. Titanium
oxide has better hydrophilicity and hydrothermal
stability than alumina and zirconia, but its
mechanical strength is moderate; therefore, tita-
nium oxide is normally used only for the separa-
tion layer supported by alumina membrane
supports. Silicon carbide membranes are more
permeable than other ceramic materials and they
often give impressive fluxes, but the major issue is
the fabrication cost, which is much higher than
others, due to the expensive raw material and
2 Ceramic Membranes
extremely high sintering temperatures, as well as
the protecting atmosphere required for sintering.
Dense ceramic membranes are used at high
temperatures, and these membranes normally are
made of ion-conductive materials or mixed ion
and electron-conductive materials. For the former
ones, an external circuit is needed to pass elec-
trons to compensate the charge of ionic species
when ions move from one side to the other side,
and work can be done within the external circuit.
This is the principle of solid oxide fuel cells
(SOFCs), and the dense membrane acts as the
electrolyte in a SOFC. For the later ones, electrons
can pass the membrane directly, and separation of
gas species can be completed by its own. The
most important category of ion-conductive mate-
rials is oxygen–ion conductor, for example, fluo-
rite type oxides including fully stabilized zirconia
and doped ceria, which are commonly used in
SOFC, and perovskite type oxides that can be
used alone to separate pure oxygen from air at
high temperatures. Another important category is
proton conductor, which also have attracted wide
interests to use them in SOFC and high-
temperature hydrogen separation.
Membrane Structure and Fabrication
Most ceramic membranes use asymmetric struc-
tures to obtain good strength and high permeation
fluxes, especially for porous membranes,
although symmetric structures are also found in
dense ceramic membranes. In an asymmetric
structure, a relatively thick and porous ceramic
supporting layer is used, which is the source of
mechanical strength of the membrane, and a thin
separating layer is coated/deposited onto the sup-
port to provide selectivity for the membrane.
The supporting layer can be formed by extru-
sion, or by pressing, followed by partial sintering.
The support is then coated/deposited with a
desired separating layer. Different coating/depo-
sition techniques have been developed for
different purposes, such as dip coating and wash
coating, sol–gel process, and chemical or physical
vapor deposition techniques.
Applications
Porous ceramic membranes have been commonly
used in water and wastewater treatment, food and
beverage processing, pharmaceuticals, and chem-
ical processing. The most widely used membrane
types are microfiltration and ultrafiltration mem-
branes, although the demand of nanofiltration
ceramic membranes is also increasing in recent
years.
Dense ceramic membranes have not really
found their industrial usages, but some pilot plants
of oxygen permeable ceramic membranes with a
considerable scale are running in the USA and
Europe, and some commercial SOFC products
are also available in the market. Some key techni-
cal obstacles need to be addressed before these
dense ceramic membranes and the membrane-
based technologies can enter into industrial
usages, such as high-temperature sealing and sys-
tem stability.
References
Armstrong PA (2015) Development of ITM oxygen tech-
nology for integration in IGCC and other advanced
power generation. United States. doi:10.2172/
1224800. http://www.osti.gov/scitech/servlets/purl/
1224800
Kneer R, Toporov D, Forster M, Christ D, Broeckmann C,
Pfaff E, Zwick M, Engels S, Modigell M (2010)
OXYCOAL-AC: towards an integrated coal-fired
power plant process with ion transport membrane-
based oxygen supply. Energy Environ Sci 3(2):198–
207
Pfaff EM, Kaletsch A, Broeckmann C (2012) Design of a
mixed ionic/electronic conducting oxygen transport
membrane pilot module. Chem Eng Technol 35(3):
455–463
D
DuraMem™ Membrane
Ludmila Georgieva Peeva
Imperial College London, London, UK
DuraMemTM is a range of highly stable organic
solvent nanofiltration (OSN) membranes
manufactured by Evonik – Membrane Extraction
Technology Ltd. (www.duramem.evonik.com).
Membranes are of integral asymmetric type and
are based on cross-linked polyimide (PI) (Great
Britain 2007; Toh et al. 2007). These membranes
are available in formats of flat sheets and spiral-
wound membrane modules within different
molecular weight cutoff range
(150–900 g mol 1) and possess excellent stability
in most of the organic solvents including polar
aprotic solvents such as dimethylformamide
(DMF) and N-methylpyrrolidone (NMP). The
membranes have a spongelike structure (Fig. 1)
and are usable in acetone, ethanol, methanol,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_949-1
tetrahydrofuran, dimethylformamide, dimethyl
sulfoxide, dimethylacetamide, isopropanol, ace-
tonitrile, methyl ethyl ketone, ethyl acetate, and
others (www.duramem.evonik.com). The mem-
branes have been operated continuously for 120 h
in DMF and THF and showed stable fluxes and
good separation performances, with DMF perme-
ability in the range of 1–-
8  10 5Lm 2h 1Pa 1(1–8 Lm 2h 1bar 1)
(Toh et al. 2007). Possible re-imidization and
loss of cross-linking at elevated temperatures
limit their range of application to temperatures
<50  C. The membranes can be operated in a
pressure range of 20–60 bar (290–870 psi).
References
Great Britain 2437519 (2007)
Toh YH, Lim FW, Livingston AG (2007) Polymeric mem-
branes for nanofiltration in polar aprotic solvents.
J Membr Sci 301:3–10
2 DuraMem™ Membrane

DuraMem™ Membrane, Fig. 1 A typical SEM micrograph of a cross section (left) and top separating layer (right) of
cross-linked PI membranes (Adapted from Toh et al. (2007))
M
Membrane Based Solvent Extraction
Lidietta Giorno
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, National
Research Council of Italy, Rende (CS), Calabria,
Italy
Synonyms
Liquid-liquid membrane extraction
In membrane based solvent extraction (MBSE)
two immiscible phases are in contact with a
porous membrane. One of the two phases wets
the membrane whilst the other does not wet it
(Fig. 1).
In membrane-based solvent extraction mass-
transfer between two immiscible solvents occurs
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_950-1
from the liquid/liquid interface immobilized at the
pore mouth of the microporous membrane that is
not wetted by one of the phases in contact. In this
way, dispersion of the liquid phase into the other is
prevented. Microfiltration or ultrafiltration mem-
branes are usually used as support to immobilize
the interface between the two immiscible phases.
In membrane based solvent extraction the mem-
brane has no selective properties, it only serves as
support for the immobilization of the interface.
Basic information on membrane based solvent
extraction are found in Prasad and Sirkar (1992),
Reed et al. (1995), Schlosser (2000, 2009).
The solvent can be regenerated by
re-extracting the solute in a stripping solution.
Figure 2 shows the schematic of a membrane
based solvent extraction and stripping using two
hollow fiber modules.
Membrane based solvent extraction is often
assisted by a carrier that reacts with the solute at
2 Membrane Based Solvent Extraction

the interface immobilized on the first module and should be taken into account as it can play an
it is released at the interface of the second module. important role. The concentration dependence of
Figure 3 shows the case of extraction of lactic acid the distribution coefficient of solutes is another
by a quaternary amine. parameter to be taken into the account. The solute
In membrane based solvent extraction medi- distribution coefficient influences the concentra-
ated by carriers, kinetics of extraction reactions tion gradient and may result in the concentration
dependent overall mass-transfer coefficient.
FEED SOLVENT In the literature, studies using models consider-
ing the constant mass-transfer coefficient in MBSE
(Viegas et al. 1998), or variable distribution coef-
SW ficients (Escalante et al. 1998; González-Munoz
et al. 2004) are reported. Models taking into
account reaction kinetics of formation and decom-
position of the extractant-solute complex(es) in
extraction and stripping interfaces are also
discussed (Juang and Huang 1997; Juang
FIBER WALL
et al. 2000; Kubišova et al. 2004; Schlosser
F S
et al. 2001). The contribution of resistance based
on reaction kinetics to the overall resistance
depends on solute and carrier concentrations. It
may range between 30 % and 80 %.
Membrane Based Solvent Extraction,
Ionic liquids result very promising in the sol-
Fig. 1 Schematic of MBSE mechanism at membrane
level. F: feed, S: solvent, Sw: solvent in fiber wall. Here vent extraction of organics (Han and Armstrong
is shown the case where the membrane is wetted by the 2007; Pletnev et al. 2008). Ionic liquids (ILs) are
organic solvent composed of organic cations and organic or inor-
ganic anions that remain in liquid state over a wide
temperature range, including room temperature.

4 7 10

Mod 1 Mod 2

6 9
8
5

11 12 13

1 2 3

Feed Extractant Stripping

Membrane Based Solvent Extraction, Fig. 2 Membrane-based solvent extraction in hollow fibre membrane
contactors. 1–3 pums, 4–10 pressure gauges, 11–13 flowmeters
Membrane Based Solvent Extraction
Phase I
Feed
(aqueous, Aacidic pH)
LaH+H2O <---> La- + H3O+
H3O+
H2O
La-
Membrane
module I
Membrane Based Solvent Extraction, Fig. 3 Mechanism separation of lactic acid by membrane-based solvent
extraction
The majority of works deals with ILs with
imidazoliumcations. A new promising group of
ILs based on phosphoniumcations (Bradaric
et al. 2003).
References
Bradaric CJ, Downard A, Kennedy C, Robertson AJ, Zhou
YH (2003) Industrial preparation of phosphonium ionic
liquids. Green Chem 5:143
Escalante H, Alonso AI, Ortiz I, Irabien A (1998) Separa-
tion of L-phenylalanine by nondispersive extraction and
backextraction equilibrium and kinetic-parameters.
Sep Sci Technol 33:119
González-Munoz MJ, Luque S, Alvarez JR, Coca J (2004)
Simulation of integrated extraction and stripping pro-
cesses using membrane contactors. Desalination 163:1
Han X, Armstrong DW (2007) Ionic liquids in separations.
Acc Chem Res 40:1079
Juang RS, Huang RH (1997) Kinetic-studies on lactic-acid
extraction with amine using a microporous membrane-
based stirred cell. J Membr Sci 129:185
Juang RS, Chen JD, Huan HC (2000) Dispersion-free
membrane extraction case-studies of metal-ion and
organic-acid extraction. J Membr Sci 165:59
Kubišova Ľ, Sabolová E, Schlosser Š, Marták J, Kertesz R
(2004) Mass-transfer in membrane based solvent
extraction and stripping of 5-methyl-2-
3
Phase II Phase III
Extractant
Stripping
(Organic
(Aqueous, basic pH)
phase)
OH-
R3N
H2O
La-
R3NH+La-
Membrane
module II
pyrazinecarboxylic acid and co-transport of sulphuric
acid in HF contactors. Desalination 163:27
Pletnev IV, Smirnova SV, Egorov VM
(2008) Liquid–liquid extraction of organic compounds.
In: Koel M (ed) Ionic liquids in chemical analysis. CRC
Press, Boca Raton, p 243
Prasad R, Sirkar KK (1992) Membrane based solvent
extraction. In: Ho WSW, Sirkar KK (eds) Membrane
handbook. Van Nostrand Reinhold, New York, p 727
Reed BW, Semmens MJ, Cussler EL (1995) Membrane
contactors. In: Noble RD, Stern SA (eds) Membrane
separation technology. Principles and applications.
Elsevier Science, Amsterdam, p 467
Schlosser Š (2000) Membrane based processes with
immobilized interface. In: Bako K, Gubicza L,
Mulder M(eds) Integration of membrane processes
into bioconversions. Kluwer, New York, p 55
Schlosser Š (2009) Extractive separations in contactors
with one and two immobilized L/L interfaces: applica-
tions and perspectives. In: Drioli E, Giorno L (eds)
Membrane operations. Innovative separations and
transformations. Wiley-VCH, Weinheim, p 513
Schlosser Š, Sabolová E, Kertész R, Kubišová Ľ
(2001) Factors influencing transport through liquid
membranes and membrane-based solvent-extraction.
J Sep Sci 24:509
Viegas RMC, Rodriguez M, Luque S, Alvarez JR,
Coelhoso IM, Crespo JPSG (1998) Mass-transfer cor-
relations in membrane extraction analysis of Wilson-
plot methodology. J Membr Sci 145:129
H
Hydrothermal Stability of Zeolite
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Universidad de Zaragoza, Zaragoza, Spain
Zeolites are microporous crystalline aluminosili-
cates, and its Si to Al ratio and ion exchange
determines its main properties. The most impor-
tant application of zeolites is catalysis, and in
particular zeolite Y and ZSM-5 are the catalysts
in the fluid catalytic cracking (FCC) process for
gasoline production in refineries. The acidity of
the zeolites, related to its aluminum content and
the shape selectivity given by the microporous
network of cavities, are the main properties that
contribute to the success of the zeolites in the
cracking reactions. The production of coke in
the FCC implies a continuous regeneration step
at temperatures up to 800  C in the presence of
steam. Under these severe hydrothermal condi-
tions, the activity and stability of zeolite is
affected mainly due to the dealumination of the
zeolite. The preparation of USY, ultrastable
zeolite Y, consists of increasing the Si/Al ratio
of the zeolite, decreasing the activity but increas-
ing hydrothermal stability. Similarly the addition
of phosphorous also stabilizes the aluminum
framework in the zeolite (Martinez 2008). Finally
the creation of the mesopores in the zeolites for
FCC is also desired to crack larger molecules.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_951-1
The introduction of mesopores is accomplished
by alkali treatment, but the thermal and hydro-
thermal stability again decreases, since the
desilication effect of the NaOH solution, and
this made some Al sites in the interior crystal
become the Al sites at the edge of the crystal,
which would be extracted easily by calcination
and steaming treatments. In general it could be
concluded that there is a trade-off in the alumi-
num content of the zeolite, as it increases acidity
and catalytic activity; however, hydrothermal
stability decreases.
Similarly some problems related to hydrother-
mal stability of zeolite A, Si/Al = 1 in dehydra-
tion of organic solvent by pervaporation, has
been reported. The damage effects of water on
LTA zeolite membranes were verified and occur
at water concentrations higher than 15 % and
temperatures of 70  C. The effects of water con-
tent in the feed and PV temperature on the mem-
brane stability were recently investigated Li
et al. (2007). The preliminary results show that
the damage of LTA zeolite membrane by water
mainly occurs in the grain boundary regions. The
amorphous-like structure of the grain boundary is
probably the principal reason for the low hydro-
thermal stability of LTA zeolite membrane at
high water concentration, as the case of
mesoporous molecular sieving materials. Solu-
tions to this problem include the use of a zeolite
with a higher Si/Al ratio, such as CHA membrane
(Sato et al. 2012), and posttreatments in zeolite
LTA such as silylation.
2 Hydrothermal Stability of Zeolite
References
Li Y, Zhou H, Zhu G, Liu J, Yang W (2007) Hydrothermal
stability of LTA zeolite membranes in pervaporation.
J Membr Sci 297(1–2):10–15
Martinez A (2008) Chapter 10: J. Cejka, J. Peréz-Pariente
and W. J. Roth (eds) application of zeolites in the
production of petrochemical intermediates. In Zeo-
lites: from model materials to industrial catalysts,
1st ed. Transworld Research Network, Kerala,
pp 227–261
Sato K, Sugimoto K, Shimotsuma N, Kikuchi T,
Kyotani T, Kurata T (2012) Development of practi-
cally available up-scaled high-silica CHA-type zeolite
membranes for industrial purpose in dehydration of
N-methyl pyrrolidone solution. J Membr Sci
409–410:82–95
S
Seeded Hydrothermal Synthesis
for Zeolite Preparation
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Universidad de Zaragoza, Zaragoza, Spain
Synonyms
Ex situ zeolite synthesis, Secondary growth
method
The hydrothermal synthesis procedures used to
prepare zeolite membranes can be classified in
two general groups: ex situ and in situ methods,
that is with and without a previous seeding step.
The secondary (seeded) growth method,
decoupling nucleation and membrane growth, is
considered as the most successful approach to
control membrane formation (Caro et al. 2000;
Arruebo et al. 2008).
This method includes a first step, seeding step,
in which a closely packed layer of colloidal zeo-
lite crystals, synthesized homogenously, is
deposited onto the surface of a support. These
seeds, act as nuclei for further crystal growth
with a secondary gel under hydrothermal synthe-
sis conditions in the second stage, see Fig. 1.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_952-1
The coating or seeding methods for zeolite
membranes are dip coating, slip casting, rubbing,
spray coating, laser ablation, spin coating, vac-
uum seeding, using of electrostatic forces, and
covalent linkage. The attachment and bonding
properties of the crystals on support depend on
the chemical potential of the support to interact or
react with the approaching zeolite crystal or crys-
tal growth front. Because the concentration
needed for secondary growth is lower than that
required for nucleation, further nucleation is
strongly decreased and almost all of the crystal
growth takes place over the existing crystal seeds.
By controlling the composition and concentration
of the secondary growth solution, the crystalliza-
tion of undesired zeolite phases and the dissolu-
tion of the support can be avoided, and the rate
and direction of crystal growth can, to a certain
extent, be controlled, see Fig. 2.
The aim of using the “ex situ” techniques is to
obtain a better control of the microstructure and a
preferential orientation of the crystals in the
membrane with a shortened crystallization time.
Preferential orientation is needed, not only for
separation purposes when high fluxes are
required, but also for size-selective chemical sen-
sors. Due to the anisotropy in the pore geometry
of the zeolite crystals, the orientation which
shows the largest channels in the direction of
the flux is preferable.
2 Seeded Hydrothermal Synthesis for Zeolite Preparation

Separation of zeolite seeds

Seed
synthesis

Membrane Seeding
synthesis

Porous support

Seeded Hydrothermal Synthesis for Zeolite Preparation, Fig. 1 Scheme of the hydrothermal synthesis of zeolite
membranes by separating the nucleation and the crystal growth steps

Seeded Hydrothermal Synthesis for Zeolite Preparation, Fig. 2 SEM analysis of silicalite membranes over
nonporous alumina substrates after 20 h of secondary growth synthesis conditions. Left: top view. Right: cross section
Seeded Hydrothermal Synthesis for Zeolite Preparation 3

Seeded Hydrothermal
Synthesis for Zeolite c
Preparation, {101}
Fig. 3 Schematic
orientation of c-oriented
MFI zeolite crystal

{100}
b

{001}

“c” oriented MFI crystals

For example, on MFI zeolite, the straight and References

sinusoidal channels run parallel to the “b” and “c”
axis respectively, see Fig. 3 Arruebo et al. 2008).
The membranes prepared by secondary growth
have rendered, in general, “c” oriented mem-
branes, i.e., sinusoidal channels perpendicular to
the support surface.
Arruebo M, Mallada R, Pina MP (2008) Chapter 10: Zeo-
lite membranes: synthesis, characterization, important
applications, and recent advances. In: Handbook of
membrane separations, 1st edn. CRC Press, Boca
Raton, pp 233–323
Caro J, Noack M, Kölsch P, Schäfer R (2000) Zeolite
membranes – state of their development and perspec-
tive. Microporous Mesoporous Mater 38:3–24
H
Hydrothermal Synthesis of Zeolite
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Universidad de Zaragoza, Zaragoza, Spain
Zeolites are crystalline, hydrated aluminosili-
cates having microporous, regular structures
that occur naturally. The synthetic zeolites early
developed by Barrer and Milton in the late 1940s
(Cundy and Cox 2005) were prepared using a
hydrothermal treatment at high temperature and
pressure mimicking the conditions for the synthe-
sis of these minerals in nature. There are more
than 200 framework types, recognized by the
International Zeolite Association (IZA, http://
www.iza-structure.org), but only a few have
been synthesized as membranes being the most
important: MFI, LTA, FAU, CHA, and MOR.
A hydrothermal treatment implies the use of
an aqueous solution, synthesis gel, which is
heated in an autoclave at a certain temperature
under autogenous pressure. The chemicals in the
synthesis gel include the silicon and aluminum
sources in the presence of a mineralizing agent
commonly sodium hydroxide or alternatively
fluoride ion and in some cases a structure-
directing agent (SDA) that facilitates the synthe-
sis of the desired zeolite structure.
In a conventional hydrothermal synthesis all
the reactants are mixed together and dissolved in
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_953-1
the highly alkaline synthesis gel and heated up in
the autoclave up to the selected temperature.
After an induction period crystalline zeolite
nuclei could be detected later, the nuclei start
growing and finally all the amorphous material
is converted into zeolite. There are several mech-
anisms proposed for the hydrothermal synthesis
of zeolites (Cundy and Cox 2005), but in general
they comprised the dissolution of the ionic spe-
cies, organization of the aluminum and silicon
tetraeda species around the structure-directing
agents forming initial primary building units,
that result in secondary building units, that finally
form the polyhedra that comprise the zeolite
structure, see Fig. 1.
The most probable mechanistic pathways in
zeolite formation are described in sequence:
induction period, nucleation, and crystal growth.
The nucleation and crystal growth could be sep-
arated, giving rise to the ▶ seeded hydrothermal
synthesis method of zeolite membranes.
The composition of the synthesis gel influ-
ences the crystallization and the zeolite formed.
Firstly the Si/Al ratio will define the ion exchange
capacity, as one atom of Si is replaced by Al a
charge defect is created. Also the hydrophylicity
of the zeolite increases as the Al content
increases, being zeolite A with a Si/Al = 1 the
most hydrophilic and silicalite with Si/Al = 1
the most hydrophobic. The solvent, as water (and
sometimes alcohols) has a direct effect on the
concentration of reactants, and therefore on the
nucleation and growth rates. Alcohols are often
2 Hydrothermal Synthesis of Zeolite
Hydrothermal Synthesis of Zeolite, Fig. 1 Steps in Hydrothermal Synthesis of Zeolites
added to retard the hydrolysis of the silicon alk-
oxide which allows controlling the crystal size by
reducing the polymerization rate of the silica. The
amount and nature of the solvent will also affect
the viscosity of the synthesis gel, and therefore
the diffusion rates of reactants during synthesis.
The presence of the structure-directing agent
(SDA), facilitates zeolite synthesis, but in zeolite
layers, and especially in membranes, may cause
complications associated to template removal.
The mineralizing agents – they also have a direct
effect on the synthesis dynamics and in the hydro-
philic/hydrophobic character of the resulting
membranes.
The synthesis time of zeolites could vary from
several hours to days in conventional ovens at
temperatures ranging from 90  C to 200  C. It is
Soluble silicates and aluminosilicates
Gel
Depolimerization of aluminosilicate
chains
Primary Building
Units
Secondary Building
Units
Polyhedra
Zeolite
important to mention that in the last decade the
microwave hydrothermal assisted method (see
▶ Microwave synthesis of zeolite membranes)
has contributed to shorten considerably synthesis
time of zeolites and zeolite membranes (Li and
Yang 2008) due to a more efficient volumetric
heating compared to conventional heating.
References
Cundy CS, Cox PA (2005) The hydrothermal synthesis of
zeolites: precursors, intermediates and reaction mech-
anism. Microporous Mesoporous Mater 82:1–78
Li Y, Yang W (2008) Microwave synthesis of zeolite
membranes: a review. J Membr Sci 316:3–17
M
Mordenite Membrane
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Universidad de Zaragoza, Zaragoza, Spain
Synonyms
MOR membrane
Mordenite (MOR) is a high-silica zeolite, with a
molecular formula Na8(H2O)24[Al8Si40O96], in
which the Si, Al content of the framework and
the cation content of the cavities are moderately
variable. The Si/Al ratio could be varied between
4 and 20. MOR-type zeolite consists of
12-Membered Ring (MR = straight channels
(6.5  7.0 Å) parallel to the c-axis,
interconnected to tortuous 8-MR channels
(2.6  5.7 Å) in the a-axis, see Fig. 1,
(International Zeolite Association commission).
Typical morphology of the crystals corresponds
to long needles that run along the c axis (see
Fig. 2), but other morphologies could be also
observed.
Mordenite membranes have been prepared by
different methods: the vapor phase transport
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_954-1
method, direct (unseeded) hydrothermal synthe-
sis with or without template, and see Seeded
Hydrothermal Synthesis for Zeolite Preparation.
This last method could be considered as the most
convenient in terms of synthesis time reproduc-
ibility and is easy to scale up.
The orientation of the zeolite mordenite crys-
tals in the MOR membranes is very important,
favoring the transport of the molecules through
the big 12MR channels, see Fig. 2. Control of the
orientation could be achieved by secondary
growth and control of the synthesis gel composi-
tion (Li et al. 2003). Figure 3 shows random
orientation of zeolite crystals in mordenite mem-
branes, (Navajas et al. 2007).
Due to the relatively big pore size 0.65 nm
these membranes have not been tested in separa-
tion of small molecules of permanent gases,
instead these membranes have been proposed as
good candidates in pervaporation separation, (see
Mordenite Membrane in Pervaporation). In par-
ticular, due to the relatively high silica to alumi-
num ration these zeolites are selected for water
pervaporation in acidic mixtures, (see Acetic
Acid Dehydration by Pervaporation of Zeolite
Membranes).
2 Mordenite Membrane

y
z
x

framework viewed along [001]

Idealized cell data: orthorhombic, Cmcm, a =18.3Å, b = 20.5Å, c =7.5Å
Channels: [001] 12 6.5 x 7.0* ↔ [001] 8 2.6 x 5.7***

7.0 7.0 5.7 5.7

2.6 2.6
6.5 6.5

limiting 8 ring along [001]

12-ring viewed along [001]
between 12-ring channels

Mordenite Membrane, Fig. 1 Framework topology of MOR and pore size of the channels. IZA structure commission

Mordenite Membrane, Fig. 2 Mordenite crystal orientation on a cordierite monolithic structure (Reprinted with
permission from Ulla et al. (2004) Chem. Commun 528–529)
Mordenite Membrane 3

Mordenite Membrane, Fig. 3 Top view and cross section of mordenite membranes prepared by secondary growth
method (Reprinted with permission from Navajas et al (2007) J Membr. Sci, 299 (1–2), 166–173)

References growth method. Microporous Mesoporous Mater

International Zeolite Association http://www.iza-
structure.org/. Visited 9 Oct 2013
Li G, Kikuchi E, Matsukata M (2003) The control of phase
and orientation in zeolite membranes by the secondary
62(3):211–220
Navajas A, Mallada R, Tellez C, Coronas J, Menendez M,
Santamaria J (2007) Study on the reproducibility of
mordenite tubular membranes used in the dehydration
of ethanol. J Membr Sci 299(1–2):166–173
M
Mordenite Membrane
in Pervaporation
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Universidad de Zaragoza, Zaragoza, Spain
Mordenite membranes belong to the inorganic
microporous (pores below 2 nm according to
IUPAC definition) membrane group. These
membranes are applied in gas separation and
pervaporation. In the case of mordenite, since
the kinetic diameter of most of the permanent
gases is bigger than the pore size of this structure
0.7 nm (see entry “▶ Mordenite Membrane”), the
membranes are not applied in gas separation, and
pervaporation is the main application envisioned
in the literature. Furthermore the relatively high
Si/Al ratio and moderate hydrophilicity make
these membranes perfect candidates for dehydra-
tion of acidic mixtures by pervaporation (see
entry “▶ Acetic Acid Dehydration by
Pervaporation of Zeolite Membranes”).
There are many reported data for
pervaporation of water/alcohol mixtures; the per-
formance is lower compared to the more
hydrophilic zeolite A membranes (Arruebo
et al. 2008). In the separation of a mixture of
H2O/isopropanol, 10%wt/90%wt at 75  C water
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_955-1
fluxes care in the order of 0.1–0.2 kg/hm2 in the
case of MOR, and in the case of H2O/isopropanol
10%wt/90%wt at same temperature, values of
2–9 2 kg/hm2 could be found. Thus, the main
application of mordenite membranes in
pervaporation is in the case of dehydration of
acidic mixtures where zeolite A membranes
degrade, while MOR membranes remain stable.
The economic feasibility of mordenite mem-
branes for pervaporation of acetic acid/water
mixtures has been also studied by the researchers
of Mitsubishi (Sato et al. 2011). The membrane
performance in pervaporation was measured in a
feed mixture of water (50 wt%)/AAc (50 wt%) to
be 10.9 kg m2/h for permeate flux and to be
0.77  10 6 mol m2/ sPa for water permeance
with separation factor of 500 at 130  C.
References
Arruebo M, Mallada R, Pina MP (2008) Chapter 10: Zeo-
lite membranes: synthesis, characterization, important
applications, and recent advances. In: Handbook of
membrane separations, 1st edn. CRC Press, Boca
Raton, pp 233–323
Sato K, Sugimoto K, Kyotani T, Shimotsuma N, Kurata
T (2011) Synthesis, reproducibility, characterization,
pervaporation and technical feasibility of preferen-
tially b-oriented mordenite membranes for dehydra-
tion of acetic acid solution. J Membr Sci
385–386:20–29
A
Acetic Acid Dehydration by
Pervaporation Zeolite Membranes
Reyes Mallada
Department of Chemical and Environmental
Engineering and Aragon Nanoscience Institute,
Nanoporous Films and Particles Group,
Zaragoza, Spain
The best performance in pervaporation for water
dehydration corresponds to zeolite A, which is the
zeolite with the lowest Si/Al ratio (equal to 1) and
therefore the highest hydrophilicity. However, the
high aluminum content of this zeolite makes it
unstable under acidic conditions and it dissolves
at low pH.
The separation of water in the presence of acetic
acid or other acids could be important in the case of
membrane reactors, active zeolite membrane reac-
tors (AZMRs), for equilibrium displacement (see
also Membrane reactor equilibrium conversion and
Pervaporation membrane reactor). The esterifica-
tion reaction using acid produces water that could
be removed continuously using a water permeable
acid resistant membrane.
The most promising results concerning separa-
tions in acid medium have been obtained with
zeolites with a moderate Si/Al ratio such as zeolite
T with Si/Al = 4 or mordenite with Si/Al ratio
from 7 to 20. Both zeolites have been tested in
water/acetic acid mixture (50/50 wt.%) showing
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_956-1
stability after the exposure to this mixture at mild
temperature around 70  C for several days.
Although the performance of these zeolites in
pervaporation for water dehydration are lower
compared to zeolite A (Arruebo et al. 2008), the
acid stability of these zeolites is higher than that
of zeolite A and makes them good candidates for
the separation of acid mixtures. The researchers
of Mitsubishi studied the technical feasibility
of mordenite membranes for dehydration of
acetic acid aqueous solution with a feed rate of
1000 kg h 1. Their results suggested that the
developed mordenite membrane deserved to the
further technically developments of up-scale and
mass-production (Sato et al. 2011). The mem-
brane performance in pervaporation was mea-
sured in a feed mixture of water (50 wt.%)/AAc
(50 wt.%) to be 10.9 kg m2/h for permeate flux
and to be 0.77  10 6 mol m2/sPa for water
permeance with separation factor of 500 at
130  C.
References
Arruebo M, Mallada R, Pina MP (2008) Zeolite mem-
branes: synthesis, characterization, important applica-
tions, and recent advances, Chapter 10. In: Handbook of
membrane separations, 1st edn. CRC Press, Boca
Raton, pp 233–323
Sato K, Sugimoto K, Kyotani T, Shimotsuma N, Kurata
T (2011) Synthesis, reproducibility, characterization,
pervaporation and technical feasibility of preferentially
b-oriented mordenite membranes for dehydration of
acetic acid solution. J Membr Sci 385–386:20–29
D
Dynamic Membrane Microfiltration
M. Y. Jaffrin
UMR 7338, University of Technology of
Compiegne, Compiegne, France
Introduction
To separate molecules or particles from a solu-
tion by cross-flow filtration through a membrane,
it is necessary to circulate the fluid at a speed of
3–6 ms 1 in a tubular or plane membrane in order
to prevent the buildup of a layer of rejected sol-
utes on the membrane while exerting a pressure
on the fluid to produce a filtrate. The combination
of high feed pressure and flow rate requires pow-
erful and expensive pumps that consume energy
and the friction creates a pressure decay along the
membrane which reduces the transmembrane
pressure (TMP). In addition, the rejected mole-
cules or particles can create a cake on a
microfiltration (MF) membrane which reduces
both filtration rate and solute transmission
through the membrane.
Dynamic filtration is a recent alternative to
classical cross-flow filtration (Lee et al. 1995;
Jaffrin 2008) consisting in creating a high shear
rate (velocity gradient) at the membrane by a disk
or a rotor rotating near the membrane or by using
rotating or vibrating membranes, while using a
low feed flow rate, only slightly larger than the
permeate flow rate.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_957-2
Advantages and Drawbacks of Dynamic
Filtration
The first advantage is a substantial increase in
permeate flux at all membranes cut-off due to
shear rates which can reach 3 105 s 1 when
using disks with radial vanes rotating at high
speed. Due to moderate fluid velocities inside
the module, the transmembrane pressure remains
relatively uniform, which contributes to flux
increase. Clarification of a suspension by MF
requires a good solute transmission which is aug-
mented by cake reduction. In ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis (RO) the
permeate flux is mainly limited by the concentra-
tion polarization layer made of molecules
rejected by the membrane. This layer is dimin-
ished by high shear rates which increases back
transport of solutes away from the membrane.
The flux keeps increasing with rising TMP until
pressures of 40 bars at high shear rates. The
combination of these two factors, high TMP and
high shear rates, yields frequently permeate
fluxes five times higher than in cross-flow filtra-
tion with the same membrane and same fluid. In
addition, in NF and RO applications, such as
wastewater treatment, it is important to have a
small microsolutes concentration in permeate.
This is the case in dynamic filtration as the diffu-
sive mass transfer through the membrane is
greatly reduced by the small solute concentration
at the membrane.
2 Dynamic Membrane Microfiltration
Dynamic Membrane
Microfiltration,
Fig. 1 Industrial VSEP
vibrating modules
(Courtesy of New Logic
Research)
The main drawbacks are higher costs of equip-
ment and maintenance due to moving parts and
more complex design and membrane area limita-
tions for some systems. The recent availability of
30 cm diameter ceramic membrane disks has
permitted the development of systems with
ceramic disks rotating around several parallel
shafts in a closed tank, with a total membrane
area exceeding 120 m2 which are cheaper to build
and to service than multicompartment modules
with metal disks rotating between fixed organic
membranes.
Rotating disks modules give a choice between
using high rotation speeds to maximize the flux
and thus minimize membrane area and invest-
ment cost, or to use moderate speeds to obtain
the same flux as with tubular membranes but
saving more than 60 % of the energy spent per
m3 of permeate with these membranes.
Industrial Filtration Modules
VSEP Vibrating Modules (New Logic
Research, Ca, USA)
Close to 400 VSEP systems have been installed
worldwide since their introduction around 1995.
They consist of a stack of circular organic mem-
branes in separate compartments oscillating azi-
muthally around a vertical shaft at a resonant
frequency of about 60 Hz. The maximum mem-
brane area is 150 m2 and the power spent in
vibrations is only 9 kW (Fig 1). It can sustain
pressures of 40 bars and is used with a wide
choice of membranes from MF to RO
Al-Akoum et al. (2002).
Single Shaft Rotating Disks Systems
Bokela GmbH (Karlsruhe, Germany) commer-
cializes the Dyno with metal disks rotating
between fixed circular membranes of 12 m2 for
MF and UF (Fig. 2).
Metso Paper (Raisio, Finland) manufactures
the Optifilter CR with blades rotating between
fixed membranes of 1 m diameter and up to
140 m2 membrane area with a 132 kW motor
(Fig.3).
Multishaft Rotating Ceramic Membrane
systems
KMPT GmbH (Vierkirchen, Germany) commer-
cializes a two-shaft module with 15 cm diameter
overlapping ceramic membranes of 16.4 m2 area
(Table 1).
Dynamic Membrane Microfiltration 3

Dynamic Membrane
Microfiltration,
Fig. 2 Dyno rotating disk
module (Bokela, Germany)

Dynamic Membrane
peripheral
Microfiltration, strip rotor
Fig. 3 Sketch of OptiFilter
CR, Metso paper Co,
Finland

support layer

clamp ring

support plate

membrane

concentrate
water out

feed filtrate
water in water out
4 Dynamic Membrane Microfiltration

Dynamic Membrane Microfiltration, Table 1 List of industrial dynamic filtration modules and their characteristics
(Jaffrin 2008)
Membrane Disk MaxTMP
Manufacturer Models Type area m2 Pore size diam, mm bar
Bokela Dyno Rotating disks 0.013–12 10 nm–1 mm 137–850 4
(Germany) organic
Andritz Kraus-M Membrane rotating 0.05–16.4 7 nm–2 mm 2
(Germany) DCF on two shafts ceramic
Novoflow SSDF Membrane rotating 1–25 7 nm–2 mm 152–500 2,5
(Germany) CRD on one shaft ceramic
Metso paper Optifilter Rotors between 15-84-140 MF-UF 550–1000 3–4
(Finland) CR membranes Organic
Spintek (US) ST Membr rot on 1 shaft 0.1–2.3 MF-UF 275
Org/ceram
New Logic VSEP 0.05–150 organic Organic MF-UF-NF- 300–500 40
Research, (US) RO

Conclusion References

Dynamic filtration is not intended for initial treat-
ment of huge volumes of fluids, but it should be
well adapted to “end of pipe treatment” when the
goal is to reach high solid concentration in
retentate or to extract valuable components in
highly charged suspensions.
Al-Akoum O, Jaffrin MY, Ding LH, Paullier P, Vanhoutte
C (2002) An hydrodynamic investigation of
microfiltration and ultrafiltration in a vibrating mem-
brane module. J Membr Sci 197:37–52
Jaffrin MY (2008) Dynamic shear-enhanced membrane
filtration: a review of rotating disks, rotating mem-
branes and vibrating systems. J Membr Sci 324:7–25
Lee SA, Russoti BG, Buckland B (1995) Microfiltration of
recombinant yeast cells using a rotating disk dynamic
filtration system. Biotechnol Bioeng 48:386–400
P
Phenol Degradation Using
Membrane Reactor
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Phenol is one of major pollutants in industrial
wastewater with high remediation priority. In
the following a summary of some studies
concerning phenol degradation in membrane
reactors is reported.
Wastewater from coal gasification has poor
biodegradability and high toxicity. A laboratory-
scale anaerobic-anoxic-oxic membrane reactor
(AAO-MBR) system was developed to investi-
gate the treatment ability of coal gasification
wastewater by Wang et al. (2012). The removal
capacity of each pollutants used in this system
was determined at different hydraulic residence
times (HRT) and mixed liquor recycle ratios (R).
The experimental results showed that this system
could effectively deal with COD and phenol
removal and remained in a stable level when the
operational parameters were altered, while the
nitrification was sensitive to operational condi-
tions. The best performance was obtained at HRT
of 48 h and R of 3. The maximum removal effi-
ciencies of COD, NH4+-N, and phenols were
97.4 %, 92.8 %, and 99.7 %, with final concen-
trations in the effluent of 71 mg/L, 9.6 mg/L, and
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_960-2
3 mg/L, respectively. Organic degradation and
transformation were analyzed by GC/MS (gas
chromatography/mass spectrometry), and it was
found that anaerobic process played an important
role in degradation of refractory compounds.
The effect of salt concentration on the perfor-
mance of a membrane bioreactor (MBR) for
treating an olefin plant wastewater was investi-
gated by Sadeghi et al. (2012). For this purpose, a
lab-scale submerged MBR with a flat-sheet ultra-
filtration membrane was used for treatment of
synthetic wastewater according to oxidation and
neutralization unit of olefin plant. The synthetic
wastewater was adjusted to have 500 mg/L chem-
ical oxygen demand (COD). Trials on different
concentrations of sodium sulfate (Na2SO4)
(020–000 ppm) in the feed were carried out
under aerobic conditions in the MBR. The results
showed that increasing the salt concentrations
causes an increase in the effluent COD, phenol,
and oil concentrations. These results are due to
reduction of the membrane filtration efficiency
and also decline in the microbial activity. But in
all the trials, the effluent COD and oil concentra-
tion were well within the local discharge limit of
100 and 10 mg/L, respectively. These results
indicate that the MBR system is highly efficient
for treating the olefin plant wastewater, and
although high salt concentrations decreased
organic contaminant removal rates in the MBR,
the effluent still met the discharge limits for
treating the olefin plant wastewater.
2 Phenol Degradation Using Membrane Reactor
In municipal wastewater treatment plant
(WWTP) effluents, the problem due to the pres-
ence of micropollutants in wastewater which may
be able to disrupt the endocrine system of some
organisms has been faced by Abargues
et al. (2012). The fate of the alkylphenols (APs)
(4-(tert-octyl) phenol, t-nonylphenol, and 4-p-
nonylphenol) and the hormones (estrone,
17 beta-estradiol, and 17 alpha-ethinylestradiol)
in a submerged anaerobic membrane bioreactor
(SAMBR) pilot plant and in a conventional-
activated sludge wastewater treatment plant
(CTP) has been compared. The obtained results
were also compared with those obtained in a
previous study carried out in an aerobic MBR
pilot plant. The results showed that the AP solu-
ble concentrations in the SAMBR effluent were
always significantly higher than those in the CT-
P. Moreover, the analyses of the suspended frac-
tion revealed that the AP concentrations in the
SAMBR reactor were usually higher than in the
CTP reactor, indicating that under anaerobic con-
ditions, the APs were accumulated in the digested
sludge. The aerobic conditions maintained both
in the CTP system and in the aerobic MBR that
favored the AP and hormone degradation and
gave rise to lower concentrations in the effluent
and in the reactor of these systems. Furthermore,
the results also indicated that the degradation of
APs under aerobic conditions was enhanced
working at high solid retention time (SRT) and
hydraulic retention time (HRT) values.
Direct coupling of separation and photocatalytic
degradation by using photocatalytic membrane is
an attractive way to solve problems like membrane
fouling by adsorbed organic macromolecules or
elimination of small organic molecules which can-
not be efficiently stopped by a membrane. A simple
and robust synthesis route to a photocatalytically
active titania membrane was developed from a
commercial TiO2 hydrosol and commercial alu-
mina supports by Djafer et al. (2010). Reproducible
defect-free layers with a thickness of about 3 mm
were prepared. The membrane performance in
term of separation and photocatalytic activity was
investigated. The pure water permeance was 150 L
h 1 m 2 bar 1 and the measured molecular weight
cut-off was around 50 kDa corresponding to an
ultrafiltration membrane. The photocatalytic effi-
ciency was tested by photooxidation under UV
irradiation of a reference organic dye (methylene
blue) for comparison with reference TiO2
photocatalysts and also with phenol as typical
organic pollutant in water. The measured values
of quantity of destroyed organic molecules per
units of time and of membrane surface area are in
the range 0.8–3.8  10 8 mol s 1 m 2.
Phenol decomposition was carried out under
UV irradiation in a recycle batch photocatalytic
membrane reactor (PMR) by Yang et al. (2011).
To overcome the problem of post-recovery of the
catalyst particles after water treatment, surface
modification of polypropylene macroporous
membrane was performed with the technique of
photoinduced reversible addition-fragmentation
chain transfer grafting polymerization of acrylic
acid. TiO2 photocatalysts were introduced into
the acrylic acid-grafted membrane surface. In
the tests on the PMR, the normalized membrane
flux reached 1.7 times that of the unmodified
membrane for the poly(acrylic acid) (PAAc)-
modified membrane. Introducing TiO2
photocatalysts into the membrane surface
reduced slightly the normalized membrane flux.
For the PMR with a grafting degree of 12.9 %
(wt) of PAAc on the membrane surface, the
corresponding decomposition percentage was
32.5 % after 6 h UV light irradiation.
The role of membrane in phenol degradation
in high-phenol-fed MBR (membrane bioreactor)
was explored by Ahn et al. (2011). Phenol elim-
ination in high-phenol-fed MBRs resulted in
complete mineralization, and the high-phenol-
fed MBR exhibited greater biomass-specific phe-
nol removal rates (0.4–1.5 mg phenol/(mg VSS.
d) than the low-phenol-fed MBR. In the high-
phenol-fed MBR, filamentous non-settling
microbes were more abundant than in the
low-phenol-fed MBR. Batch experiment, high-
acclimated, and non-settling microbes were sep-
arately collected from the high-phenol-
acclimated bioreactor, and their specific phenol
degradation was determined at 5.1 mg phenol/
(mg VSS.d). The greater specific phenol degra-
dation rate of the non-settling microbes than the
observed phenol elimination rate in the high-
Phenol Degradation Using Membrane Reactor
phenol-fed MBR indicated that the high-phenol-
acclimated and non-settling microbes had greater
degradation activity than the rest of sludge
microbes in the bioreactor. According to these
findings, the role of membrane in the high-
phenol-fed MBR was identified as the contain-
ment of non-settling and biodegradative
microbes in bioreactor, and in turn, the
membrane-driven increase of non-settling phenol
degrading microbes enhanced phenol elimination
in the high-phenol-fed MBR.
A novel process to biodegrade phenol present
in an acidic (1 M HCl) and salty (5 % w/w NaCl)
synthetically concocted wastewater was studied
by Livingston (1993). The process utilized a
membrane bioreactor, in which the phenol present
in the wastewater was separated from the inor-
ganic components by means of a silicone rubber
membrane. Transfer of the phenol from the waste-
water into a biological growth medium allowed
biodegradation to proceed under controlled con-
ditions which were unaffected by the presence of
inorganic species in the synthetic wastewater. At
a wastewater flow rate of 18 mL h 1 (contact time
6 h), 98.5 % of phenol present in the wastewater at
an inlet concentration of 1,000 mg L 1 was
degraded; at a contact time of 1.9 h, 65 % of the
phenol was degraded. Phenol degradation was
accompanied by growth of a biofilm on the mem-
brane tubes and by conversion of approximately
80 % of the carbon entering the system to CO2
carbon. Analysis of the transport of phenol across
the membrane revealed that the major resistance
to mass transfer derived from the diffusion of
phenol across the silicone rubber membrane.
A mathematical model was used to describe the
transfer of phenol across the membrane and the
subsequent diffusion and reaction of phenol in the
biofilm attached to the membrane tube. This anal-
ysis showed that (a) the attached biofilm signifi-
cantly lowers the mass transfer driving force for
phenol across the membrane, and (b) oxygen con-
centration limits the phenol degradation rate in
the biofilm. These conclusions from the model
are consistent with the experimental results.
The effect of adaptation of mixed culture in the
phenol biodegradation was studied by Marrot
et al. (2006). The degradation experiments were
3
carried out at different phenol concentrations
from 0.5 to 3 g L 1. Biological treatment showed
to be economical and practical leading to a com-
plete removal of phenol. High concentrations of
phenol were inhibitory for growth, so it was for
the rates of substrate utilization that were greater at
low initial concentrations. Haldane kinetics model
for single substrate was used to obtain maximum
specific growth rates (mm = 0.438 h 1), half satu-
ration (K = 29.54 mg L 1), and substrate inhibi-
tion constant (K i = 72.45 mg L 1). These results
were in agreement with those reported in the liter-
ature for phenol removal abilities in different sys-
tems, although the concentration in phenol was
significant, and the Haldane model was acceptable.
References
Ahn S, Song I, Choung Y, Park J (2011) Improved phenol
degradation in high-phenol-fed MBR by membrane-
driven containment of non-settling biodegradation
microbes. Desalin Water Treat 31:320–325
Abargues MR, Robles A, Bouzas A, Seco A (2012)
Micropollutants removal in an anaerobic membrane
bioreactor and in an aerobic conventional treatment
plant. Water Sci Technol 65:2242–2250
Djafer L, Ayral A, Ouagued A (2010) Robust synthesis
and performance of a titania-based ultrafiltration mem-
brane with photocatalytic properties. Sep Purif
Technol 75:198–203
Livingston AG (1993) A novel membrane bioreactor for
detoxifying industrial waste-water. 1. Biodegradation
of phenol in a synthetically concocted waste-water.
Biotechnol Bioeng 41:915–926
Marrot B, Barrios-Martinez A, Moulin P, Roche N (2006)
Biodegradation of high phenol concentration by acti-
vated sludge in an immersed membrane bioreactor.
Biochem Eng J 30:174–183
Sadeghi F, Mehrnia MR, Nabizadeh R, Sarrafzadeh MH
(2012) Treatment of synthetic olefin plant wastewater
at various salt concentrations in a membrane bioreac-
tor. Clean-Soil Air Water 40:416–421
Yang S, Gu JS, Yu HY, Zhou J, Li SF, Wu XM, Wang
L (2011) Polypropylene membrane surface modifica-
tion by RAFT grafting polymerization and TiO2
photocatalysts immobilization for phenol decomposi-
tion in a photocatalytic membrane reactor. Sep Purif
Technol 83:157–165
Wang ZX, Xu XC, Gong Z, Yang FL (2012) Removal of
COD, phenols and ammonium from Lurgi coal gasifi-
cation wastewater using A(2)O-MBR system.
J Hazard Mater 235:78–84
P
Phenol Production by Membrane
Reactor
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
The great interest in the oxidation reaction of
benzene to phenol is linked to some disadvan-
tages of the cumene process, such as environmen-
tal impact, production of an explosive
intermediate and the fact that this is a multistep
process that involves a low yield of phenol and a
high capital investment. Moreover, the high ace-
tone production as a coproduct, which results in
an oversupply in the market, is another drawback.
Various studies concerning a new approach based
on a one-step and acetone-free method for phenol
production have been reviewed by Molinari and
Poerio (2010). Particular attention was devoted to
phenol production processes using various con-
figurations of membrane reactors (MRs) and a
photocatalytic membrane reactor (PMR). In par-
ticular, the biphasic MR allowed to achieving
high selectivity values (97–98 %). The various
methods have been classified according to oxi-
dant type such as N2O, O2, and H2O2. All of them
indicated that direct oxidation of benzene to phe-
nol is a difficult task and further efforts are
needed to search and to replace the three-step
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_961-2
traditional process with a process of direct oxida-
tion to convert benzene in phenol.
Phenol production through the direct hydrox-
ylation of benzene with hydrogen peroxide using
a catalytic membrane reactor was studied by
Molinari et al. (2006). The reaction was carried
out in a biphasic system separated by a mem-
brane. This new system showed a high selectivity
to phenol, minimizing its overoxidation in
overoxygenated by-products. The effect of vari-
ous reaction parameters such as the addition of
hydrogen peroxide mode, amount of hydrogen
peroxide, type of membrane, type of catalyst,
and organic acid was investigated. The results
showed that iron(II) sulfate as the catalyst,
18 mmol of hydrogen peroxide pumped for 4 h
in the aqueous phase as oxidant feeding, acetic
acid and polypropylene hydrophobic porous sup-
port gave the best system performance in terms of
produced phenol (17.42 mmol), selectivity to
phenol (99.94 %), benzene conversion to phenol
(1.20 %), and conversion of hydrogen peroxide to
phenol (96.78 %).
Use of vanadium based catalysts and product
recovery in benzene hydroxylation to phenol was
studied in a two-phase membrane reactor by
Molinari et al. (2012). Benzene permeates,
through the hydrophobic polypropylene mem-
brane, in the aqueous phase containing the cata-
lyst while phenol permeates back accumulating
in the organic phase. The following fundamental
aspects have been studied: dose of hydrogen per-
oxide, initial oxidation states of vanadium
2 Phenol Production by Membrane Reactor
catalysts, duration of catalytic tests, and lifetime
of the membrane in terms of physical and chem-
ical resistance. It was observed that by feeding
the oxidant by a micro pump, working in the
“bulk tube” mode, phenol yield, final phenol con-
centration in the organic phase, phenol turnover
number, and system productivity increased, and
no tar was formed. Initial oxidation state of vana-
dium catalysts influenced system performance:
indeed improved results in terms of yield
(35.2 % vs. 25.1 %), conversion of hydrogen
peroxide to phenol (36.6 % vs. 25.9 %), and
productivity (0.97 g g(cat) 1 h 1 vs. 0.78 g g
(cat) 1 h 1) were obtained by using vanadium
(III) chloride compared to vanadium(IV) acetyl
acetonate. Higher phenol extraction/recovery in
the organic phase (61.1 % vs. 46.3 %) and then
higher selectivity (97.5 % vs. 92.8 %) were
obtained by increasing test duration from 270 to
510 min. A weak membrane resistance was
observed after 246 h of consecutive catalytic
runs on the same membrane piece, showing deg-
radation of the membrane material
(polypropylene) caused by the OH radical gener-
ated in the reacting mixture.
The one-step hydroxylation of benzene to phe-
nol with oxygen and hydrogen was studied by
Shu et al. (2009). It is a promising process, but
there are severe challenges associated with the
low phenol production. It was shown that the
reaction can be greatly promoted by the simulta-
neous use of a dense palladium membrane as a
catalyst and as a hydrogen distributor. This reac-
tion concept with palladium membranes was
tested under different reaction conditions, but it
was found that the palladium membranes were
almost inert for both the target reaction and the
benzene combustion. The authors summarized
and compared their results with those reported
in the literature investigating the effects of the
membrane preparation method and the combus-
tion of hydrogen and benzene. The hypotheses on
the mechanism and feasibility of the membrane
concept are also given.
A simple, low-cost design of glass capillary
microreactor for the catalytic oxidation of ben-
zene to phenol at ambient conditions was studied
by Basheer (2013). Polyvinylchloride-nanofiber-
membrane-supported titania nanoparticles (TiO2-
PVC) as catalyst was used by producing in situ
hydroxyl radicals as oxidant. The reaction was
monitored by gas chromatography–mass spec-
trometry (GC-MS). The reaction conditions
were optimized and the performance of the
microreactor was then compared with the con-
ventional laboratory scale reaction which used
hydrogen peroxide as oxidant. The microreactor
gave a better yield of 14 % for phenol compared
to 0.14 % in the conventional laboratory scale
reaction. Reaction conditions such as reaction
time, reaction pH, and applied potential were
optimized. With optimized reaction conditions
selectivity higher than 37 % and conversion of
benzene higher than 88 % were obtained.
The study of a new reactor design with sepa-
rate membranes for distributed dosage of hydro-
gen and oxygen, respectively, into
microstructured reaction channels for the direct
conversion of benzene to phenol in the gas phase
in a palladium membrane reactor has been inves-
tigated by Bortolotto and Dittmeyer (2010). The
highest phenol selectivity so far obtained on a
palladium-coated PdCu foil at 423 K was 9.6 %
with carbon dioxide being the dominant product.
References
Basheer C (2013) Nanofiber-Membrane-Supported TiO2
as a catalyst for oxidation of benzene to phenol.
J Chem 2013, Article ID 562305, 7 pages
Bortolotto L, Dittmeyer R (2010) Direct hydroxylation of
benzene to phenol in a novel microstructured mem-
brane reactor with distributed dosing of hydrogen and
oxygen. Sep Purif Technol 73:51–58
Molinari R, Poerio T (2010) Remarks on studies for direct
production of phenol in conventional and membrane
reactors. Asia-Pac J Chem Eng 5:191–206
Molinari R, Poerio T, Argurio P (2006) One-step produc-
tion of phenol by selective oxidation of benzene in a
biphasic system. Catal Today 118:52–56
Molinari R, Argurio P, Poerio T (2012) Vanadium(III) and
vanadium(IV) catalysts in a membrane reactor for
benzene hydroxylation to phenol and study of mem-
brane material resistance. Appl Catal Gen
437:131–138
Shu SL, Huang Y, Hu XJ, Fan YQ, Xu NP (2009) On the
membrane reactor concept for one-step hydroxylation
of benzene to phenol with oxygen and hydrogen.
J Phys Chem C 113:19618–19622
P
Phenol Recovery Using Membrane
Contactor
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Phenol recovery from different aqueous solutions
(industrial wastewater and process water) is of
wide interest from environmental and industrial
point of view. Among the various recovery pro-
cesses, some of the involving membranes are
described in the following.
The recovery of phenol from aqueous solu-
tions with CYANEX (R) 923 was studied by
Cichy et al. (2001). Classical dispersive extrac-
tion and three membrane extraction-stripping
systems (bulk liquid membranes, three-phase
hollow-fiber contactor, and two hollow-fiber
module setup) were used. It was found that
CYANEX (R) 923 was a convenient carrier for
recovery of phenol from aqueous streams in
extraction-stripping membrane processes. The
problem of emulsion formation, so important in
dispersive extraction, was avoided. Both mass-
transfer experiments in different membrane sys-
tems and measurement of the dynamic interfacial
tension demonstrated the importance of the inter-
facial phenomena occurring in the stripping
stage. A blocking of this interface was observed
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_962-2
that resulted in a decrease of phenol mass
transfer.
Pertraction of dimethylcyclopropane-
carboxylic acid (DMCCA) and phenol in a new
hollow-fiber (HF) contactor of three liquid phases
with distributed U-shaped bundles of micropo-
rous HF was studied by Schlosser et al. (2002).
Trioctylamine (TOA), Hostarex A327, and
Cyanex 47 1 X have been used as carriers. The
performance of this contactor is similar to other
HF contactors. Its advantage is that both bundles
of fibers can elongate without deformation of
fibers and maldistribution of fibers in the bundles.
Pulsation of the membrane phase increases the
transport rate by 35–61 %, and it reaches a pla-
teau value at the pulsation velocity of about
1.1 mm
s 1. With increasing velocity of the
feed in the fiber lumen, the value of the overall
mass-transfer coefficient increases, but soon a
steady value is approached at the velocity of
about 5.5 cm
s 1. The diffusion resistances in
a series model do not describe the pertraction of
DMCCA well. The suggested new diffusion-
reaction model, considering the resistance based
on the kinetics of the stripping reaction, fits
experimental data well. Not only the rate of the
acid-carrier complex decomposition but also that
of the DMCCA dimer decomposition has to be
considered. The estimated values of the apparent
reaction rate constant were for the membrane
with TOA 1.91
10 6 m
s 1 and for pure
n-alkanes 5.78
10 6 m
s 1. The kinetic resis-
tance on the stripping interface represents
2 Phenol Recovery Using Membrane Contactor
20–60 % of the overall mass-transfer resistance,
and its value is comparable to the diffusion resis-
tance of both walls.
Application of membrane techniques
(pervaporation and membrane-based solvent
extraction) and adsorption to the removal of phe-
nol from solutions modeling wastewater from
phenol production by cumene oxidation process
was investigated by Kujawski et al. (2004). The
transport and separation properties of composite
membranes PEBA, PERVAP 1060, and
PERVAP 1070 in pervaporation of water-phenol
mixtures were determined. It was found that the
best removal efficiency of phenol was obtained
using the PEBA membrane. MTBE, cumene, and
the mixture of hydrocarbons were applied in the
membrane-based phenol extraction. Extra-flow
contactor with Celgard X-30 polypropylene
hollow-fiber porous membranes was used in the
experiments. MTBE was found the most efficient
extractant. Adsorption of phenol on the different
Amberlite resins was also investigated. Among
the Amberlite resins of various grades used, the
Amberlite XAD-4 had the best properties in the
phenol removal from the aqueous solutions. It
was shown that regeneration of the adsorbent
bed could be effectively performed with sodium
hydroxide solution.
The extraction and stripping of phenol using a
solution of tributyl phosphate in kerosene in a
hydrophobic polypropylene hollow-fiber mem-
brane contactor was studied by Shen
et al. (2009). The effect of the aqueous and the
organic phase flow rates on the overall mass-
transfer coefficient for both extraction and strip-
ping steps was investigated. Experimental values
of the overall mass-transfer coefficient were
determined and compared with predicted values
from the resistance in series model. Results
showed that the overall mass-transfer coefficients
for extraction were about one order of magnitude
greater than those measured during the stripping
process. The experimental values were in good
agreement with the predicted values for the
extraction module. However, the predicted
values were slightly overestimated for the strip-
ping module. The individual mass-transfer resis-
tances were analyzed, and the rate-controlling
steps of mass transfer were also identified in
both extraction and stripping modules. The
major resistance in extraction and stripping was
in the aqueous phase and in the membrane phase,
respectively.
The removal of phenols from wastewater has
been investigated under various operational con-
ditions using hydrophobic hollow-fiber mem-
brane contactors (Shen et al. 2012).
Experimental overall mass-transfer coefficients
were obtained in both handmade and Liqui-
Cel™ modules. Model predictions based on a
resistance in series model with solvent-filled
membrane pores matched well with experimental
values for tributyl phosphate/Shellsol extraction
systems. However, the predictions were in poor
agreement with experimental data obtained when
50 % pentanol/xylene was used to treat industrial
wastewater in the handmade module. Further
analysis showed that the operational pressure on
the aqueous side and the breakthrough pressure
for the two solvents probably influenced the posi-
tion of the interface within the membrane pores.
This change in wetting patterns resulted in sig-
nificant differences in mass transfer and solute
recovery which can be accounted for by adjusting
the position of the interface within the membrane
fiber.
References
Cichy W, Schlosser S, Szymanowski J (2001) Recovery of
phenol with CYANEX((R)) 923 in membrane
extraction-stripping systems. Solvent Extr Ion Exch
19:905–923
Kujawski W, Warszawski A, Ratajczak W, Porebski T,
Capala W, Ostrowska I (2004) Removal of phenol
from wastewater by different separation techniques.
Desalination 163:287–296
Shen SF, Smith KH, Cook S, Kentish SE, Perera JM,
Bowser T, Stevens GW (2009) Phenol recovery with
tributyl phosphate in a hollow fiber membrane
contactor: experimental and model analysis. Sep
Purif Technol. 69:48–56
Shen SF, Kentish SE, Stevens GW (2012) Effects of
operational conditions on the removal of phenols
from wastewater by a hollow-fiber membrane
contactor. Sep Purif Technol 95:80–88
Schlosser S, Sabolova E (2002) Three-phase contactor
with distributed U-shaped bundles of hollow-fibers
for pertraction. J Membr Sci 210:331–347
P
Phenol Separation on PV Membrane
Reactor
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Phenol separation from different aqueous and
nonaqueous solutions (industrial wastewater and
process water) using pervaporation
(PV) membranes is of wide interest from envi-
ronmental and industrial point of view. In the
following, applications of these membranes are
described.
A general review on different membrane pro-
cesses and membrane reactors in petrochemical
industry, such as olefin/paraffin separation pro-
cesses, light solvent separation, solvent
dewaxing, phenol and aromatic recovery, dehy-
drogenation, oxidative coupling of methane, and
steam reforming of methane were discussed in
detail by Ravanchi et al. (2009). Besides, separa-
tion using polymer-inorganic nanocomposite
membranes and wastewater treatment using
membrane bioreactors are reported. The avail-
able technologies for the abatement of phenol
from water and gaseous streams were briefly
reviewed, and the recent advancements summa-
rized by Busca et al. (2008). In this work separa-
tion technologies, such as distillation, liquid-
liquid extraction with different solvents,
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_963-2
adsorption over activated carbons and polymeric
and inorganic adsorbents, membrane
pervaporation, and membrane-solvent extraction,
are discussed. Destruction technologies such as
non-catalytic, supercritical, and catalytic wet air
oxidation; ozonation; non-catalytic, catalytic,
and enzymatic peroxide wet oxidation; electro-
chemical and photocatalytic oxidation; supercrit-
ical wet gasification; destruction with electron
discharges; as well as biochemical treatments
are also considered. In particular, for the abate-
ment of phenol from gases, condensation, absorp-
tion in liquids, adsorption on solids, membrane
separation, and thermal, catalytic, photocatalytic,
and biological oxidation are also described and
the experimental conditions and performances of
the different techniques compared.
Application of membrane techniques
(pervaporation and membrane-based solvent
extraction) and adsorption to the removal of phe-
nol from solutions modeling wastewater from
phenol production by cumene oxidation process
was investigated by Kujawski et al. (2004a). The
transport and separation properties of composite
membranes PEBA, PERVAP 1060, and
PERVAP 1070 in pervaporation of water-phenol
mixtures were determined. It was found that the
best removal efficiency of phenol was obtained
using the PEBA membrane. MTBE, cumene, and
the mixture of hydrocarbons were applied in the
membrane-based phenol extraction. Extra-Flow
contactor with Celgard X-30 polypropylene
hollow-fiber porous membranes was used in the
2 Phenol Separation on PV Membrane Reactor
experiments. MTBE was found the most efficient
extractant. Adsorption of phenol on the different
Amberlite resins was also investigated. Among
the Amberlite resins of various grades used, the
Amberlite XAD-4 had the best properties in the
phenol removal from the aqueous solutions. It
was shown that regeneration of the adsorbent
bed could be effectively performed with sodium
hydroxide solution.
Application of pervaporation and adsorption
to the removal of phenol from solutions modeling
wastewater from phenol production with cumene
oxidation process was investigated by Kujawski
et al. (2004b). The transport and separation prop-
erties of composite membranes PEBA, PERVAP
1060, and PERVAP 1070 in pervaporation of
water-acetone, water-phenol, and water-phenol-
acetone mixtures were determined. It was found
that all membranes were selective toward phenol.
The PEBA membrane showed the best selectiv-
ity. However, this membrane is not actually
available on the commercial scale. Thus, in the
practical applications, PERVAP-1060 and
PERVAP-1070 could be used. Adsorption of
phenol on the different Amberlite resins was
also investigated. Among the Amberlite resins
of various grades used, the Amberlite XAD-4
had the best properties in decontamination of
aqueous phenol solutions. It was shown that
regeneration of the adsorbent bed could be effec-
tively performed with sodium hydroxide
solution.
The separation of a phenol-water mixture
using a polyurethane membrane by a
pervaporation method was investigated by
Hoshi et al. (1997). Polyurethane was selected
as a membrane material because its affinity for
phenol was considered to be high and was pre-
pared by the polyaddition of
1,6-diisocyanatohexane and polytetramethyle-
neglycol. The polyurethane layer was
sandwiched with a porous polypropylene mem-
brane (Celgard ® 2500). Pervaporation measure-
ments were carried out under vacuum on the
permeate side, and the permeate vapor was col-
lected with a liquid nitrogen trap. The phenol
concentration in the permeate solution increased
from 0 to 65 wt.% with increasing feed
concentration of phenol from 0 to 7 wt.%. The
total flux also increased up to 930 g
m 2
h 1 with
increasing phenol partial flux. In the sorption
measurement at 60  C, the concentration of phe-
nol in the membrane was 68 wt.%, which was
higher than that of the permeate solution.
The effect of the methylene group length in
poly(alkylene glycols) on permselectivity and
solubility of phenol was studied by Hoshi
et al. (2000) in dilute aqueous solution through
polyurethane membranes by pervaporation. The
poly(alkylene glycols) were obtained by poly-
condensation of 1,6-hexanediol, 1,8-octanediol,
and 1,10-decanediol with a sulfuric acid catalyst.
Polyethyleneglycol and polytetramethyle-
neglycol were commercially available. Progress
of the polymerization in the poly(alkylene gly-
cols) was confirmed by FTIR, 1H-NMR analysis,
and size-exclusion chromatography (SEC) mea-
surements. The polyurethanes were obtained by
polyaddition reaction of
1,6-hexamethylenediisocyanate and the poly
(alkylene glycol) and were confirmed by FTIR
analysis and SEC measurements. The phenol
concentration in a permeate liquid increased
from 25.1 to 36.2 wt.%, and the phenol partial
flux also increased from 49.3 to 68.9 g
m 2
h 1
with increasing the methylene group length in the
poly(alkylene glycols), whereas the water partial
flux slightly decreased. As a result of sorption
measurements, the change in the degree of swell-
ing was small, and the phenol concentration in the
membrane increased from 42.1 to 70.8 wt.%. The
increase in the methylene group length of the
poly(alkylene glycols) should contribute to an
increase in the hydrophobicity of the polyure-
thane so that the solubility of phenol to the mem-
brane should increase. The phenol concentration
in the permeate liquid and the phenol partial flux
increased with an increase in the methylene
group length of the poly(alkylene glycols) due
to the increase in the phenol solubility for the
polyurethane membranes.
Phenol Separation on PV Membrane Reactor
References
Busca G, Berardinelli S, Resini C, Arrighi L (2008) Tech-
nologies for the removal of phenol from fluid streams:
a short review of recent developments. J Hazard Mater
160:265–288
Hoshi M, Kogure M, Saitoh T, Nakagawa T (1997) Sep-
aration of aqueous phenol through polyurethane mem-
branes by pervaporation. J Appl Polym Sci
65:469–479
Hoshi M, Ieshige M, Saitoh T, Nakagawa T (2000) Sepa-
ration of aqueous phenol through polyurethane mem-
branes by pervaporation. III. Effect of the methylene
3
group length in poly(alkylene glycols). J Appl Polym
Sci 76:654–664
Kujawski W, Warszawski A, Ratajczak W, Porebski T,
Capala W, Ostrowska I (2004a) Removal of phenol
from wastewater by different separation techniques.
Desalination 163:287–296
Kujawski W, Warszawski A, Ratajczak W, Porebski T,
Ostrowska I (2004b) Application of pervaporation and
adsorption to the phenol removal from wastewater.
Sep Purif Technol 40:123–132
Ravanchi MT, Kaghazchi T, Tahereh, Kargari A (2009)
Application of membrane separation processes in pet-
rochemical industry: a review. Desalination
235:199–244
F
Flat Sheet Membrane Photocatalytic the initial 4NP concentration (40 mg/l) after a
Reactor transient period of 300 min.
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende, CS, Italy
When membrane configuration is flat type and it
is coupled to a photocatalytic reaction, the reactor
can be named flat-sheet membrane photocatalytic
reactor.
A recirculation cell containing various types
of flat-sheet membranes which were able to retain
the suspended catalyst and partially selective to
the pollutant was studied by Molinari
et al. (2001). The membranes were NTR7410
and NTR7450 (Nitto Denko), N30F and
NF-PES-010 (Hoechst), and MPCB0000R98
(SEPAREM). The measured permeate flux was
in the range 5–30 l/h m2 at 4 bar, and all mem-
branes showed both a rejection and a capacity to
adsorb the pollutant with a transitory phase vary-
ing from 80 to 400 min at 4 bar. This behavior
could be a benefit for the process because oscil-
lations in the pollutant concentration were not
transmitted in the permeate. Three factors, rejec-
tion, photocatalytic degradation, and adsorption,
were able to maintain the 4-nitrophenol (4NP)
concentration in the permeate at very low values.
For the continuous system, the lowest 4NP con-
centration in the permeate was 6–7 % (w/w) of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_964-4
In another method, the catalyst, TiO2 P25
Degussa, was immobilized by physical deposi-
tion on a flat-sheet polymeric membrane, and
4NP was used as a model molecule to evaluate
the reactor performance (Molinari et al. 2000).
A preliminary investigation of the stability, under
UV irradiation, of some eligible polymeric mem-
branes was carried out by using scanning electron
microscopy (SEM), optical microscopy (OM),
determinations of water permeation flux (WPF),
and total organic carbon (TOC). These tests
showed that commercial membranes made of
fluoride + PP (FS 50 PP-Dow), polysulfone +
PP (GR 51 PP-TechSep), and polyacrylonitrile
(PAN-TechSep) seemed to be quite stable to
UV light over a 24 h period of irradiation. Immo-
bilization of TiO2 onto membranes by
ultrafiltrating TiO2 suspensions showed an opti-
mal layer density slightly >2.04 mg TiO2 per cm2
of membrane surface area. Results obtained from
membrane reactor studies indicated that the
observed initial rate constants for the degradation
of 4NP were almost independent on the amount
of TiO2 employed over the range
0.76–4.08 mg/cm2. A 50 % weight degradation
of 4NP after 5 h of irradiation in the presence of
air was obtained. An almost complete degrada-
tion of 4NP, instead, was observed in the pres-
ence of TiO2 suspended in the solution and pure
oxygen. The permeate deriving from the mem-
brane photoreactor was clear, and 4NP
2 Flat Sheet Membrane Photocatalytic Reactor
concentration was approximately equal to that
found in the retentate. The possibility of the con-
tinuous reuse of the photocatalyst and the contin-
uous separation of products from the reaction
medium gave some advantages over traditional
approaches.
A flat-sheet membrane photocatalytic reactor
operates, generally, with suspended solids (the
catalyst) and air bubbling (oxygen feed), so, in
the following, some cases of interest for operat-
ing such reactors are reported.
Selection of a membrane configuration is a
crucial step in the design process and has a high
impact on further plant operations. Despite
increasing experience with full-scale applica-
tions, practical knowledge concerning the impact
of different membrane configurations on process
performance and operational costs is still lacking.
Full-scale performance data of a membrane bio-
reactor (MBR) comparing the use of flat-sheet
and hollow-fiber membranes and analyses of the
consequences on operation, performance, and
treatment efficiency have been reported by
Krzeminski et al. (2012). Hollow-fiber configu-
rations, compared to the flat sheet, are designed
for higher fluxes, operated at lower concentra-
tions, cleaned more often, and protected by
stricter pretreatment. Filterability of activated
sludge from municipal MBRs was better than
from industrial MBRs and did not depend on
membrane configuration. The energy consump-
tion depends more on the influent type than on the
membrane configuration.
An aerated flat-sheet module focusing on the
effect of bubble distribution on the spatial varia-
tion of surface mass transfer with intermittent
slug bubbling was studied by Field et al. (2011).
This mode of operation will delay the onset of the
transmembrane pressure jump if biomass
removal is more dependent upon maximum
shear stress than mean shear stress. Two basic
setups were considered: an orifice in the middle
of the aeration tube, at the base, and two symmet-
rically placed orifices in the aeration tube. With
relatively low air rates, a single orifice generates a
higher average enhancement than two orifices,
but the reverse was found at a relatively higher
air rate. The enhancement in the center area of the
module was relatively higher than that of the edge
regions when using a single orifice, but more
uniformity was achieved with two.
Exploration of two major commercialized flat-
sheet and hollow-fiber membranes in a submerged
membrane fungi reactor fed with a synthetic tex-
tile wastewater revealed striking differences in the
extent and mechanism of fouling between the two
types, indicating a case-specific scope of choice
between them for industrial wastewater treatment
(Hai et al. 2005). The hollow-fiber membrane
exhibited fouling with a cake layer composed of
fungi and starch, intensity being proportional to
the operating flux (0.05–0.3 m/d). Conversely, the
flat-sheet membrane suffered from immediate
internal pore blocking beyond a critical flux of
0.2 m3 m 2 d 1. During the experiment with
major constituents of the synthetic wastewater
separately, while media containing only starch
and only dye induced negligible fouling, flux-
dependent pore blocking was evident for both the
hollow-fiber (0.288 m3 m 2 d 1) and flat-sheet
membranes (1.3 m3 m 2 d 1) for the mixture of
starch and dye. Despite that a remarkable 99 %
color and 97 % TOC removal were achieved by
both membranes, fouling with different modes and
intensity for the two types under similar conditions
and for the same type of membrane under different
exposure conditions warrants development of
suitable modules for such recalcitrant wastewater.
The oxygen transfer across a microporous,
flat-sheet membrane with and without a nitrifying
membrane-aerated biofilm (MAB) was studied
by Shanahan and Semmens (2006). Clean mem-
brane oxygen transfer was quantified via average
mass transfer coefficients and local fluxes calcu-
lated from profiles of dissolved oxygen
(DO) along the membrane length. Stoichiometric
calculations and DO profiles were used to
characterize oxygen transfer with a nitrifying
MAB. Comparison of the local fluxes with clean
and biofilm-coated membranes revealed that
oxygen transfer was decreased in upstream sec-
tions of the membrane during cultivation of an
MAB due to reduced advection and/or turbulence
near the membrane surface. By contrast, oxygen
transfer was increased in downstream sections of
the membrane via bacterial respiration. Oxygen
Flat Sheet Membrane Photocatalytic Reactor
fluxes generally decreased in the downstream
direction with biofilm-coated membranes; how-
ever, variability in biofilm structure and mem-
brane coverage altered this trend on several
occasions. Furthermore, biofilm structures were
observed to form via sloughing and settling of
biomass at the membrane surface. Thus mem-
brane configuration may have a significant influ-
ence on oxygen transfer rates in membrane
reactors.
References
Field RW, Zhang KS, Cui ZF, Hwang BK (2011) Flat
sheet MBRs: analysis of TMP rise and surface mass
transfer coefficient. Desalination Water Treat
35:82–91
3
Hai FI, Yamamoto K, Fukushi K (2005) Different fouling
modes of submerged hollow-fiber and flat-sheet mem-
branes induced by high strength wastewater with con-
current biofouling. Desalination 180:89–97
Krzeminski P, Gil JA, van Nieuwenhuijzen AF, van der
Graaf JHJM, van Lier JB (2012) Flat sheet or hollow
fibre – comparison of full-scale membrane bio-reactor
configurations. Desalination Water Treat 42:100–106
Molinari R, Mungari M, Drioli E, Di Paola A, Loddo V,
Palmisano L, Schiavello M (2000) Study on a
photocatalytic membrane reactor for water purifica-
tion. Catal Today 55:71–78
Molinari R, Grande C, Drioli E, Palmisano L, Schiavello
M (2001) Photocatalytic membrane reactors for deg-
radation of organic pollutants in water. Catal Today
67:273–279
Shanahan JW, Semmens MJ (2006) Influence of a nitrify-
ing biofilm on local oxygen fluxes across a micro-
porous flat sheet membrane. J Membr Sci 277:65–74
P
Photocatalytic Membrane Reactor:
Conversion of Organic Compounds
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Photocatalytic synthesis in membrane reactors is
still at a preliminary research stage, despite the
great potentiality of photocatalytic processes,
especially when they are coupled with a mem-
brane separation system.
The possibility of using a membrane
photoreactor for organic synthesis, developing a
hybrid system in which the photocatalytic reac-
tion and the separation of the desired product
occurs in one step is of high interest.
Some results obtained in a photocatalytic
membrane contactor (PMC) for the one-step syn-
thesis of phenol, and its simultaneous separation,
are reported by Molinari et al. (2009). TiO2 has
been used as catalyst, benzene as both reactant
and extraction solvent, and a polypropylene
membrane to separate the organic phase from
the aqueous reactive environment. To avoid sec-
ondary products and to obtain an efficient phenol
production, the use of a membrane system, with
high phenol permeability and complete rejection
of the catalyst, coupled with the photocatalytic
process, seems a useful solution. The membrane
photoreactor built in this study consists of an
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_965-2
external lamp placed on a batch reactor
containing the aqueous solution with the catalyst
in suspension; by means of a peristaltic pump, the
solution is withdrawn from the photocatalytic
reactor to a membrane contactor module in
which a benzene solution is present as strip phase.
A set of preliminary experiments were
performed in order to select the operating condi-
tions to be employed in the batch and membrane
systems. Due to the low solubility of benzene in
water and to its high volatility, it was necessary to
work with an excess of substrate in solution. By
comparing the data in batch experiments
obtained at pH values equal to 5.5 and 3.1, it
was observed that the more acidic pH condition
allowed to obtain a slightly increase of phenol
production in the aqueous phase and a constant
flux in the organic phase after 2 h (1.27 mmol/
hm2). Moreover, the area of the three main HPLC
peaks detected at retention times of 3.0, 3.6, and
3.9 min indicated that a lower formation and
extraction of these intermediates occurred at the
acidic pH.
Other works concerning photocatalytic con-
versions are reported in the following. Selective
oxidation of various primary and secondary alco-
hols was studied by Pillai and Sahle-Demessie
(2002) in a gas phase photochemical reactor
using immobilized TiO2 catalyst. An annular
photoreactor was used at 463 K with an average
contact time of 32 s. The system was found to be
specifically suited for the selective oxidation of
primary and secondary aliphatic alcohols to their
2 Photocatalytic Membrane Reactor: Conversion of Organic Compounds
corresponding carbonyl compounds. Benzylic
alcohols gave higher conversions, however,
with more secondary reaction products. The reac-
tion mechanism for various products formed was
explained. The effects of different reaction
parameters, such as O2/alcohol ratio, water
vapor, UV light, and contact time, were studied.
The presence of oxygen was found to be critical
for the photooxidation. Water vapor in the feed
was also found to be beneficial, although it was
not as critical as in hydrocarbon oxidation, where
it was necessary for hydroxylating the catalyst
surface and sustaining its activity. In alcohol oxi-
dation, surface hydroxylation could be partially
provided by the hydroxyl groups of the alcohol
itself. Catalyst deactivation was also observed
and it was attributed to the surface accumulation
of reaction products. However, the catalyst
regained its original activity after regeneration
by calcination in air for 3 h at 723 K.
Selective photocatalytic oxygenation of vari-
ous substrates was achieved using organic
photocatalysts via photoinduced electron transfer
reactions of photocatalysts with substrates and
dioxygen under visible light irradiation
(Fukuzumi and Ohkubo 2013). Photoinduced
electron transfer from benzene to the singlet
excited state of the 3-cyano-1-
methylquinolinium ion enabled the oxidation of
benzene by dioxygen with water to yield phenol
selectively. Alkoxybenzenes were obtained when
water was replaced by alcohols under otherwise
the same experimental conditions. Photocatalytic
selective oxygenation reactions of aromatic com-
pounds was also achieved using an electron
donor-acceptor, 9-mesityl-10-methylacridinium
ion acting as a photocatalyst, and dioxygen as
an oxidant under visible light irradiation.
The most recent advances in the application of
heterogeneous photocatalysis to synthesize valu-
able compounds by selective oxidation and
reduction are reported by Palmisano et al. (2010).
The photocatalytic oxidation of 4-
methoxybenzyl alcohol in water was performed
in a fixed bed continuous annular reactor by using
a home-prepared TiO2 catalyst supported on
Pyrex glass beads (Yurdakal et al. 2010). The
investigation was aimed to modeling the complex
kinetics of the photoprocess which occurs
through two parallel pathways: (i) partial oxida-
tion to the corresponding aldehyde and (ii) total
oxidation to CO2 and H2O. On these grounds, the
influence of liquid flow rate, inlet concentrations
of alcohol and oxygen, catalyst amount, and irra-
diation power on the photoreactivity were stud-
ied. A kinetic model like that of Langmuir-
Hinshelwood satisfactorily fitted the experimen-
tal results and allowed determination of the
values of model parameters. It was found that
all these parameters are positively affected by
an increase of radiant energy absorbed by the
catalyst. All the reactivity results indicate that
the partial oxidation pathway is favored by the
low flux of absorbed photons and by low oxygen
coverage on the TiO2 surface; opposite condi-
tions favor the mineralization pathway.
The photoproduction of vanillin was studied
in aqueous medium starting from trans-ferulic
acid, isoeugenol, eugenol, or vanillyl alcohol by
using both commercial and home-prepared TiO2
samples as photocatalysts (Augugliaro
et al. 2012). The visible light-induced oxidation
of trans-ferulic acid by TiO2 photocatalysis was
also carried out under visible light via the forma-
tion of a charge-transfer complex (Parrino
et al. 2012). A drawback for this type of photore-
action is the relatively low selectivity observed
and the presence of other products. The combi-
nation of photocatalysis and pervaporation by
using nonporous membranes has been suggested
to separate the vanillin or other aldehydes from
the irradiated suspension to avoid their subse-
quent oxidation, increasing in such a way the
selectivity (Camera Roda et al. 2010; Camera
Roda et al. 2013). The mild experimental condi-
tions used suggest that heterogeneous
photocatalysis could be in some cases an alterna-
tive green route for replacing environmentally
hazardous processes with safe and energy effi-
cient routes.
References
Augugliaro V, Camera Roda G, Loddo V, Palmisano G,
Palmisano L, Parrino F, Puma MA (2012) Synthesis of
Photocatalytic Membrane Reactor: Conversion of Organic Compounds
vanillin in water by TiO2 photocatalysis. Appl Catal
Environ 111–112:555–561
Camera Roda G, Augugliaro V, Loddo V, Palmisano L,
Palmisano G (2010) Production of aldehydes by oxi-
dation in aqueous medium with selective recovery of
the product by means of pervaporation. Patent
RM10A000319
Camera Roda G, Augugliaro V, Cardillo A, Loddo V,
Palmisano G, Palmisano L (2013) A pervaporation
photocatalytic reactor for the green synthesis of vanil-
lin. Chem Eng J 224:136–143. DOI: 10.1016/j.
cej.2012.10.037
Fukuzumi S, Ohkubo K (2013) Selective photocatalytic
reactions with organic photocatalysts. Chem Sci
4:561–574
Molinari R, Caruso A, Poerio T (2009) Direct benzene
conversion to phenol in a hybrid photocatalytic mem-
brane reactor. Catal Today 144:81–86
3
Palmisano G, García-López E, Marcı̀ G, Loddo V,
Yurdakal S, Augugliaro V, Palmisano L (2010)
Advances in selective conversions by heterogeneous
photocatalysis. Chem Commun 46:7074–7089
Parrino F, Augugliaro V, Camera Roda G, Loddo V,
López-Muñoz MJ, Márquez-Álvarez C, Palmisano G,
Palmisano L, Puma MA (2012) Visible light induced
oxidation of trans-ferulic acid by TiO2 photocatalysis.
J Catal 295:254–260
Pillai UR, Sahle-Demessie E (2002) Selective oxidation of
alcohols in gas phase using light-activated titanium
dioxide. J Catal 211:434–444
Yurdakal S, Loddo V, Palmisano G, Augugliaro V,
Berber H, Palmisano L (2010) Kinetics of 4-
methoxybenzyl alcohol oxidation in aqueous solution
in a fixed bed photocatalytic reactor. Ind Eng Chem
Res 49:6699–6708
P
Photocatalytic Membrane Reactor:
Degradation of Organic Compounds
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende, CS, Italy
Degradation of organic compounds in
photocatalytic membrane reactors has been one
of the first applications in the combination of
photocatalysis and membranes. The possibility
of using a membrane photoreactor for degrada-
tion of organics, developing a hybrid system in
which the photocatalytic reaction and the separa-
tion of the desired product occur in only one
device, is of high interest. Some results obtained
in this application are reported in the following.
The ability of cross-flow ultrafiltration (UF),
combined with photocatalytic reactions, to sepa-
rate TiO2 photocatalysts from treated water in
photocatalytic drinking water treatment was
investigated by Lee et al. (2001). The effect of
natural organic matter (i.e., humic acids) and
cross-flow velocities on UF fluxes and organic
removal was explored with and without UV irra-
diation in the photocatalytic reactor. The interac-
tion between the two solutes in the system, humic
acids and TiO2 photocatalysts, played a signifi-
cant role in the formation of dense cake layers at
the membrane surface, leading to a greater flux
decline during ultrafiltration of TiO2 particles.
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_966-2
According to visual observations of the used
membranes and the estimation of back-transport
velocities of the solutes, a substantial amount of
TiO2 deposited on the membrane induced a
higher amount of humic acids to accumulate at
the membrane through the adsorption onto TiO2
particles. The humic-acid-laden TiO2 particles
offered more than four times higher specific
cake resistance with a substantially increased
compressibility coefficient than TiO2 particles
alone. The higher the cross-flow velocities, the
greater the UV254 removal achieved. This was
because the rise of cross-flow velocities contrib-
uted to the reduction of concentration polariza-
tion at the membrane surface, thereby resulting in
a decrease of the driving force for humic acids to
pass through the membrane. When photocatalytic
reactions took place with UV illumination,
UV254 removal efficiencies of the permeate
were improved markedly, and also the permeate
flux was kept at a constant level without any sign
of fouling. Although humic acids were not
completely mineralized by photocatalysis, the
degradation of the humic acids helped to enhance
the UF flux, as they were transformed to less
adsorbable compounds.
A photocatalytic reaction system, composed
of solution and gas spaces divided by a thin
Teflon film and TiO2-coated mesh or cloth, for
the treatment of contaminated aqueous solutions
was developed to be operated with enhanced
aeration without bubbling of air in the solution
(Villacres et al. 2003). First, the photocatalytic
2 Photocatalytic Membrane Reactor: Degradation of Organic Compounds
activities of TiO2 particles immobilized on two
kinds of support material, stainless steel mesh
(SSM) and fiberglass cloth (FGC), were investi-
gated for photocatalytic oxidation of 2-propanol,
as a model volatile organic compound, dissolved
in aerated aqueous solution. The TiO2 particles
immobilized on both support materials exhibited
photocatalytic activity to oxidize 2-propanol into
acetone and carbon dioxide (CO2), and the activ-
ity levels of the TiO2 particles immobilized on
the two kinds of support materials were compa-
rable. Presumably due to the presence of a small
amount of metal species originating in SSM that
might work as reduction catalysts, molecular
hydrogen H2 was also liberated on the TiO2-
immobilized SSM. Results of analysis of weight
loss after photoirradiation suggested that the sta-
bility of the TiO2-immobilized FGC was better
than that of the TiO2-immobilized SSM. On the
basis of these results, FGC was employed in
construction of a photocatalytic reactor equipped
with an O2-permeable Teflon membrane in order
to make oxygen pass from a gas space to a solu-
tion space and to keep the surface of the
immobilized TiO2 photocatalyst, facing an aque-
ous solution containing volatile organic com-
pounds, saturated with dissolved O2. From the
results of photocatalytic oxidative decomposition
of 2-propanol, it was clarified that the surfaces of
TiO2 particles could be sufficiently supplied with
O2 from the gas space through the membrane to
accelerate the oxidation.
Dyes are organic compounds used in textile,
food, and drug industries, and their abatement
represents one of the main problems in the treat-
ment processes because generally they are very
stable toxic compounds. Two commercial
azo-dyes, i.e., Congo Red (C32H22N6Na2O6S2)
and Patent Blue (C27H31N2NaO6S2), in aqueous
solution were degraded in a photocatalytic mem-
brane reactor (Molinari et al. 2004) by using TiO2
Degussa P25 as the catalyst. Different system
configurations and irradiating sources were stud-
ied, and the influence of some operational param-
eters such as the pressure in the membrane cell
and the initial concentration of the substrates
were determined. A comparison between
suspended and entrapped TiO2 was also done.
The experimental results showed a satisfactory
degradation efficiency of the photocatalytic
membrane process. The influence of various
parameters (e.g., feed concentration,
recirculation rate) has been discussed to obtain
high reaction rates, operating stability, and high
membrane rejection, both for substrates and
by-products. Congo Red was photodegraded
with higher rate under the same experimental
conditions probably due to its higher adsorption
onto the catalyst surface. It was possible to treat
successfully highly concentrated solutions
(500 mg/L) of both dyes by means of a continu-
ous process obtaining good values of permeate
fluxes (30–70 L/m2h); this could be interesting
for industrial applications. The reactor containing
the suspended photocatalyst was significantly
more efficient than the reactor containing the
catalyst entrapped into the membrane.
An advanced oxidation process (AOP) with
reactor capacity of 150 L, using ultraviolet
(UV) radiation and TiO2 photocatalyst, was eval-
uated for the destruction of toxic organic chemi-
cal, bisphenol A (BPA) by Thiruvenkatachari
et al. (2005). TiO2, in the form of powder, was
suspended as slurry in the water avoiding the
commonly adopted practice of immobilizing it
onto a carrier material such as glass, concrete,
or ceramics. Adsorption of BPA by TiO2 was
evaluated and was performed as a pretreatment
to AOP. The combined effect of ozone with the
AOP process was also studied. Coupling ozone
with UV/TiO2 brought about a synergistic effect
on BPA degradation and 10 ppm of BPA, and the
intermediate organic compounds were
completely removed within 3 h. The highlight
of this study was the simultaneous degradation
of BPA and separation of TiO2 particles from
water after the photocatalytic treatment, in order
to obtain reusable quality water. Separation of
TiO2 particles was carried out by a unique
two-stage coagulation and settling process
followed by submerged hollow fiber
microfiltration membrane technique. With initial
turbidity of 4,000 NTU, the turbidity of the final
permeate water was well below 0.1 NTU. Some
of the main advantages of this hybrid treatment
system include the possibility of large-scale
Photocatalytic Membrane Reactor: Degradation of Organic Compounds
treatment, complete and efficient BPA and its
organic intermediates degradation, easy separa-
tion and reuse of TiO2 that resulted free from
chemical coagulant contaminants, reusable qual-
ity water, and potentiality for continuous opera-
tion with simple process modifications.
A study of the photodegradation of different
pharmaceuticals [furosemide, ranitidine
(hydrochloride), ofloxacine, phenazone,
naproxen, carbamazepine, and clofibric acid] in
aqueous medium at various pHs by using a batch
photoreactor and a photocatalytic membrane
reactor working in recirculation regime was car-
ried out by Molinari et al. (2006). Polycrystalline
TiO2 was used as the photocatalyst, and different
membranes (NTR 7410, PAN GKSS HV3/T,
N 30F, NF PES 10) were tested. A different
adsorption of the substrates onto the catalyst sur-
face was observed owing to the hydrophilic/
hydrophobic character of the catalyst, depending
on the pH. The photodegradation of the seven
molecules in the batch reactor was successfully
carried out and the behavior was in accordance
with pseudo-first-order kinetics. Furosemide and
ranitidine were selected to carry out the study of
rejection and photodegradation in the hybrid
membrane system. The permeate flux of the
treated water was in the 31.5–60.0 L/(hm2)
range for NTR 7410 membrane, whereas rejec-
tion values in the range 10–60 % for furosemide
and 5–30 % for ranitidine in the dark (without
photoreaction) were found. The degradation in
the hybrid membrane photoreactor showed that
the photocatalyst was retained by the membrane
in the reaction ambient, while the membrane
rejection toward the pollutants was not very sat-
isfactory. A net decrease of the rejection down to
0 was observed in the contemporary presence of
light, photocatalyst, and oxygen.
The combination of a dialysis membrane and a
photocatalytic reactor into an original membrane
photoreactor (MPR) to mineralize organic com-
pounds contained in artificial turbid waters which
were obtained by using natural clay named ben-
tonite was studied by Azrague et al. (2007). Var-
ious systems have been described in the
literature, combining photocatalysis with
pressure-driven membrane techniques, such as
3
nanofiltration (NF) and ultrafiltration (UF), but
these systems can lead to membrane fouling.
Only the combination of photocatalysis and
membrane distillation avoids this problem, but
it needs energy to reach pervaporation phenom-
ena. The MPR system worked at ambient temper-
ature, with the membrane used as a barrier for
particles and to extract the organic compounds
from the turbid water without transmembrane
pressure. Thus it was possible to separate the
polluted turbid water from the photoreactor com-
partment and to separate TiO2 continuously from
the treated water. The photocatalytic reaction and
dialysis were studied separately before the MPR
process was developed. A model pollutant,
2,4-dihydroxybenzoic acid (2,4-DHBA), was
mineralized from turbid waters by
photocatalysis. By means of the membrane, the
TiO2 remained in the photoreactor compartment
without filtration and bentonite was kept away
from the photoreactor.
The degradation of toxic organic compounds
such as trichloroethylene (TCE) in water, using a
combined photocatalysis/microfiltration
(MF) system, was focused by Choo
et al. (2008). The performances of the hybrid
system were investigated in terms of the removal
efficiency of TCE and membrane permeability, in
the presence or absence of humic acids and at
different pHs. The fate of TCE during the
photocatalytic reactions was checked in order to
evaluate the feasibility of the photocatalytic
membrane reactor (PMR). Greater TCE degrada-
tion (>60 %) was achieved with an increase in
the TiO2 dosage (up to 1.5 g/L) in PMR, but a
substantially large TiO2 dosage brought about a
decrease in TCE degradation efficiency. The
photocatalytic decomposition of TCE appeared
to be more effective at acidic pH conditions than
at a neutral or alkaline pH. The alkalinity and the
addition of humic acids into the feedwater did not
produce a significant effect on TCE degradation,
while humic acids (whose dose was 1 mg/L as
TOC) in the feedwater played a role in a decline
of permeability by 60 %. Membrane permeability
in the PMR was also affected by tangential veloc-
ities. An improvement of 60 % in flux was
achieved when the tangential velocity increased
4 Photocatalytic Membrane Reactor: Degradation of Organic Compounds
from 0.19 to 1.45 m/s. This occurred because
flow regimes can govern the deposition of TiO2
particles on the membrane surface.
References
Azrague K, Aimar P, Benoit-Marquie F, Maurette MT
(2007) A new combination of a membrane and a
photocatalytic reactor for the depollution of turbid
water. Appl Catal Environ 72:197–204
Choo KH, Chang DI, Park KW, Kim MH (2008) Use of an
integrated photocatalysis/hollow fiber microfiltration
system for the removal of trichloroethylene in water.
J Hazard Mater 152:183–190
Lee SA, Choo KH, Lee CH, Lee HI, Hyeon T, Choi W,
Kwon HH (2001) Use of ultrafiltration membranes for
the separation of TiO2 photocatalysts in drinking water
treatment. Ind Eng Chem Res 40:1712–1719
Molinari R, Pirillo F, Falco M, Loddo V, Palmisano
L (2004) Photocatalytic degradation of dyes by using
a membrane reactor. Chem Eng Process 43:1103–1114
Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
erogeneous photocatalytic degradation of pharmaceu-
ticals in water by using polycrystalline TiO2 and a
nanofiltration membrane reactor. Catal Today
118:205–213
Thiruvenkatachari R, Kwon TO, Moon IS (2005) A total
solution for simultaneous organic degradation and par-
ticle separation using photocatalytic oxidation and
submerged microfiltration membrane hybrid process.
Korean J Chem Eng 22:938–944
Villacres R, Ikeda S, Torimoto T, Ohtani B (2003) Devel-
opment of a novel photocatalytic reaction system for
oxidative decomposition of volatile organic com-
pounds in water with enhanced aeration. J Photochem
Photobiol A Chem 160:121–126
P
Photocatalytic Processes by
Membrane Operations
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
A photocatalytic process combined with mem-
brane operations is a set of reduction and oxida-
tion photocatalytic reactions occurring in the
presence of a photocatalyst (see “▶ Photocatalytic
Process”) and a membrane giving rise to one or
more products (see “▶ Photocatalytic Membrane
Reactors”) starting from organic or inorganic sub-
strate(s).
Photocatalysis and, in particular, heteroge-
neous photocatalysis is a process of great poten-
tiality for pollutants abatement. To improve the
overall performance of the photoprocess, hetero-
geneous photocatalysis has been often combined
with physical or chemical operations, which
affect the chemical kinetics and/or the overall
efficiency. Various possibilities to couple hetero-
geneous photocatalysis with other technologies
to photodegrade organic and inorganic pollutants
dissolved in actual or synthetic aqueous effluents
have been described by Augugliaro et al. (2006).
These combinations increase the photoprocess
efficiency by decreasing the reaction time with
respect to the separated operations or they
decrease the cost with respect to heterogeneous
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_967-4
photocatalysis alone, generally in terms of light
energy. Depending on the operation coupled with
heterogeneous photocatalysis, two categories of
combinations exist. When the coupling is with
ultrasonic irradiation, photo-Fenton reaction,
ozonation, or electrochemical treatment, the
combination affects the photocatalytic mecha-
nisms thus improving the efficiency of the
photocatalytic process. When the coupling is
with biological treatment, membrane reactor,
membrane photoreactor, or physical adsorption,
the combination does not affect the
photocatalytic mechanisms, but it improves the
efficiency of the overall process. The choice of
the coupling is related to the type of wastewater
to be treated. A synergistic effect, giving rise to
an improvement of the efficiency of the
photocatalytic process, has been reported in the
literature for many cases.
The influence of the type of nanofiltration
membrane, initial concentration of pollutant,
and pH on the photodegradation rate was inves-
tigated by Molinari et al. (2002) in discontinuous
and continuous configurations in a photocatalytic
membrane system with the lamp immersed in the
suspension inside the photoreactor by using poly-
crystalline TiO2 (Degussa P25) as the catalyst
and humic acids, organic dyes, and 4-nitrophenol
as the pollutants. Two membranes were tested,
i.e., NF-PES-010 (Celgard, Germany) of
polyethersulfone and NTR-7410 (Nitto Denko,
Japan) of sulfonated polyethersulfone. The last
one was chosen for all of the photoreactivity
2 Photocatalytic Processes by Membrane Operations
experiments because permeability and rejection
tests indicated that it was able to hold both cata-
lyst and small molecules carrying the same mem-
brane charge (negative), thanks to the Donnan
exclusion. Despite the fluxes ranged between
20 and 40 L h 1 m 2 in operating conditions at
6 bar and these values were interesting for appli-
cation purposes, the rejections of NTR-7410
nanofiltration membrane, obtained during opera-
tion of the membrane photoreactor in the degra-
dation of humic acids, patent blue dye, and 4-
nitrophenol, were significantly lower than those
obtained in the absence of photodegradation,
probably because of the small molecular size of
the by-products and of the intermediate species
produced during the photodegradation process.
This means that in order to select a suitable mem-
brane, rejection should be determined during
operation of the photoreactor.
A batch-recirculated photoreactor was com-
bined with a hollow-fiber membrane ultrafiltra-
tion (UF) unit for heterogeneous photocatalysis
applications. The operation and modeling of the
UF process on the performance of the integrated
photoreactor-UF process was studied by
Sopajaree et al. (1999). Methylene blue and tita-
nium dioxide (Degussa P-25) were used as the
test pollutant and photocatalyst, respectively. The
influence of cross-flow velocity, transmembrane
pressure, and TiO2 dose on the permeate flux
through the hollow-fiber membrane was
described. The data were modeled on the basis
of concentration polarization and gel layer for-
mation at the membrane surface/feed slurry
boundary.
The photocatalytic degradation of natural
organic matter (NOM) is an attractive option in
the treatment of drinking water (Choo
et al. 2008). The performance of a submerged
photocatalytic membrane reactor (PMR) was
investigated with regard to the removal of NOM
and the control of membrane fouling.
The efficiency of a hybrid system combining
photocatalysis and membrane filtration in a single
module was investigated. Low-pressure sub-
merged hollow-fiber membranes were used to
retain the TiO2 particles in the system by Chin
et al. (2007) during the photodegradation of
bisphenol A (BPA) as the model pollutant. Aera-
tion was applied in the submerged membrane
photoreactor (SMPR) to provide (i) mixing,
(ii) dissolved oxygen, (iii) mechanical agitation
(to prevent agglomeration of TiO2 particles), and
(iv) shear forces (to remove TiO2 particles from
the membrane surface). It was found that inter-
mittent permeation enhanced the sustainability of
the submerged membranes but showed no effect
on the photoactivity of the system. An intermit-
tence aeration frequency (IF) of 0.1 was sufficient
to reduce the fouling rate of the membrane under
the experimental conditions. The SMPR appears
to be very effective and can achieve removal of
low-concentration organics (such as BPA) in a
compact, low-energy system. The combined
photocatalytic and membrane processes have
been more recently addressed also toward the
selective production of high-value molecules in
mild experimental conditions by using suitable
photocatalysts, solvent, and starting substrates
and membranes (Molinari et al. 2009a, b;
Augugliaro and Palmisano 2010).
References
Augugliaro V, Palmisano L (2010) Green oxidation of
alcohols to carbonyl compounds by heterogeneous
photocatalysis. ChemSusChem 3:1135–1138
Augugliaro V, Litter M, Palmisano L, Soria J (2006) The
combination of heterogeneous photocatalysis with
chemical and physical operations: a tool for improving
the photoprocess performance. J Photochem Photobiol
C Photochem Rev 7:127–144
Chin SS, Lim TM, Chiang K, Fane AG (2007) Hybrid
low-pressure submerged membrane photoreactor for
the removal of bisphenol A. Desalination 202:253–261
Choo KH, Tao R, Kim MJ (2008) Use of a photocatalytic
membrane reactor for the removal of natural organic
matter in water: effect of photoinduced desorption and
ferrihydrite adsorption. J Membr Sci 322:368–374
Molinari R, Borgese M, Drioli E, Palmisano L, Schiavello
M (2002) Hybrid processes coupling photocatalysis
and membranes for degradation of organic pollutants
in water. Catal Today 75:77–85
Molinari R, Caruso A, Palmisano L (2009a)
Photocatalytic membrane reactors in the conversion
or degradation of organic compounds. In: Drioli E,
Giorno L (eds) Membrane operations, innovative sep-
arations and transformations. Wiley-VCH, Weinheim,
pp 335–361
Photocatalytic Processes by Membrane Operations
Molinari R, Caruso A, Poerio T (2009b) Direct benzene
conversion to phenol in a hybrid photocatalytic mem-
brane reactor. Catal Today 144:81–86
Sopajaree K, Qasim SA, Basak S, Rajeshwar K (1999) An
integrated flow reactor-membrane filtration system for
3
heterogeneous photocatalysis. Part II: experiments on
the ultrafiltration unit and combined operation. J Appl
Electrochem 29:1111–1118
P
Photodegradation
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Photodegradation concerns the breaking of a
molecule to smaller molecules (degradation
and/or mineralization) by means of the absorp-
tion of photons of suitable wavelength such as
that found in the infrared radiation, visible light,
and ultraviolet light of the solar spectrum.
Photodegradation also includes the change of
the shape of a molecule such as protein denatur-
ation and the addition of other atoms or mole-
cules. One type of photodegradation reaction is
oxidation which is used to purify some drinking
water and wastewater to destroy pollutants.
Photodegradation can be photochemical and
photocatalytic: in the first case only light is
used, while in the second case a combination of
light and a semiconductor photocatalyst is used.
In the photocatalytic oxidation process, organic
pollutants are destroyed in the presence of semi-
conductor photocatalysts (e.g., TiO2 and ZnO),
an energetic light source, and an oxidizing agent
such as oxygen or air. Photocatalytic degradation
in aqueous medium is mainly dependent on the
solution pH, catalysts and their composition,
organic substrate type (usually pollutants) and
concentration, light intensity, catalyst loading,
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_968-6
ionic composition of wastewater, types of sol-
vent, oxidant concentration, and calcination tem-
peratures of the photocatalyst (Ahmed
et al. 2010).
In the degradation of organic pollutants, vari-
ous compounds such as dyes (Molinari
et al. 2003), drugs (Molinari et al. 2006), pesti-
cide and herbicide derivatives dominant in storm
water, and wastewater effluent have been treated.
In the photocatalytic process, the hydroxyl radi-
cal, which is generated from the oxidation of
adsorbed water as OH , is the primary oxidant
species, while the presence of oxygen prevents an
electron–hole pair recombination. In the
photocatalytic degradation of pollutants, when
the reduction process of oxygen and the oxidation
of pollutants do not proceed simultaneously,
there is an electron accumulation in the CB,
thereby causing an increase in the rate of recom-
bination of e and h+. Thus it is of paramount
importance to prevent electron accumulation in
efficient photocatalytic oxidation. In
photocatalysis, TiO2 has been studied extensively
because of its high activity, desirable physical
and chemical properties, low cost, and availabil-
ity. Among the TiO2 crystalline forms, anatase
and rutile forms have been investigated exten-
sively as photocatalysts. Anatase has been
reported to be more active as a photocatalyst
than rutile.
Heterogeneous photocatalysis involving zinc
oxide (ZnO) emerges as a promising new route
for water purification process in terms of the
2 Photodegradation
degradation and mineralization of dyes
discharged into wastewater from textile and
other industrial processes (Lam et al. 2012),
although ZnO can give rise to anodic
photocorrosion in aqueous systems, depending
on the experimental conditions chosen.
Removal of nitrogen-containing organic com-
pounds in wastewater by TiO2 photocatalytic
degradation is the result of a strong interaction
among pollutant structures, TiO2 properties, and
photocatalytic reaction conditions. It is also clear
that for each organic pollutant, a unique set of
conditions may be needed for the optimal perfor-
mance (Jing et al. 2011).
Solid-phase photocatalytic degradation for
eco-friendly disposal of polymer such as waste
plastics has been also studied. Composite plastics
embedding photocatalysts into polymer matrix
have excellent photocatalytic degradation activ-
ity. They could be degraded effectively in ambi-
ent air under sunlight exposure (Yang
et al. 2011).
Photoelectrochemical cell and the factors that
affect efficient production of electricity and
hydrogen by photocatalytic degradation of
(principally) organic and (secondarily) inorganic
waste materials are reported by Lianos. Materials
used for making a photoanode and the rest of the
components of the cell as well as the models of
cell efficiency and photodegradation procedures
during cell operation have been also described
(Lianos 2011).
Efficient photochemical systems for environ-
mental remediation can be constituted by a semi-
conductor and a surface-adsorbed antenna
molecule (dyes or other color species). The
major advantage of these systems is that they
are able to achieve the degradation of organic
pollutants by using visible light from the sun as
energy and O2 in the air as the oxidant under
ambient conditions (Chen et al. 2010).
References
Ahmed S, Rasul MG, Martens WN, Brown R, Hashib MA
(2010) Heterogeneous photocatalytic degradation of
phenols in wastewater: a review on current status and
developments. Desalination 261:3–18
Chen CC, Ma WH, Zhao JC (2010) Semiconductor-
mediated photodegradation of pollutants under
visible-light irradiation. Chem Soc Rev 39:4206–4219
Jing JY, Liu MH, Colvin VL, Li WY, Yu WW
(2011) Photocatalytic degradation of nitrogen-
containing organic compounds over TiO2. J Mol
Catal A-Chem 351:17–28
Lam SM, Sin JC, Abdullah AZ, Mohamed AR (2012) Deg-
radation of wastewaters containing organic dyes
photocatalysed by zinc oxide: a review. Desalin
Water Treat 41:131–169
Lianos P (2011) Production of electricity and hydrogen by
photocatalytic degradation of organic wastes in a
photoelectrochemical cell. The concept of the
photofuelcell: a review of a re-emerging research
field. J Hazard Mater 185:575–590
Molinari R, Pirillo F, Falco M, Loddo V, Palmisano
L (2003) Photocatalytic oxidation of dyes in a mem-
brane reactor. J Catal Mater Environ 2:77–80
Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
erogeneous photocatalytic degradation of pharmaceu-
ticals in water by using polycrystalline TiO2 and a
nanofiltration membrane reactor. Catal Today
118:205–213
Yang CJ, Peng TY, Deng KJ, Zan L (2011) Solid-phase
photocatalytic degradation of waste plastics. Prog
Chem 23:874–879
P
Photoreactor
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende CS, Italy
A photoreactor is a chemical reactor device
which brings photons, a photocatalyst, and reac-
tants into contact, as well as collects the reaction
products deriving from physicochemical trans-
formations. It can assume different shapes and
modes of operation and can be operated in vari-
ous environments of temperature and pressure.
Design a photoreactor means to establish type,
mode of operation, size, and optimal operative
conditions. Two general types of photoreactors
exist such as batch and plug flow: in the first one,
the mixing of reacting mixture is favored as high
as possible in order to assume a perfectly mixed
reactor, while in the second type, mixing is hin-
dered in order to assume a perfectly segregated
reactor. With respect to the operation mode,
photoreactors are classified in three general
types: (i) discontinuous reactor which during the
operation does not exchange matter with the
ambient; (ii) semicontinuous reactor which
exchanges reagents or products with the ambient;
and (iii) continuous reactor, for which there is a
continuous and equal inlet and outlet of mass.
The discontinuous reactor is simple and needs
only few accessories; it is suitable for
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_969-4
experimental kinetics studies, and it is industri-
ally used when the amount of matter to be treated
is quite small. The semicontinuous reactor is
flexible but more difficult to model; it allows a
good control on the reaction rate, as the reaction
may be affected by the addition of reagents or by
the subtraction of products. The continuous reac-
tor is suitable for industrial purposes when big
amount of matter must be treated and/or the reac-
tion rate is extremely high. It needs many acces-
sory devices, but it is possible to achieve a very
good control on the product quality (Loddo
et al. 2009). The utilization of radiation and
solid catalysts in a synergic effect for performing
chemical transformations of species present in
liquid or gaseous mixtures makes the heteroge-
neous photocatalytic reactors more complex than
the heterogeneous catalytic ones.
The main components of a photocatalytic sys-
tem are the photoreactor and the radiation. For
thermal catalytic processes, the reactor configu-
ration is chosen on the basis of (i) mode of oper-
ation, (ii) phases present in the reactor, (iii) flow
characteristics, (iv) needs of heat exchange, and
(v) composition and operative conditions of the
reacting mixture source (Braun et al. 1991). In
addition to previous parameters, the choice of the
heterogeneous photoreactors is conditioned by
the fact that their geometry and materials must
guarantee the penetration of radiation all over the
reacting mixture having in mind that the absorbed
photon energy should be equal or higher than the
bandgap of the used photocatalyst. In the case of
2 Photoreactor
stirred photoreactors, the presence of the
photocatalyst, usually a powdered micro- or
nanocrystalline semiconductor, affects in a com-
plex way the depth of radiation penetration.
Photoreactors and, thus, photocatalytic pro-
cesses are applicable in wastewater treatment,
energy production, chemical synthesis, and
greenhouse gas mitigation. They have the poten-
tial to address both the consumption of
nonrenewable fossil fuels and global warming,
two of the greatest problems facing humankind.
The state-of-the-art in solar photoreactor design
to assess those systems which are most applicable
for industrial-scale implementation has been
reviewed by Braham and Harris (2009). Designs
for parabolic trough, compound parabolic,
inclined plate, double-skin sheet, rotating disk,
water bell, fiber optic, and fixed/fluidized bed
photoreactors are qualitatively discussed and
compared. Compound parabolic photoreactors
are most suited to near-term applications at pilot
scale (>1000 L/day) due to their advantageous
light-collecting properties and well-known
design methodology.
Engineered photocatalysts, photoreactor sys-
tems, process optimizations and modelings of the
photooxidation processes for water treatment,
and a number of potential and commercial
photocatalytic reactor configurations, in particu-
lar the photocatalytic membrane reactors, are
discussed by Chong et al. (2010). The main tech-
nical barrier that impedes commercialization of
semiconductor photocatalytic process was the
post-recovery of the catalyst particles after
water treatment. But, nowadays, membrane
photoreactors have shown to solve this drawback
(Molinari et al. 2002).
The existence of mass transfer limitations in
slurry photocatalytic reactors and experimental
validation was made in a flat reactor that was
part of a recycling system by Ballari et al.
(2010). When the photocatalytic reaction is not
fast, employing catalyst loadings below 1 g L 1,
irradiation rates at the reactor wall below
1  10 6 Einstein cm 2 s 1, and good mixing
operation (Re >1700), mass transport limitations
in the bulk of the fluid can be considered virtually
nonexistent.
The photocatalyst with designed physico-
chemical properties is the key in the process.
Recent research progress toward the design and
preparation of porous photocatalysts with struc-
tural, compositional, and morphological proper-
ties suitable for use in a photocatalytic reactor for
water treatment via advanced oxidation processes
have been reviewed by Pan et al. (2010). Various
synthetic strategies for fabricating porous
photocatalysts with well-defined microscopic
morphologies and nano/mesoscopic active
nanobuilding blocks and the synthesis-
component-structure-property relationship work-
ing in photocatalyst design are discussed.
References
Ballari MD, Alfano OM, Cassano AE (2010) Mass trans-
fer limitations in slurry photocatalytic reactors: exper-
imental validation. Chem Eng Sci 65:4931–4942
Braham RJ, Harris AT (2009) Review of major design and
scale-up considerations for solar photocatalytic reac-
tors. Ind Eng Chem Res 48:8890–8905
Braun AM, Maurette MT, Oliveros E (1991) Photochem-
ical technology. Wiley, New York
Chong MN, Jin B, Chow CWK, Saint C (2010) Recent
developments in photocatalytic water treatment tech-
nology: a review. Water Res 44:2997–3027
Loddo V, Augugliaro V, Molinari R, Palmisano L (2009)
Photocatalytic membrane reactors, Chapter 10. In:
Basile A, Gallucci F (eds) Simulation of membrane
reactors. Nova Science Publishers, New York,
pp 401–443
Molinari R, Palmisano L, Drioli E, Schiavello M (2002)
Studies on various reactor configurations for coupling
photocatalysis and membrane processes in water puri-
fication. J Membr Sci 206:399–415
Pan JH, Dou HQ, Xiong ZG, Xu C, Ma JZ, Zhao XS
(2010) Porous photocatalysts for advanced water puri-
fications. J Mater Chem 20:4512–4528
H
Hydrogen Production by Water
Splitting
Raffaele Molinari
Dip. to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Hydrogen is a promising energy vector in many
industries such as metallurgical industry, thermal
treatments, petrochemical industry, food industry,
electrical energy production, electronic industry,
and mechanical industry because of the zero
environmental impact of the combustion products
(only water). Main sources of hydrogen are fossil
(reforming of petroleum, reforming of natural gas,
carbon gasification) and nuclear thermochemical
and renewable processes (electrolysis from eolic
and photovoltaic electrical energy, solar thermo-
chemical processes, biomass gasification). Steam
reforming of hydrocarbons is the dominant tech-
nology, but today an interesting renewable source
for hydrogen production is water splitting. The
theoretical energy to split water to produce H2
and O2 (e.g., under solar light) is
H2 O þ hn ! H2 þ 1⁄2 O2
DG ¼ 237 kJ mol1
Energy for water splitting can be supplied by
various processes such as electrolysis,
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_970-6
photochemical, photocatalytic, and thermal
decomposition.
Photocatalytic water-splitting technology
using nano-sized TiO2 has great potential for
low-cost, environmentally friendly solar-
hydrogen production to support the future hydro-
gen economy (Fujishima and Honda 1972). Pres-
ently, the solar-to-hydrogen energy conversion
efficiency is too low for the technology to be
economically sound. The main barriers are the
rapid recombination of photo-generated electron/
hole pairs and the backward reactions and the
poor activation of TiO2 by visible light (only
3–5 % of photons present in the solar light can
photoactivate it). In response to these deficien-
cies, some investigators studied the effects of
addition of sacrificial reagents and carbonate
salts to prohibit rapid recombination of electron/
hole pairs and backward reactions. Other
research focused on the enhancement of
photocatalysis by modification of TiO2 by
means of metal loading, metal ion doping, dye
sensitization (O’Regan and Grätzel 1991), com-
posite semiconductor, anion doping, and metal
ion implantation. Metal ion implantation and
dye sensitization are very effective methods to
extend the activating spectrum to the visible
range. Therefore, they play an important role in
the development of efficient photocatalytic
hydrogen production (Ni et al. 2007). The metal
ion-implanted TiO2 could efficiently work as a
photocatalyst under visible light irradiation.
Some field tests under solar light irradiation
clearly revealed that the Cr ion- or V ion-implanted
TiO2 samples showed 2–3 times higher
photocatalytic reactivity than the un-implanted
TiO2. Instead, a visible light-responsive TiO2
thin-film photocatalyst, developed by a single pro-
cess using a radio frequency magnetron sputtering
(RF-MS) deposition method, showed high
photocatalytic reactivity for various reactions
such as reduction of NOx, degradation of organic
compounds, and splitting of H2O under visible
and/or solar light irradiations (Takeuchi
et al. 2012). Cation- or anion-doped metal oxides
or metal oxynitride was used to prepare visible
light-responsive TiO2 thin films by a radio fre-
quency magnetron sputtering method that were
applied for the separate evolution of H2 and O2
from water under visible or solar light irradiation
(Matsuoka et al. 2007). A photochemical water-
splitting system, composed by two reactors
divided by a proton-conducting membrane in
which photocatalytic half reactions of water
reduction and water oxidation took place, was
proposed by Zamfirescu et al. Complex molecular
devices based on ruthenium(bipyridine)(3)(2+)
photosensitizers were dissolved in both reactors,
which generate electrons or holes when exposed to
high-energy photonic radiation, and acted as cata-
lysts for water splitting. These molecular devices
for water reduction have a unique property to
enhance the existence time of photoelectrons,
such that the likelihood of generated electron
pairs to produce a molecule of hydrogen is
increased (Zamfirescu et al. 2011). Thermochem-
ical cycles using water as raw material and
nuclear/renewable energies as sources of energy
are believed to be a safe, stable, and sustainable
route of hydrogen production. Among the well-
studied thermochemical cycles, the sulfur-iodine
(S-I) cycle is capable of achieving an energy effi-
ciency of 50 %, making it one of the most efficient
cycles among all water-splitting processes (Kar
et al. 2012).
The S-I cycle is characterized by three basic
reactions as shown below:
1. I2 þ SO2 þ 2H2 O ! 2HI þ H2 SO4 ð120  CÞ
2. 2H2 SO4 ! 2SO2 þ 2H2 O þ O2 ð830  CÞ
3. 2HI ! I2 þ H2 ð450  CÞ
In order to overcome the low efficiency due
to the poor equilibrium decomposition of HI in
the third reaction, ongoing research is dedi-
cated toward the development of a hydrogen-
permselective membrane reactor. Proper iden-
tification of suitable membranes (e.g., asym-
metric silica membrane) and introduction of
membrane reactor is proposed to improve the
efficiency of the overall cycle and make hydro-
gen production more economical. The chal-
lenges are associated toward the development
of a membrane reactor which can be applied in
highly corrosive environment like HI under a
high temperature of about 500  C (Kar
et al. 2012). Perovskites are investigated as
potential redox catalyst materials for the ther-
mochemical production of hydrogen where
water is dissociated giving rise to the produc-
tion of pure hydrogen during the oxidation step.
The oxidation and reduction steps can be com-
bined in a membrane reactor constructed from
dense perovskite membranes toward a continu-
ous and isothermal operation. At steady state
and 900  C, 25  7 cm3(STP)H2 m2 min1 is
produced in purified state (Nalbandian
et al. 2009). In a perovskite hollow-fiber mem-
brane, the oxygen permeation flux increased 3.5
times more than that of the blank membrane
when feeding reactive CH4 onto the permeation
side of the membrane. The membrane was used
as a reactor to shift the equilibrium of thermal
water dissociation for hydrogen production
because it allows the selective removal of the
produced oxygen from the water dissociation
system. It was found that the hydrogen produc-
tion rate increased from 0.7 to 2.1 mLH2 min1
cm2 at 950  C after depositing a perovskite Pd
porous layer onto the perovskite membrane
(Jiang et al. 2010).
Hydrogen Production by Water Splitting
References
Fujishima A, Honda K (1972) Electrochemical photolysis
of water at a semiconductor electrode. Nature
238:37–38
Jiang HQ, Liang FY, Czuprat O, Efimov K, Feldhoff A,
Schirrmeister S, Schiestel T, Wang HH, Caro J (2010)
Hydrogen production by water dissociation in surface-
modified BaCoxFeyZr1-x-yO3-delta hollow-fiber mem-
brane reactor with improved oxygen permeation.
Chem Eur J 16:7898–7903
Kar S, Binclal RC, Prabhakar S, Tewari PK (2012) The
application of membrane reactor technology in hydro-
gen production using S-I thermochemical process: a
roadmap. Int J Hydrog Energy 37:3612–3620
Matsuoka M, Kitano M, Takeuchi M, Tsujimaru K,
Anpo M, Thomas JM (2007) Photocatalysis for new
energy production – recent advances in photocatalytic
water splitting reactions for hydrogen production.
Catal Today 122:51–61
3
Nalbandian L, Evdou A, Zaspalis V (2009) La(1-x)Sr(x)
MO(3) (M = Mn, Fe) perovskites as materials for
thermochemical hydrogen production in conventional
and membrane reactors. Int J Hydrog Energy
34:7162–7172
Ni M, Leung MKH, Leung DYC, Sumathy K (2007)
A review and recent developments in photocatalytic
water-splitting using TiO2 for hydrogen production.
Renew Sustain Energy Rev 11:401–425
O’Regan B, Grätzel M (1991) A low-cost, high-efficiency
solar cell based on dye-sensitized colloidal TiO2 films.
Nature 353(6346):737–740
Takeuchi M, Matsuoka M, Anpo M (2012) Ion engineer-
ing techniques for the preparation of the highly effec-
tive TiO2 photocatalysts operating under visible light
irradiation. Res Chem Intermed 38:1261–1277
Zamfirescu C, Dincer I, Naterer GF (2011) Analysis of a
photochemical water splitting reactor with supramo-
lecular catalysts and a proton exchange membrane. Int
J Hydrogen Energy 36:11273–11281
W
Water Splitting
Raffaele Molinari
Dip.to di Ingegneria per l’Ambiente e il
Territorio e Ingegneria Chimica (DIATIC),
Università della Calabria, Rende (CS), Italy
Water splitting means a chemical transformation
that separates water into its elements which are
molecular oxygen (O2) and molecular hydrogen
(H2). The transformation can be done by various
processes such as electrolysis, photochemical,
photocatalytic, thermal decomposition.
Electrolysis is a method of separating ele-
ments chemically bounded into compounds by
passage of an electric current through them: in
the case of electrolysis of water, the latter is
decomposed (splitted) into gases O2 and H2.
When energy is obtained from light, photochem-
ical and photocatalytic devices can be used, and
the system that splits water into hydrogen and
oxygen is also named artificial photosynthesis
(Devens et al. 2009).
Water splitting over a semiconductor
photocatalyst using solar energy is a promising
process for the large-scale production of clean,
recyclable H2 at temperatures close to the ambi-
ent one. Numerous attempts have been made to
develop photocatalysts that function under visi-
ble light irradiation to efficiently utilize solar
energy (Kazuhiko 2011; Valdes et al. 2012).
The photocatalytic splitting of water under
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_971-2
visible light irradiation is a greatly desired reac-
tion system for hydrogen production. However,
powdered photocatalysts always produce a gas
mixture of hydrogen and oxygen in such a reac-
tion, and thus, a separation process for the gas
mixture is required before the hydrogen can be
effectively utilized. Construction of a
photocatalytic system enabling the separate evo-
lution of hydrogen and oxygen from water (e.g.,
by means of a membrane) under visible light
irradiation and absence of sacrificial agents
using a Z-scheme (Abe 2010) is, therefore, of
vital interest. In this Z-scheme methodology,
hydrogen and oxygen are generated photocata-
lytically in different cells that are illuminated
and separated by a membrane. An electrolyte is
used to ensure the electroneutrality in each cell
and to allow charge transfer from one compart-
ment to the other. One suitable electrolyte is the
Fe2+/Fe3+ redox pair. A Nafion membrane is a
suitable barrier between the two compartments of
the reactor because of its chemical and physical
properties (Seger et al. 2007). The uptake
characteristic of different cations (Fe3+, Cu2+,
and Ni2+) by Nafion 117 which is commonly
used as separator for different chemical processes
was also investigated (Ramı̀rez et al. 2010).
Thermal decomposition (or thermolysis) is
another approach for water splitting: it is a chem-
ical transformation that breaks a substance into at
least two chemical substances when heated. At
elevated temperatures (e.g., 2200  C), water mol-
ecules can decompose, but using catalysts, lower
2 Water Splitting
temperatures can be used to obtain hydrogen and
oxygen.
Solar energy can be used for thermal decom-
position of water via an integrated thermochem-
ical reactor/receiver system (Agrafiotis
et al. 2005). A multichannel honeycomb ceramic
supports coated with active redox reagent pow-
ders, in a configuration similar to that encoun-
tered in an automobile catalytic converter, have
been used. Iron-oxide-based redox materials,
capable to operate under a complete redox
cycle, could take oxygen from water producing
pure hydrogen at reasonably low temperatures
(800  C) and could be regenerated at tempera-
tures below 1300  C. Ceramic honeycombs capa-
ble of achieving temperatures in that range when
heated by concentrated solar radiation were
assembled in a dedicated solar receiver/reactor.
The operating conditions of the solar reactor were
optimized to achieve adjustable, uniform temper-
atures up to 1300  C throughout the honeycomb,
making thus feasible the operation of the com-
plete cycle by a single solar energy converter
(Agrafiotis et al. 2005).
References
Abe R (2010) Recent progress on photocatalytic and
photoelectrochemical water splitting under visible
light irradiation. J Photochem Photobiol C: Photochem
Rev 11:179–209
Agrafiotis C, Roeb M, Konstandopoulos AG, Konst
Nalbandian L, Zaspalis VT, Sattler C, Stobbe P, Steele
AM (2005) Solar water splitting for hydrogen produc-
tion with monolithic reactors. Solar Energy
79:409–421
Devens G, Moore TA, Moore AL (2009) Solar fuels via
artificial photosynthesis. Acc Chem Res
42:1890–1898
Kazuhiko M (2011) Photocatalytic water splitting using
semiconductor particles: history and recent develop-
ments. J Photochem Photobiol C Photochem Rev
12:237–268
Ramı̀rez J, Godı̀nez LA, Mèndez M, Meas Y, Rodriguez
FJ (2010) Heterogeneous photo-electro-Fenton pro-
cess using different iron supporting materials. J Appl
Electrochem 40:1729–1736
Seger B, Vinodgopal K, Kamat PV (2007) Proton activity
in Nafion films. Probing exchangeable protons with
methylene blue. Langmuir 23:5471–5476
Valdes A, Brillet J, Gratzel M, Gudmundsdottir H, Hansen
HA, Jonsson H, Klupfel P, Le Formal F, Man IC,
Martins RS, Norskov JK, Rossmeisl J, Sivula K,
Vojvodic A, Zach M (2012) Solar hydrogen produc-
tion with semiconductor metal oxides: new directions
in experiment and theory. Phys Chem Chem Phys
14–1:49–70
C

Characterization of Porous hydrophobic or carrying positive or negative

and Dense Membranes charges), the structure of the membrane
(whether it is symmetric or asymmetric), and
Lidietta Giorno1, Enrico Drioli1 and Heiner their mechanical, chemical, and thermal stability.
Strathmann2 The methods used to characterize porous mem-
1
Institute on Membrane Technology, National branes include simple filtration and retention
Research Council of Italy, ITM-CNR, National measurements, microscopic techniques, surface
Research Council of Italy, Rende (CS), Calabria, tension measurements, and the determination of
Italy pore radii by liquid/gas or liquid/liquid replace-
2
Institute for Chemical Technology, Stuttgart ment. The chemical and mechanical stability at
University, Stuttgart, Germany various temperatures is usually measured in long-
term tests. Which of the membrane characteriza-
tion methods are applied depends on the use of
Membrane characterization is a key part in mem- the membrane.
brane research and development. In fact, the
design of membrane processes and systems
depends on reliable data relating to membrane
The Pure Water Flux of Micro-
properties. To identify a membrane type to be
and Ultrafiltration Membranes
used for a particular process, it is crucial to
know its properties.
A characteristic property of micro- and ultrafil-
Since membranes are very different in their
tration membranes is their “pure water flux” or
properties and applications, a large number of
“pure water permeability.” The flux J through a
different techniques are required for their charac-
porous medium is proportional to the applied
terization. Some of the most important membrane
hydrostatic pressure and inversely proportional
characterization procedures described in the lit-
to the solvent viscosity. It is expressed in Darcy’s
erature or recommended by membrane manufac-
law, which is given by:
turers are illustrated.
Porous micro- or ultrafiltration membranes are
Lp Dp
generally characterized in terms of their flux, Jv ¼ (1)


their pore size, their pore size distribution, and
their molecular mass cutoff. Other important
Here Jv is the membrane flux, Lp is the hydrody-
characteristics are the nature of the membrane
namic solvent permeability,
is the viscosity of
material (whether it is hydrophilic or
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_993-1
2 Characterization of Porous and Dense Membranes
Characterization of Porous and Dense Membranes,
Fig. 1 Scanning electron micrographs of (a) a sintered
membrane prepared from a polymer powder, (b) a mem-
brane prepared by stretching an extruded polytetrafluor-
oethylene film perpendicular to the direction of extrusion,
(c) of a capillary pore polycarbonate membrane made by
the solution passing through the pores of the
membrane, and Dp is the applied pressure.
track etching, (d) a porous cellulose nitrate membrane
prepared from a homogeneous polymer solution by
water vapor precipitation, and (e) a porous polypropylene
membrane precipitated by thermal gelation from a hot
polymer solution
For the determination of the pure water flux, it
is very important to use a certain water quality.
Generally deionized or distilled water with a
Characterization of Porous and Dense Membranes
Characterization
of Porous and Dense
stress
Membranes,
Fig. 2 Stress versus strain
diagram of a membrane
sample indicating the
elastic and plastic
deformation and the
breakpoint
elastic
deformation
conductivity of <5 mS cm1, which is treated by
microfiltration to remove suspended materials, is
used as a test solution. The flux is determined at
different applied pressures and plotted as a func-
tion of the pressure. From the slope of the plot,
the hydrodynamic permeability is obtained. Prior
to the flux measurements, the membranes should
be pressurized by filtration of pure water at a
hydrostatic pressure that is at the upper limit of
the recommended operating pressure for one to
two hours to compress the membrane to a stable
value that will not further deform when used at
lower pressures. Possible preservatives, often
present in membranes, must be eliminated by a
washing procedure.
Some inorganic membranes, like Al2O3-based
types, show an apparent internal pore clogging
when deionized water is used in the pure water
flux measurements. In these cases an electrolyte
solution is used for determining the membrane
flux, e.g., a NaCl or KCl solution. Since there
exists no standard method for the determination
of the pure water flux, companies use their own
standards, which makes a reliable comparison of
pure water fluxes rather difficult.
Typical pure water fluxes of microfiltration
membranes vary from 500 to 50,000 L m2 h1
bar1, while pure water fluxes of ultrafiltration
membranes vary from 50 to 800 L m2 h1 bar1.
In practical applications, fluxes are normally
much lower, and a steep flux decline is observed
during the first period of operation. This flux
decline is mainly determined by membrane
3
break point
plastic
strain
deformation
fouling which is generally more pronounced for
microfiltration than for ultrafiltration.
Microscopic Techniques
A variety of microscopic techniques are used to
study membrane structures, such as scanning
electron microscopy, field emission electron
microscopy, transmission electron microscopy,
and atomic force microscopy. The advantage of
these techniques is that direct visual information
of the membrane morphology is obtained. The
different microscopic techniques require differ-
ent preparation methods and have different reso-
lution. Scanning electron microscopy, e.g., has a
resolution of up to 5 nm and provides good infor-
mation on the structures of micro- and ultrafiltra-
tion membranes including pore sizes and pore
shapes. To reach a high resolution, high electron
beam energy has to be applied, which can damage
the membrane samples. Another problem is that
in electron microscopy, a conductive layer must
coat the samples. This is generally done in a high
vacuum, which can lead to a change of the struc-
ture of membranes made from hydrophilic
polymers.
The pore sizes and pore shapes of ultrafiltra-
tion membranes can also be determined by trans-
mission electron microscopy which has a
resolution of 0.4–0.5 nm or by field emission
electron microscopy which has a resolution of
0.6–0.7 nm. The transmission electron
4 Characterization of Porous and Dense Membranes
microscopy technique requires a significantly
more complex preparation procedure and is
mainly applied to determine the surface porosity
of ultrafiltration membranes (Fane et al. 1981).
Because of the high resolution, pores in ultrafil-
tration membranes can be visualized by field
emission electron microscopy (Kim et al. 1990).
Sample preparation for scanning electron
microscopy and field emission electron micros-
copy analysis is relatively easy compared to the
sample preparation for transmission electron
microscopy. To visualize the cross sections of a
membrane, e.g., it is immersed in ethanol or a
water/ethanol mixture prior to cooling in liquid
nitrogen. The sample is fractured providing a
rather clean fracture and glued with conductive
glue to a sample holder and sputtered with a thin
layer of gold. The sputtered layer should be thin-
ner than the structure features of the membrane to
be studied. Recently, low-vacuum scanning elec-
tron microscopy, i.e., so-called environmental
scanning electron microscopy, has become avail-
able which makes it possible to scan a sample
without a conductive coating. However, the res-
olution of these microscopes is limited to magni-
fications of ca. 7500. Figures 1 and 2 show typical
pictures of membrane structures that can be
obtained by scanning electron microscopy
techniques.
Besides electron microscopy, atomic force
microscopy is also applied to study membrane
surface structures. Atomic force microscopy has
a resolution of ca. 1 nm (Fritsche et al. 1992; Hilal
and Johnson 2010). Sample preparation is fairly
simple, since no conductive coating is required.
Therefore, samples need not be dried and
exposed to vacuum. AFM can operate in air and
liquid phases; therefore, membranes can be stud-
ied in the environments used during their opera-
tion. This is very valuable for determining
influence of physical-chemical parameters (such
as pH, ionic strength, charge) and functional mol-
ecules on membrane surface properties.
The Mechanical Properties
of Membranes
The mechanical stability and swelling behavior
of the membranes is determined by the degree of
cross-linking or crystallinity of the polymer
matrix and the concentration of the fixed charges.
The structure of membranes based on a highly
crystalline polymer such as the fluorocarbon
polymers are studied using transmission electron
microscopy and small angle X-ray diffraction
(Gierke et al. 1982). The degree of cross-linking
is closely related to the swelling behavior and the
mechanical properties of the membranes. But it
also affects the permselectivity. Infrared spec-
troscopy measurements can provide some infor-
mation on the type and degree of cross-linking of
ion-exchange membranes.
A mechanical characterization of
ion-exchange membranes involves the determi-
nation of its swelling and dimensional stability in
different test solutions and tensile strength and
hydraulic permeability measurements. All
mechanical characterization tests should be car-
ried out with well-equilibrated membranes in a
controlled environment. The tensile strength and
information concerning the plastic or elastic
deformation of a membrane is obtained from a
stress versus strain diagram as shown schemati-
cally in Fig. 2.
The strain versus stress curves of
ion-exchange membranes generally show three
distinct areas. At relatively low strain, the mem-
branes show elastic deformation; with increasing
strain, the membranes show plastic deformation,
and at a certain point they break. Since the
mechanical properties of membranes generally
change drastically with the water content of the
membranes, they must be determined with dry
membranes and with membranes equilibrated in
water or different solutions similar to those used
in practical applications.
The swelling of membranes depends on a
number of different parameters such as the nature
of the basic membrane polymer, the nature of the
ion-exchange groups and their concentration in
the membrane, the counterions, the cross-linking
density, the homogeneity of the membrane, and
Characterization of Porous and Dense Membranes
the composition of the solution with which the
membrane is in contact. Especially the concen-
tration of the solution has a significant effect on
the water sorption of the membrane because of
osmotic effects that are directly related to the
chemical potential difference of the water in the
membrane and in the solution. The state of the
water in the membrane can also be rather differ-
ent. Part of the water is so-called “free” water.
Another part of the water is strongly bound within
the hydration shell of the counterions and the
fixed charges of the membrane, while again
another part is more loosely bound to the basic
polymer matrix. The different water structures in
ion-exchange membranes are studied by differ-
ential scanning calorimetry, infrared spectros-
copy, and nuclear magnetic resonance
(Komoroski and Mauritz 1982). Studies of the
water structure within the membrane and its
interaction with the membrane polymer, fixed
charges, and counterions require more sophisti-
cated spectroscopic measurements. The total
water uptake of the membrane in equilibrium
with an electrolyte solution, however, can be
determined quite easily by measuring the weight
difference between a membrane in the wet and
dry state. To determine the water content of a
membrane, a sample is equilibrated in a test solu-
tion. After removing the surface water from the
sample, the wet weight of the swollen membrane
is determined. The sample is then dried at ele-
vated temperature over phosphorus pentoxide
under reduced pressure until a constant weight
is obtained. The water content of a membrane is
obtained in weight percent by:
W wet  W dry
wt% swelling ¼  100 (2)
W wet
Here Wwet and Wdry are the weight of a mem-
brane sample in the wet and the dry state.
Membrane Separation Properties
Determined by Filtration Test
Both micro- and ultrafiltration are pressure-
driven membrane processes using porous
5
membranes. The separation of various compo-
nents is based on a sieving mechanism, i.e., this
membrane retains particles or molecules that are
larger in size than the pores of a membrane.
A relation as a function of the particle size and
the pore size for the membrane retention can be
defined by a relation between the pore and the
particle radius (Ferry 1936). If the particles are
spherical and have a radius rs and the membrane
pores are cylindrical with a radius rp, the follow-
ing relation can be applied to describe the mem-
brane solute rejection:
  
rs 2 2
R¼ 1 1 (3)
rp
For the radius of the molecule, either the radius of
gyration or the hydrodynamic radius can be used.
The Ferry model is rather simplified, but gives a
good approximation of the expected retention
when particle size and the membrane pore radius
are known.
Retention and Molecular Weight Cutoff
To describe the retention of ultrafiltration mem-
branes, usually the molecular weight cutoff is
used. The molecular weight cutoff determination
is very sensitive to the experimental conditions,
i.e., the solutes and their concentration used in the
test, the applied pressure, and the temperature.
Therefore, a comparison of retention data given
by different manufacturers is generally
problematic. As test conditions for determining
the ultrafiltration membrane cutoff, a transmem-
brane pressure of 100 kPa, a feed solution con-
centration of 0.1 %, and a test temperature of
25  C are recommended. Furthermore, a maxi-
mum of agitation of the feed solution at the mem-
brane surface is required to minimize
concentration polarization effects, and small
amounts of solution should be filtered to assure
a constant feed concentration.
The retention is generally expressed in % and
defined by:
6 Characterization of Porous and Dense Membranes
Characterization
of Porous and Dense
Membranes,
Fig. 3 Schematic drawing
that illustrates the capillary
effect of a membrane pore
 
CP
R¼ 1 100 (4)
Cf
Here R is the retention or rejection of a membrane
and Cf and Cp are the feed and the permeate
concentration.
The retention of molecules having identical
molecular weights may be rather different when
their shape is different. Globular proteins, e.g.,
are rejected easier than branched polysaccharides
or flexible polymers (Porter 1979). Adsorption of
the solute to the membrane surface, e.g., might
result in high “apparent” retention values when
the experiment is performed for a very short time
period. Accumulation of solutes at the membrane
surface due to concentration polarization effects
can also obscure the retention measurements and
must be considered when the true, i.e., intrinsic,
retention shall be determined. Using low pres-
sures, low feed concentrations, and a high degree
of agitation can more or less eliminate these
effects.
Manufactures of ultrafiltration membranes
generally make use of marker molecules, e.g.,
dextrans and proteins, for the determination of
the molecular weight cutoff value of their mem-
branes. In addition to the molecular weight cutoff
of a membrane, the sharpness of the cutoff is
important for the practical application. The
sharpness of the cutoff of a membrane is deter-
mined by measuring the retention of the mem-
brane for components of different molecular
weights and plotting the retention versus the
force
rp
wetting liquid
molecular weight of the retained components.
The sharpness of the cutoff of a membrane
depends mainly on the pore size distribution of
the membrane. For practical applications, the
cutoff of a membrane should be as sharp as
possible.
The Bacterial Challenge Test
Micro- and ultrafiltration membranes are often
used in the food and pharmaceutical industry for
the sterilization of solutions. In this application, it
is important that membranes retain undesired
microorganisms as completely as possible, i.e.,
the retention for microorganisms should be close
to 100 %. Therefore, these membranes are
exposed to a bacterial challenge test. In this test,
the membrane is challenged with a solution
containing a minimum concentration of organ-
isms such as Pseudomonas diminuta per cm3 of
solution (Cheryan 1998). The data obtained in
bacterial challenge tests are normally expressed
in terms of the log reduction value, which is given
by the logarithms of the ratio of feed to filtrate
concentration. The bacterial challenge test is a
destructive test and is therefore not suited as an
on-line quality control test. For this application,
the nondestructive diffusion test and the bubble
point integrity test are generally applied.
Characterization of Porous and Dense Membranes
Characterization
of Porous and Dense
Membranes,
Fig. 4 Schematic drawing
illustrating the gas/liquid
gas flow
displacement measurement
to determine the pore size
and pore size distribution of
microfiltration membranes
bubble point
(maximum pore size)
Membrane Properties Determined by
Membrane Pore Size Measurement
In addition to filtration tests, micro- and ultrafil-
tration membranes are characterized by deter-
mining their pore size and pore size distribution.
A number of techniques such as liquid/gas and
liquid/liquid displacement, mercury intrusion,
permporosimetry, thermoporosimetry, etc. are
used for the determination of the membrane
pore size and pore size distribution. One of the
more simple methods is the so-called bubble
point test.
The Bubble Point Test
The bubble point test is a structure integrity test in
which the largest pore or hole in a membrane is
determined. The bubble point method is based on
the capillary effect of small pores due to surface
tension forces. In equilibrium these forces are
balanced with gravity of the liquid in the pores.
The principle is shown in Fig. 3.
This equilibrium between surface tension
forces and gravity of the liquid in the pore can
be expressed by the following equation:
2pr p s cos f ¼ r 2p phrg
Here rp is the pore radius, s is the surface tension
of the liquid in contact with air, cosf is the
contact angle between the liquid and the wall of
7
minimum pore size
dry flow
mean flow pore size
50% of dry flow
wet flow
pressure
the pore, h is the height of the liquid column, r is
liquid density, and g the acceleration of gravity.
The term h r g in Eq. 5 can be replaced by the
pressure p. This results in the Laplace equation,
which is given by:
2s cos f
rp ¼ (6)
p
The bubble point method is a fairly simple tech-
nique where the pores of a membrane are filled
with a liquid. From the bottom side of the mem-
brane, nitrogen gas or air is introduced with
increasing pressure. At a certain pressure, the
gas will replace liquid in the largest pores perme-
ating the membrane, and a bubble rising from the
membrane surface can be observed.
Equation 6 referred to as Laplace equation
gives a relation for the surface tension between
the liquid and the gas and the required pressure to
open up pores of a certain size. In the bubble
point test, mostly water or isopropanol is used,
since the surface tension of water/air is approxi-
mately 3.5 times higher than for isopropanol/air.
Other techniques to determine the pore size
and pore size distribution of a porous membrane
that are also based on the Laplace equation, but
(5) cover different pore size ranges when the same
pressure range is applied, are mercury
porosimetry, gas-liquid displacement, and
liquid-liquid displacement.
8 Characterization of Porous and Dense Membranes
damper
HPLC
pump
liquid A
membrane
containing liquid B
Characterization of Porous and Dense Membranes, Fig. 5 Schematic representation of a typical liquid-liquid
displacement setup (Capannelli et al. 1983)
The Mercury Porosimetry
In mercury porosimetry, a dry membrane is
exposed to a certain volume of liquid mercury.
The pressure applied to the mercury is slowly
increased, while simultaneously the amount of
mercury forced into the porous structure is mea-
sured. The largest pores will be filled first and the
required pressure for the mercury to penetrate the
porous structure increases with decreasing pore
size. The required pressure corresponds to a cer-
tain pore radius and the amount of mercury that
disappears in the membrane corresponds to the
total volume of these pores. The interfacial ten-
sion of mercury and air is very high. Therefore,
relatively high pressures are required to fill small
pores. In polymer membranes, only pores having
a radius in excess of 1 mm can be detected reliably
by mercury porosimetry. Furthermore, this tech-
nique does not give distinction between dead-end
pores and interconnected pores.
Gas-Liquid Displacement
The gas-liquid displacement technique is identi-
cal to the bubble point method. The pores of the
membrane are generally filled with an organic
solvent which has a lower surface tension than
water. The solvent is forced out of the membrane
pores by nitrogen gas, which is introduced with
p recorder
computer
digital
balance
increasing pressure. As the pressure increases,
the liquid will be replaced by nitrogen in the
largest pores first, and a convective gas flow
through these pores will occur. The gas flow is
measured as a function of the applied pressure.
When all the pores are opened, a linear relation-
ship between pressure and gas flow is observed
when the pressure is further increased. Figure 4
shows schematically typical gas fluxes obtained
as a function of pressure with a dry and a liquid-
filled membrane.
The mean flow pore size is given by the point
where the 50 % “dry” flow curve crosses the
“wet” flow curve. The maximum pore size is
given by the point where a first flow through the
liquid-filled membrane is observed. The mini-
mum pore size is given by the point where the
fluxes of the dry and the liquid-filled membrane
become identical. The Laplace equation
describes the relationship between the pore radius
and the applied pressure.
Liquid-Liquid Displacement
Liquid-liquid displacement differs from
gas-liquid displacement in the displacing
medium; a second liquid instead of a gas dis-
places the liquid inside the pores. The two liquids
applied should be immiscible. A typical liquid
Characterization of Porous and Dense Membranes 9

Characterization of Porous and Dense Membranes, Table 1 Different porosimetry techniques and the influence
of the interfacial tension on the pressure required opening pores of 10 nm
Pressure
Technique System (mN/m) (Bar)
Mercury porosimetry (G-L) Air/mercury 480 749
Bubble point (G-L) Air/water 72.3 145
Coulter porometry (G-L) Air/Porofil ® 16 32
Gas-liquid displacement (G-L) Air/isobutanol 20.7 41
Liquid-liquid displacement (L-L) Water/isobutanol 1.85 3.7
Liquid-liquid displacement (L-L) Water/isobutanol/methanol 0.35 0.7

pair used is water/isobutanol. Both liquids are
first saturated with each other before one of the
liquids is used to fill the pores and the other liquid
is applied as replacement liquid. The experimen-
tal setup for the determination of pore sizes by
liquid-liquid displacement is shown in Fig. 5.
A slow increase the replacement liquid pressure
pushes the liquid out of the largest pores first.
With increasing in pressure, the liquid in the
smaller pores will also be replaced. The pore
size distribution can be calculated from a plot of
the flux versus the applied pressure (Capannelli
et al. 1983; Wienk et al. 1994).
Whether isobutanol or water is used as
displacing liquid depends very much on the
nature of the membrane material. Due to swelling
phenomena, different results might be obtained
depending on the liquid placed inside the pores.
The relation between the pore radius and the
pressure required to open pores of a certain size is
again described by the Laplace equation, and the
pore size distribution can now be calculated when
the flux as a function of the pressure is measured.
Like in gas-liquid displacement, only active
pores contributing to transport are taken into
account. Pore diameters of approximately
5–100 nm can be analyzed using liquid-liquid
displacement. The advantage of liquid-liquid dis-
placement over gas-liquid displacement is the
lower interfacial tension between liquid pairs
compared to a gas/liquid pair. Therefore, pores
of the same size can be opened at much lower
pressures in liquid-liquid displacement.
There are more methods that can be used to
determine pore sizes in porous membranes
(Cuperus et al. 1992a, b) such as permporometry
or thermoporometry, which is based on the
microcalorimetric analysis of a solid-liquid tran-
sition using a sensitive differential scanning cal-
orimetry. Permporometry is a technique based on
gas adsorption/desorption measurements where
pores are either filled by controlled condensation
of a vapor phase or where filled pores are emptied
by controlled evaporation of the liquid inside the
pores. The relation between the relative vapor
pressure and the pore radius is given by the Kel-
vin equation. Thermoporometry is based on the
microcalorimetric analysis of a solid-liquid tran-
sition using a sensitive differential scanning
calorimetry.
Table 1 shows the pressures required to open
pores of 10 nm for different displacement sys-
tems. A second advantage is that membranes are
characterized in a wetted state, and therefore the
test conditions are closer to the real operating
conditions.
Dense Membrane Characterization
Dense membranes are generally used for the sep-
aration of low molecular mass materials such as
gases, salts, or solvents. The transport mechanism
in these membranes is based on the solution and
diffusion of components within the membrane
matrix. The intrinsic properties of the basic mem-
brane material are often more relevant for char-
acterizing their transport behavior than is the
macroscopic membrane structure. Characteriza-
tion methods used with microporous structures
10
have therefore been supplemented with other pro-
cedures, such as sorption and diffusion measure-
ments or determination of the glass transition
temperature and crystallinity of the basic mem-
brane material. For ion-exchange membranes, the
measurement of electrokinetic properties is
required.
In addition to the determination of diffusion
and partition (solubility) coefficients, measure-
ments providing information on the physical
structure of the polymer, such as differential
scanning calorimetry, X-ray studies, or determi-
nation of the free volume in a polymer, are impor-
tant. These methods are described in Koros and
Chem (1987), Berens and Hopfenberg (1982),
and Morel and Paul (1982). Permeability and
selectivity are the most interesting parameters;
they are determined in permeation tests and
expressed in terms of rejection coefficients
(in reverse osmosis) or separation coefficients
(in gas separation and pervaporation). These
coefficients are usually not constant but a func-
tion of composition, temperature, and pressure.
Furthermore, boundary layer effects at the mem-
brane surface often obscure the determination of
membrane fluxes and selectivities in practical
measurements.
The methods used to determine the structural
properties of ion-exchange membranes are simi-
lar to those used for characterizing other polymer
membranes. Because ion-exchange membranes
are used mainly in separation processes with
electrical potential driving forces, their perme-
ability and selectivity are determined under
experimental conditions closely related to their
practical use, and their properties are expressed in
terms commonly used in electrochemistry (e.g.,
electrical resistance, ion-transfer numbers,
charge densities) (Cussler 1971, 1984).
References
Berens AR, Hopfenberg HB (1982) Diffusion of organic
vapors at Low concentrations in glassy PVC, polysty-
rene and PMMA. J Membr Sci 10:283
Characterization of Porous and Dense Membranes
Capannelli G, Vigo F, Munary S (1983) UF characteriza-
tion methods. J Membr Sci 15:289
Cheryan M (1998) Ultrafiltration and microfiltration hand-
book. Lancaster Publishing Company, Lancaster
Cuperus FP, Bargeman D, Smolders CA (1992a)
Permporometry. The determination of active pores in
ultrafiltration membranes. J Membr Sci 71:75
Cuperus FP, Bargeman D, Smolders CA (1992b) Critical
points in the analysis of membrane pore structure by
thermoporometry. J Membr Sci 66:45
Cussler EL (1971) Membranes which pump. AICHE
J 17:1300–1303
Cussler EL (1984) Diffusion. Academic, Cambridge, MA
Fane AG, Fell CJD, Waters AG (1981) The relationship
between membrane pore characteristics and flux for
ultrafiltration membranes. J Membr Sci 9:245
Ferry JD (1936) Ultrafilter membranes and ultrafiltration.
Chem Rev 18:373
Fritsche A.K., Arevalo AR, Moore MD, O’Hara C (1992)
Surface Structure and Morphology of Polyacrylonitrile
Membranes by Atomic Force Microscopy. J. Membr
Sci. 46:167
Gierke TD, Munn GE, Wilson FC (1982) Morphology of
perfluorosulfonated membrane products – wide- angle
and small-angle x-ray studies. ACS Symp Ser
180:195–216
Hilal N, DJ Johnson (2010). The use of atomic force
microscopy in membrane characterisation. Compre-
hensive Membrane Science and Engineering. E. Drioli
and L. Giorno. Oxford, Elsevier Science. 521–538
Kim KJ, Fane AG, Fell CJD, Suzuki T, Dickson MR
(1990) Quantitative microscopic study of surface char-
acteristics of ultrafiltration membranes. J Membr Sci
54:89
Komoroski RA, Mauritz KA (1982) Perfluorosulfonated
ionomer membranes. In: Eisenberg A, Yeager HL
(eds) ASC symposium series 180. American Chemical
Society, Washington, DC
Koros WJ, Chern RT (1987) Separation of gaseous mix-
tures using polymer membranes. In: Rousseau RW
(ed) Handbook of separation process technology.
Wiley, New York
Morel G, Paul DR (1982) CO2 sorption and transport in
miscible polyphenylene oxide/polystyrene blends.
J Membr Sci 10:273
Porter MC (1979) Membrane filtration. In: Schweizer PA
(ed) Handbook of separation techniques for chemical
engineers. Mac Graw-Hill, New York
Wienk IM, Folkers B, van den Boomgaard T, Schmolders
CA (1994) Critical factors in the determination of the
pore size distribution of UF membranes using a liquid
displacement method. Sep Sci Technol 29:1433
I
Ion-Exchange Membrane
Characterization
Lidietta Giorno1, Enrico Drioli1 and
Heiner Strathmann2
1
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, National
Research Council of Italy, Rende (CS), Calabria,
Italy
2
Institute for Chemical Technology, Stuttgart
University, Stuttgart, Germany
Characterization of ion-exchange membranes is
closely related to their preparation. The most
interesting properties of ion-exchange mem-
branes are (Spiegler 1958):
• Τhe electrical resistance in different electro-
lyte solutions
• The type and density of fixed charges and their
distribution in the membrane matrix
• The permselectivity of the membrane for dif-
ferent ions
• Τhe transport rate of neutral components,
especially water
• The mechanical and chemical stability and the
swelling in different electrolyte solutions
A series of procedures and techniques are
applied to determine the different membrane prop-
erties. Microscopic examination yields
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_994-1
information on heterogeneity of the membrane
structure and in case of reinforced membranes
the type of reinforcement used. The electrical
charge of an ion-exchange membrane can be
determined qualitatively by using indicator solu-
tions. A drop of a 0.05 % solution of methylene
blue and methyl orange on a membrane sample
stains a yellow spot on top of an anion-exchange
membrane and a deep blue spot on top of a cation-
exchange membrane, respectively. For a quantita-
tive characterization, more complex procedures
such as the determination of the ion-exchange
capacity or the electrical resistance and transport
properties for different ions of the membrane are
applied. Additional information can be obtained
by impedance spectroscopy and chronopoten-
tiometric measurements or from the determination
of osmotic and electroosmotic water transfer.
Bipolar membranes are further characterized in
terms of the water dissociation capability and salt
leakage under operating conditions (Strathmann
et al. 1993).
Hydraulic Permeability of Ion-Exchange
Membranes
Hydraulic permeability measurements provide
information on the diffusive or convective trans-
port of components through a membrane under a
hydrostatic pressure driving force. In most prac-
tical applications of electrodialysis, the hydraulic
permeability due to diffusion plays a minor role
2 Ion-Exchange Membrane Characterization

for the overall performance of the membrane in a of their electrochemical properties such as the
given process. However, for the determination of fixed charge density, the electrical resistance,
pinholes in ion-exchange membranes will affect the ion permselectivity, and the transport of non-
the performance of a membrane severely in appli- ionic components such as water or of other neu-
cations with a hydrostatic pressure differences tral molecules under operating conditions.
across the membrane. Pinholes can be detected
quickly by placing a wet membrane sheet on a
sheet of white absorbent paper. Then, a 0.2 %
The Ion-Exchange Capacity of a
solution of methylene blue for an anion-exchange
Membrane
membrane or a 0.2 % solution of erythrosin B for
a cation-exchange membrane is spread over the
The ion-exchange capacity of membranes is a
entire surface of the membrane. If no spots of the
crucial parameter which affects almost all other
dye can be observed on the paper, the membrane
membrane properties. It is usually expressed in
is free of large pinholes. The hydraulic perme-
milliequivalent per gram of dry membrane. Exper-
ability of the membrane is determined at room
imentally, the ion-exchange capacity of strong
temperature using deionized water and a hydro-
acidic or strong basic ion-exchange membranes
static pressure driving force in a conventional
is readily determined by titration with NaOH or
filtration cell as used in reverse osmosis or ultra-
HCl, respectively. For these tests, cation- and
filtration experiments. The permeability can then
anion-exchange membranes are equilibrated in
be calculated from the volumetric flow rate.
1N HCl or 1N NaOH, respectively, and then
The economics of processes using
rinsed free from chloride or sodium ions with
ion-exchange membranes in different applications
deionized water. The ion-exchange capacity of
is determined to a large extent by the chemical
the samples is determined by back titration with
stability of the membranes under process condi-
1N NaOH or 1N HCl, respectively. Weak base
tions. Generally, the changes in membrane proper-
anion-exchange membranes are characterized by
ties are time and temperature dependent. Reliable
equilibration in 1N NaCl and titration with stan-
information about the long-term stability of the
dardized 0.1N AgNO3 solution. The samples are
membranes is of importance for a process design
then dried, and the ion-exchange capacity is cal-
and cost calculation. For a fast evaluation, mem-
culated based on the dry membrane. The accuracy
brane samples are exposed to oxidizing agents or
of the measurement depends on the complete
acids and bases and other chemical components in
exchange of ions in the membrane which can
much higher concentration and at higher tempera-
take some time. The concentration of the fixed
ture than expected in practical use. Structural
ion in commercial membranes is in the range
mechanical changes are determined by visual or
between 1 and 3 milliequivalent per gram. The
microscopic investigation and standard mechanical
experimentally measured ion-exchange capacity
and electrochemical tests comparing exposed with
of a membrane is an average value assuming that
unexposed membrane samples. Since the useful
the ions are homogeneously distributed over the
life of membranes under process conditions is gen-
entire polymer matrix. In many heterogeneous
erally in the range of a couple of years, membrane
membranes, such as most of the perfluorinated
stability tests are very time consuming. However,
cation-exchange membranes, the fixed ions are
in many cases long-term pilot plant tests are man-
clustered, and the local fixed ion concentration
datory to get a reliable estimation of the life of the
may be significantly higher than the average value.
membranes in practical applications.
The performance of ion-exchange membranes
in the various processes is determined to a very
large extent by their electrochemical properties.
Therefore, a major task in characterizing
ion-exchange membranes is the determination
Ion-Exchange Membrane Characterization
volt meter
calomel electrode
1 n KCl-solution
electrode
solution A A
gas
(O2)
anode
+ porous plug
- -
test solution
Ion-Exchange Membrane Characterization, Fig. 1 Schematic drawing of a test cell for determining the resistance
of ion-exchange membranes with direct current
Determination of the Electrical
Resistance of Ion-Exchange Membranes
The electrical resistance of ion-exchange mem-
branes is an important parameter determining to
the energy consumption in electrodialysis
(Strathmann et al. 2006). The specific membrane
resistance is usually reported as O cm or O
m. From the engineering point of view, the mem-
brane area resistance in units of O cm2 or O m2 is
more useful and generally given in the literature
describing commercial products. The electrical
resistance of a membrane is determined by the
ion-exchange capacity and the mobility of the ion
within the membrane matrix. The ion mobility in
the membrane depends strongly on the nature of
the mobile and fixed ion species. It is furthermore
affected by the temperature.
The area resistance of ion-exchange mem-
branes can be determined by direct current
(DC) or alternating current (AC) measurements.
In DC measurements the membrane is installed in
3
Haber-Luggin capillary
electrode
C solution
gas
(H2)
cathode
-
- +
test solution
a cell which consists of two chambers containing
the test solution separated by the test membrane
as indicated in Fig. 1.
The two electrodes used to provide the elec-
trical potential driving force to obtain a certain
current are separated by membranes from the test
solution to avoid gas bubbles to disturb the mea-
surement. As test solution a 1 or 0.5 mol/L
Na2SO4 solution is used. The same solution is
also used to rinse the electrode chambers and
remove the gases produced at the electrodes.
The actual potential drop in DC measurements
across the membrane is determined with calomel
electrodes attached to Haber-Luggin capillaries
placed with their tips close to the membrane
surface. The potential drop between the Haber-
Luggin capillaries is measured with and without
the membrane in the test cell as a function of the
current density passing through the cell. The
resistance is given by the slope of the current
versus the voltage drop curve. To obtain the
membrane resistance, the resistance of the cell
4 Ion-Exchange Membrane Characterization
without the membrane is subtracted from the
resistance of the cell with the membrane.
The area resistance is given by:
U Am
r mþs ¼ RAm ¼ (1)
i d
The membrane resistance is:
r m ¼ r mþs  r s (2)
Here R is the resistance, Am is the area of the
membrane, U is the voltage drop measured
between the Haber-Luggin capillaries and I is
the current density, rm+s and rs are the area resis-
tances of the cell with and without the membrane
between the Haber-Luggin capillaries, and rm is
the area resistance of the membrane.
The determination of the membrane resistance
by direct current measurements is quite accurate
as long as the position of the Haber-Luggin cap-
illaries is as close as possible to the membrane
and kept identical in the test with and without the
membrane. To avoid boundary layer effects, the
bulk solution must be well mixed. But even if the
boundary layer effects are well controlled, the
direct current measurements are always
connected with a transport of ions resulting in a
concentration change in the electrolyte solution
at the membrane surface which affects the accu-
racy of the measurement.
Concentration changes at the membrane sur-
face are avoided in resistance measurements with
alternating current. A typical test cell used for
resistance measurements with alternating current
is shown in Fig. 3. The membrane resistance is
determined from resistance measurements in a
cell with and without membrane. The resistance
of the membrane can be calculated from the fol-
lowing relation:
The area resistance rm is related to the specific
resistance by:
r m ¼ rmþs ðd m þ dÞ  rs d (3)
Here rm are the area resistances of the membrane,
rm+s and rs are the specific resistances of the cell
with and without the membrane, and dm and d are
the thickness of the membrane and the distance
between the electrodes.
The specific resistance r is:
r¼R (4)
Here Am is the cross-sectional area of the cell as
indicated in Fig. 2 and R is the resistance mea-
sured between the electrodes.
For an accurate determination of the mem-
brane resistance, it is important that the differ-
ence between the measurement of the cell
resistance with and without a membrane is as
large as possible. Since the specific resistances
of the membrane and the electrolyte solution are
in the same order of magnitude and the mem-
brane thickness dm is small, the distance d has to
be as small as possible.
Comparing the direct and alternating current
membrane characterization processes often sig-
nificant differences in the measured resistances of
more than 50 % is often observed. The alternating
current measurements give a much lower mem-
brane resistance than the direct current measure-
ments. This is a general finding. However, the
magnitude of the difference in the results depends
on the membrane structure. In very heteroge-
neous membranes, the difference is larger than
in more homogeneous membrane structures. The
reason for the different results is that in direct
current measurements, the ions are physically
transported through the membrane matrix,
whereas in alternating current measurements,
the ions are only oscillating around their loca-
tions. Assuming the structure of an
ion-exchange membrane consists of a micro-
scopic scale of a solid neutral polymer phase
and electrolyte-filled pores, then the mobility of
the ions in the pore liquid is high. But their
transport through the membrane is hindered by
the solid polymer structure which acts as a bot-
tleneck between pores. This type of structure is
typical for fluorocarbon membranes. In alternat-
ing current measurements, the transport of the
ions on a very small scale, i.e., in a pore, is
measured. In direct current measurements, the
transport of the ions is measured on a
Ion-Exchange Membrane Characterization 5

Ion-Exchange A U
Membrane
Characterization,
Fig. 2 Schematic drawing
of a test cell used for
membrane resistance
measurements using
alternating current

membrane

dm

electrolyte solution

Rm Ion-exchange membranes display a variety of

Rs electrical properties that suggest that they can be
modeled as a combination of electrical analog
Cm
components. For example, an applied potential
can produce a current flow through the mem-
Ion-Exchange Membrane Characterization, brane, and this is indication that the membrane
Fig. 3 Equivalent resistance-capacitance circuit for a has a finite resistance. In addition, the charged
simple membrane in an electrolyte solution neglecting groups at the membrane/solution interface pro-
electrode resistances and capacities
vide sites for the redistribution of charges at the
membrane surface when the potential is changed.
macroscopic scale which includes also the pas-
This charge redistribution is similar to that
sage through a bottleneck between electrolyte-
observed for a capacitor in which a potential
filled pores. The direct current and alternating
change produces a change in the net charges.
current difference is treated in detail in the liter-
The electrolyte solutions and the electrodes on
ature (Zabolotsky and Nikonenko 1993).
both sides of the membrane also have a certain
A rather simple and reliable method of mea-
resistance. The properties of the ion-exchange
suring resistances is based on impedance spec-
membrane, the solution, and the electrodes can
troscopy. The difference between the alternating
be described electrically by an equivalent circuit
current resistance measurements and the imped-
as indicated in Fig. 3, where Cm and Rm are the
ance spectroscopy is that in the first case, the
membrane capacitance and resistance, respec-
frequency of the alternating current is kept con-
tively, and Rs is the resistance of electrodes and
stant, while in impedance spectroscopy the fre-
the electrolyte solution.
quency of the alternating current is changed, and
To determine membrane resistances by
the response to the changing frequency is deter-
impedance spectroscopy, the entire system, i.e.,
mined by a spectrometer.
the membrane, the electrolyte, and the electrodes,
6 Ion-Exchange Membrane Characterization
is treated as a “black box.” An alternating sinu-
soidal voltage of a given frequency and ampli-
tude is applied to the system. The resulting
current is measured, and then the phase shift
compared to the input signal is determined. The
procedure is repeated at different frequencies (see
entry “Impedance Spectroscopy, Membrane
Characterization by).
References
Spiegler KS (1958) Transport process in ionic mem-
branes. Trans Faraday Soc 54:1408–1428
Strathmann H, Bauer B, Rapp HJ (1993) Better bipolar
membranes. Chemtech 23:17
Strathmann H, Giorno L, Drioli E (2006) An introduction
to membrane science and technology. CNR Publisher,
Roma. ISBN 88-8080-063-9
Zabolotsky VI, Nikonenko VV (1993) Effect of structural
membrane inhomogeneity on transport properties.
J Membr Sci 79:181–198
M

Membrane Rugosity where Ar is the real (actual) surface area and Ag is

the geometric surface area.
Paul Melvyn Williams Membrane rugosity is synonymous with mem-
Swansea University, College of Engineering, brane roughness (see entry on ▶ membrane
Swansea, UK roughness).

Membrane Rugosity: Membrane rugosity is a

References
measure of small-scale variations or amplitude
in the height of a surface. The rugosity IUPAC (1997). Compendium of Chemical Terminology,
(or roughness factor) of a surface, fr, is calculated 2nd ed. (the "Gold Book"). Compiled by A.D.
using the ratio (IUPAC et al. 1997): McNaught and A. Wilkinson, Blackwell Scientific
Publications, Oxford, UK
Ar
fr ¼
Ag

# # Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_998-1
M
Membrane Roughness
Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
Membrane Roughness: Surface roughness is a
measure of the texture of a surface. For mem-
branes, the roughness may be defined as the devi-
ation of the actual membrane surface topography
from an ideal atomically smooth surface. Rough-
ness plays an important role in determining how
the membrane surface will interact with its envi-
ronment. For example, surface roughness is
important in evaluating the performance of a
membrane as it may influence the transmembrane
transport and fouling potential of the membrane
(Hobbs et al. 2006). The surface roughness may
also correlate with other material characteristics
such as the pore-size distribution and molecular
weight cutoff (Bowen and Doneva 2000). Mem-
brane roughness is usually quantified by one or
more of a range of parameters. The most common
parameters used are:
(i) Peak-to-valley roughness
The peak-to-valley roughness describes
the maximum observed range in a sample
area and is given by the distance between
the highest peak (Zmax) and the lowest val-
ley (Zmin) on the measured surface, where
Z indicates the vertical height of the surface:
# Crown 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_999-1
Rpv ¼ Zmax  Zmin
(ii) Average roughness
The average roughness (Ra) is the most
widely used because it is a simple parameter
to obtain when compared to others. The
average roughness is calculated using
 
N 
X Zn  Z
Ra ¼
n¼1
N
where Zn is the height at sample point n, Z is
the height of the center plane, and N is the
total number of points in the sample area.
(iii) Root-mean-squared roughness.
The root-mean-squared roughness (RRMS) is
a statistical measure used in many different
fields. The RRMS value is given by the stan-
dard deviation of the Z values for the sample
area:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N  
uX Z n  Z 2
RRMS ¼ t
n¼1
N
The RMS roughness of a surface is similar to
the average roughness, with the only difference
being in the use of the mean-squared absolute
values of the surface roughness profile. As the
RMS roughness contains square terms, large
deviations from the average height are weighted
more heavily than for the mean roughness.
2 Membrane Roughness
Experimental determination of the membrane
surface roughness is almost always conducted
using atomic force microscopy (AFM). However,
there is some difficulty when comparing results
reported in literature due to the variation in the
methods applied and the sample areas examined
(Boussu et al. 2005).
References
Boussu K, Van der Bruggen B, Volodin A, Snauwaert J,
Van Haesendonck C, Vandecasteele C (2005)
Roughness and hydrophobicity studies of
nanofiltration membranes using different modes of
AFM. J Colloid Interface Sci 286:632–638
Bowen WR, Doneva TA (2000) Atomic force microscopy
characterization on ultrafiltration membranes: corre-
spondence between surface pore dimensions and
molecular weight cut-off. Surf Interface Anal
29:544–549
Hobbs C, Taylor J, Hong S (2006) Effect of surface rough-
ness on fouling of RO and NF membranes during
filtration of a high organic surficial groundwater.
J Water Supply Res Technol AQUA 55:559–570
M

Membrane Topography for membrane topography include scanning elec-

Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
Membrane topography: At the nanoscale mem-
branes are not flat surfaces. Membrane topogra-
phy is concerned with the study of the membrane
surface shape and features. In a broader sense,
membrane topography is concerned with detail in
general about membrane surfaces. Some of the
more popular surface characterization techniques
tron microscopy (SEM) and atomic force micros-
copy (AFM). Each of these tools is capable of
providing atomic-level quantitative analyses of
the morphological characteristics of membrane
surfaces. Using these tools, it is possible to char-
acterize membrane properties like surface rough-
ness, porosity, and pore size distribution (Bowen
and Hilal 2009; Barbosaa and Silva 2012)
(Fig. 1).

# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1000-1
2 Membrane Topography

Membrane Topography, a
Fig. 1 The three-
dimensional images of 20.0 nm
membranes by AFM. (a)
0.0 nm
A6DT and (b) PA6DT-C
(Cheng et al. 2011)
0.8 µm
0.8 µm
0.6
0.6
0.4
0.4
0.2 0.2

b
20.0 nm

0.0 nm

0.8 µm
0.8 µm
0.6
0.6
0.4 0.4
0.2 0.2

References Bowen WR, Hilal N (2009) Atomic force microscopy in

Barbosaa EF, Silva LP (2012) Nanoscale characterization
of synthetic polymeric porous membranes: scrutiniz-
ing their stiffness, roughness, and chemical composi-
tion. J Membr Sci 407–408:128–135
process engineering: an introduction to AFM for
improved processes and products. Elsevier, Oxford
Cheng S, Oatley DL, Williams PM, Wright CJ (2011) Pos-
itively charged nanofiltration membranes: review of
current fabrication methods and introduction of a
novel approach. Adv Colloid Interface Sci 164:12–20
N
NF Membrane Characterization
Methods
Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
A variety of techniques and approaches are rou-
tinely used for characterizing the physical and
chemical properties of nanofiltration
(NF) membrane surfaces (Web Report #4102
2012). The main fundamental properties which
are usually characterized, in no particular order,
include molecular weight cut-off (MWCO), pore
size (and pore-size distribution), pure water flux,
surface charge (or zeta potential), hydrophobicity
and/or hydrophilicity, and membrane morphol-
ogy and surface roughness.
The molecular weight cut-off is found by fil-
tering a range of molecules (very often polyeth-
ylene glycol (PEG)) with known molecular
weights. The molecular weight of the molecule
that is 90 % retained by the membrane is usually
defined as the MWCO of that membrane.
The pore size of the membrane may be found
via atomic force microscopy (AFM) measure-
ments or more usually by filtering an uncharged
molecule like glucose and fitting the Nernst-
Plank equation for uncharged solutes to the
results, using the membrane pore size as the
fitting parameter. NF membranes are typically
rated by MWCO rather than nominal pore size.
# Crown 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1001-1
The flux or pure water flux for a membrane is
typically expressed as volume per area per unit of
time. Flux is used to express the rate at which
pure water permeates a NF membrane. Typical
units of measurement are gallons per square foot
per day (i.e., GFD or GSFD) or liters per square
meter per hour (l/m2/h)
Streaming potential measurements are most
often used to calculate the zeta potential of an
NF membrane surface. This is an indicator of the
membrane surface charge under variable solution
chemistries.
Measuring the contact angle that is formed
when a droplet of water is placed on the mem-
brane surface is used to quantify the hydropho-
bicity/hydrophilicity of the membrane surface.
AFM and scanning electron microscopy
(SEM) are both powerful techniques used to
quantify and visualize the morphology or rough-
ness of membrane surfaces. SEM in particular is
used to visualize the cross-sectional morphology
of NF membranes.
References
Childress, A.E., Brant, J.A., Rempala, P. Phipps Jr., D.W.
and Kwan, P., (2012) Web Report #4102 - Evaluation
of membrane characterization methods. Water
Research Foundation, 6666 West Quincy Avenue,
Denver, CO 80235 (web link: http://www.waterrf.
org/publicreportlibrary/4102.pdf)
M
Membrane Charge
Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
Membrane charge: Membranes acquire a charac-
teristic electric surface charge when contacted
with an aqueous solution. For both organic and
inorganic membranes, the surface of a membrane
can become charged due to the dissociation of
specific ionizable groups on the surface. These
ionization reactions depend on the pH and the
electrolyte in the bulk solution in contact with
the membrane. The charge and resulting potential
of the membrane depend strongly on the pH of
the system because the majority of the membrane
functional groups protonate and deprotonate over
the pH range.
As a direct result of the fabrication materials
traditionally employed in membrane manufac-
ture, most membranes are either neutral or nega-
tively charged in an aqueous processing
environment (Tsuru et al. 1998; Childress and
Elimelech 1996). However, positively charged
membranes can be produced by surface
# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1002-1
modification of the membrane (Cheng
et al. 2011). The most common technique for
evaluating the membrane surface charge (zeta
potential) is via streaming potential measure-
ments (Hunter 1981).
The charge of the membrane is significant to
membrane performance because charge affects
the electrostatic repulsion between the ions or
charged molecules and the membrane surface.
This can also have an impact on membrane foul-
ing as well.
References
Cheng S, Oatley DL, Williams PM, Wright CJ (2011) Pos-
itively charged nanofiltration membranes: review of
current fabrication methods and introduction of a
novel approach. Adv Colloid Interface Sci 164:12–20
Childress AE, Elimelech M (1996) Effect of solution
chemistry on the surface charge of polymeric reverse
osmosis and nanofiltration membranes. J Membr Sci
119:253–268
Hunter RJ (1981) Zeta potential in colloid science: prin-
ciples and applications. Academic, London
Tsuru T, Takezoe H, Asaeda M (1998) Ion separation by
porous silica-zirconia nanofiltration membranes.
AIChE J 44:765–768
M
Membrane Charge (Zeta Potential)
Effect
Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
Membrane surface charge (zeta potential)
effect: The membrane surface charge or zeta
potential is most often characterized using the
streaming potential method (Hunter 1981) (see
“▶ Membrane Charge Characterization”). The
charge of a membrane is significant to membrane
performance because charge affects the electro-
static repulsion between the ions or charged mol-
ecules and the membrane surface.
Due to the materials used in the fabrication of
membranes, most membrane surfaces show a
negative charge at neutral pH values (i.e., pH 7).
However, due to the amphoteric nature of the
chemical groups on the surface of a membrane,
the charge may be altered by adjusting the solu-
tion conditions (i.e., pH and electrolyte concen-
tration) (Cheng et al. 2011). Surface
modifications may also be made to membranes
in order to change the charge from negative to
positive (Cheng et al. 2011; Kobayashi
et al. 1996).
Membrane surface charge has a big influence
on the rejection of charged species (i.e., salt,
charged dyes, amino acids, etc.) for nanofiltration
membranes. The isoelectric point (Hunter 1981)
# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1003-1
(the pH at which point where there is no effective
charge) of a membrane can be determined from
the minimum rejection value obtained when fil-
tering a charged species (like sodium chloride
(NaCl)), by varying the pH value at a fixed elec-
trolyte concentration and constant applied pres-
sure (Cheng et al. 2011).
For ultrafiltration membranes, the charge on
the membrane surface will affect the interactions
between the membrane and the particles in the
feed solution. If the charge on both the membrane
surface and the particles is of the same sign,
repulsion will occur, and there will be less fouling
and concentration polarization at the membrane
surface. However, if the charge on the membrane
surface is of the opposite sign to the particles,
attractive forces will dominate and the membrane
will foul easily, thus reducing performance. The
membrane charge can have a significant effect on
the flux obtained (Bacchin et al. 2006).
The determination of the membrane surface
zeta potential can also be used as an indicator
for membrane fouling (Lawrence et al. 2006;
Al-Amoudi et al. 2007). The effect of foulants
can be investigated, and based on the measure-
ment results, the membrane surface can be spe-
cifically treated to decrease membrane fouling
and extend the membrane lifetime (Lawrence
et al. 2006; Al-Amoudi et al. 2007).
2 Membrane Charge (Zeta Potential) Effect
References
Al-Amoudi A, Williams PM, Mandale S, Lovitt RW
(2007) Cleaning results of new and fouled
nanofiltration membrane characterized by zeta poten-
tial and permeability. Sep Purif Technol 54:234–240
Bacchin P, Aimar P, Field RW (2006) Critical and sus-
tainable fluxes: theory, experiments and applications.
J Membr Sci 281:42–69
Cheng S, Oatley DL, Williams PM, Wright CJ (2011) Pos-
itively charged nanofiltration membranes: review of
current fabrication methods and introduction of a
novel approach. Adv Colloid Interf Sci 164:12–20
Hunter RJ (1981) Zeta potential in colloid science: prin-
ciples and applications. Academic, London
Kobayashi T, Nagai T, Ono M, Fujii N (1996) Charged
membranes for ultrafiltration treatment of synthetic
waste water containing peptone. J Chem Tech
Biotechnol 65:49–55
Lawrence ND, Perera JM, Iyer M, Hickey MW, Stevens
GW (2006) The use of streaming potential measure-
ments to study the fouling and cleaning of ultrafiltra-
tion membranes. Sep Purif Technol 48:106–112
M

Membrane Charge Characterization streaming potential across the membrane

(Nystrom et al. 1994).
Paul Melvyn Williams
Swansea University, College of Engineering,
Swansea, UK
Electroosmosis

A simple “dipped cell” apparatus can be used for

The surface charge density and thus membrane
measuring the electroosmotic flow rate across a
charge of a porous membrane are related to the
microporous membrane (Bowen and Clark
zeta potential of the membrane. There are several
1984). The membrane is held at the end of a
procedures that allow characterization of the
deep tube immersed in the thermostated electro-
membrane zeta potential and thus surface charge.
lyte. Two electrodes are used. The first one is
positioned behind the membrane and the second
one is positioned outside the tube. At the begin-
Streaming Potential
ning of the experiment, the liquid level both
inside and outside the tube are the same.
When an electrolyte solution flows across or
A constant current is then applied between the
through a stationary, charged membrane, the
two electrodes which induces an electroosmotic
flow of liquid tangential to the material drags
flow of electrolyte in the tube. Overflowed elec-
the excess charges near to the material wall
trolyte is transferred to an electronic balance.
downstream. This causes the build-up of an elec-
Zeta potential was determined by measuring the
tric field which drives a current in the reverse
rate of electroosmosis across the membrane.
direction. The streaming potential that is induced
The literature shows that the streaming poten-
may be measured using electrodes. The zeta
tial method has been much more widely studied
potential is calculated from the measured stream-
in comparison to electroosmosis phenomena.
ing potential using the Helmholtz-Smoluchowski
For nanofiltration membranes, it is also possi-
equation (Smoluchowski 1905; Abramson 1934)
ble to evaluate the effective membrane charge
with the Fairbrother and Mastin substitution
density, Xd, by fitting experimental data of the
(Fairbrother and Mastin 1924). The streaming
variation of electrolyte rejection with concentra-
potential may be measured either across the sur-
tion (Bowen et al. 1997). However, this parame-
face of the membrane, by forming a thin channel
ter is essentially a fitting parameter and has no
and pumping the electrolyte through this channel,
real physical basis.
or through the pores enabling measurement of the
# Crown 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1004-1
2 Membrane Charge Characterization
References
Abramson HA (1934) Electrokinetic phenomena and their
application to biology and medicine, vol 66, ACS
monograph series. Chemical Catalog, New York
Bowen WR, Clark RA (1984) Electroosmosis at micropo-
rous membranes and the determination of zeta-
potential. J Colloid Interface Sci 97:401–409
Bowen WR, Mohammad AW, Hilal N (1997) Character-
isation of nanofiltration membranes for predictive pur-
poses: use of salts, uncharged solutes and atomic force
microscopy. J Membr Sci 126:91
Fairbrother F, Mastin H (1924) CCCXII – studies in
electro-endosmosis. Part I. J Chem Soc
125:2319–2330
Nystrom M, Pihlajamaki A, Ehsani N (1994) Characteri-
zation of ultrafiltration membranes by simultaneous
streaming potential and flux measurements. J Membr
Sci 87:245–256
Smoluchowski, M. 1905. Zur theorie der elektrischen
kataphorese und der oberflachenleitung. Physikalische
Z. 6:529–536
S
Surface Tension
Paul Melvyn Williams
College of Engineering, Swansea University,
Swansea, UK
Surface tension: The term surface tension refers
to the observation that the surface of a liquid
behaves as though it were covered with a thin
“skin” which resists attempts to puncture it. This
property is caused by cohesion of similar mole-
cules and is responsible for many of the behaviors
of liquids. In the bulk of the liquid, each molecule
# Crown 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1005-1
is pulled equally in every direction by neighbor-
ing liquid molecules, resulting in a net force of
zero. The molecules at the surface do not have
other molecules on all sides of them and therefore
are pulled inward. This creates some internal
pressure and forces liquid surfaces to contract to
the minimal area. Surface tension has the dimen-
sion of force per unit length or of energy per unit
area. The two are equivalent. In SI surface ten-
sion is measured in N/m or in J/m2 (although the
more common units in cgs are dynes/cm or
erg/cm2, respectively).
E
Enantioselective Transport of Amino membranes and liquid membranes. The method
Acids by Membrane Operations using liquid membranes is described in another
Keiji Sakaki
National Institute of Advanced Industrial Science
and Technology (AIST), Research Institute for
Sustainable Chemistry, Tsukuba, Ibaraki, Japan
Amino acids are molecules that contain an
amino group (–NH2), a carboxylic acid group
(–COOH), and a side chain in each structure and
are the structural units of proteins. The most of
amino acids found in nature are categorized as
a-amino acid in which the amino group is
attached to the carbon atom adjacent to the car-
boxylic acid group. An a-amino acid can exist in
either of two optical isomers except glycine, and
the isomer is normally described as L- or D-amino
acid. The majority of amino acids in living organ-
isms are L-isomers. Optical isomers, including
amino acids, frequently show different bioactiv-
ity from each other. So, optical resolution of
amino acids has been an important subject in
various industries dealing with pharmaceuticals,
foods, agrochemicals, and so on.
Optical resolution with membrane processes
has potential merits over other separation
methods like crystallization or chromatography.
Membrane operation can be carried out continu-
ously and it enables the large-scale separation.
Optical resolution of amino acids can be achieved
by the function of chiral recognition sites of solid
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1012-3
site, so solid membranes for enantioselective sep-
aration are explained here. A main research topic
on enantioselective membranes is the design of
the membranes that have the chiral recognition
sites. Some enantioselective solid membranes
have been reported as follows.
Membranes Prepared from Chiral
Polymers
Polypeptide and polysaccharide, like cellulose,
alginate, and chitosan, and their derivatives are
chiral polymers, and membranes from these chi-
ral polymers have been applied to the
enantioselective separation of racemic amino
acids. The separation factor of these membranes
toward racemic tryptophan is usually in the range
of 1.1–5.0 (Higuchi et al. 2010). Membranes pre-
pared from polymers with chiral branch have
been also reported.
Membranes Added with Chiral Selectors
Enantioselective membranes can be prepared by
the addition of chiral selectors that show
enantioselective affinity toward amino acids.
Cyclodextrins, bovine serum albumin (BSA),
and DNA have been used as chiral selectors.
The membranes added with these chiral selectors
2 Enantioselective Transport of Amino Acids by Membrane Operations
showed the separation factor of 1.1–2.7 toward
amino acids (Higuchi et al. 2010).
Molecular Imprinting Membranes
(MIMs)
Molecular imprinting membranes are fabricated
by incorporating the template molecules into the
membranes and then removing the template mol-
ecules. The formed cavities in the membranes
show the specific affinity with the template mol-
ecules and their analogue (Yoshikawa
et al. 1995). Although MIMs currently show
low enantioselectivity, this method has the poten-
tial of higher enantioselectivity (Xie et al. 2008).
Solid enantioselective membranes can be
divided into two classes: diffusion-selective
membranes and sorption-selective membranes
(van der Ent et al. 2001; Xie et al. 2008). A -
diffusion-selective membrane is defined as a
membrane with no specific chiral selectors for
the chiral interaction but consists of a chiral poly-
mer. Diffusion selectivity is caused by the chiral
discrimination during diffusion. On the other
hand, in a sorption-selective membrane, chiral
selectors are embedded in a polymer matrix. To
reach permeation selectivity in sorption-selective
membranes, the selectively adsorbed population
has to be mobile. An electrical potential is some-
times used for the purpose.
References
Higuchi A, Tamai M, Ko Y, Tagawa Y, Wu Y, Freeman B,
Bing J, Chang Y, Ling Q (2010) Polymeric membranes
for chiral separation of pharmaceuticals and
chemicals. Polym Rev 50:113–143
van der Ent EM, van’t Riet K, Keurentjes JTF, van der
Padt A (2001) Design criteria for dense permeation-
selective membranes for enantiomer separations.
J Membr Sci 185:207–221
Xie R, Chu L, Deng J (2008) Membranes and membrane
processes for chiral resolution. Chem Soc Rev
37:1243–1263
Yoshikawa M, Izumi J, Kitano T (1995) Molecularly
imprinted polymeric membranes for optical resolution.
J Membr Sci 108:171–175
S
Supported Liquid Membrane
for Enantioselective Separation
Keiji Sakaki
National Institute of Advanced Industrial Science
and Technology (AIST), Research Institute for
Sustainable Chemistry, Tsukuba, Ibaraki, Japan
An enantiomer is one of two stereoisomers that
are mirror images of each other and
nonsuperposable. This feature of an enantiomer
is called “chirality.” Many chiral molecules not
only appear in nature but also can be synthesized
artificially. Amino acids and sugars are the rep-
resentative chiral molecules found in nature, and
they exist in the form of one isomer. Enantio-
meric pairs frequently show different biological
activity from each other. So the technology to
separate enantiomers has been an important sub-
ject in the industries dealing with pharmaceuti-
cals, foods, agrochemicals, and so on. However,
enantioselective separation has been a challeng-
ing subject because each enantiomer has the same
physical and chemical properties.
Some methods have been reported for enan-
tiomeric separation, for example, preferential
crystallization, chromatographic separation,
enzyme-mediated resolution, and membrane-
based separation (Xie et al. 2008). Among them,
membrane-based method has some advantages
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1013-3
over the other methods, such as low energy
demand, continuous operation, and easy scale-
up. Both liquid membrane and solid membrane
have been applied to enantiomeric separation.
The important factor of membrane-based
enantioselective separation is the way how to
give the function of chirality recognition to mem-
branes. In the process using solid membranes,
chirality recognition exists in main polymer
chain, chiral polymer branch, and doped chiral
selector or cavity formed by molecular imprint-
ing (Higuchi et al. 2010). On the other hand, in
the separation with liquid membranes,
enantioselective carriers are usually doped in
the liquid membranes. In a supported liquid
membrane (SLM), a liquid containing
enantioselective carriers is impregnated into a
porous support membrane. The separation con-
cept in SLM process is shown in Fig. 1. On the
membrane surface in the feed phase, a doped
carrier combines with one isomer more preferen-
tially than the other, and the carrier-isomer com-
plex diffuses in the liquid membrane toward the
strip phase. On the membrane surface of strip
phase, the carrier releases the isomer. In the
SLM process, the driving force is the concentra-
tion gradient of co- or counterions (indicated as
X in Fig. 1) between feed and strip phases. Typ-
ical carriers used in SLM processes are crown
ethers. Figure 2 shows the structure of one of
crown ethers that shows high enantioselectivity
2 Supported Liquid Membrane for Enantioselective Separation

Feed Liquid Membrane Strip HOH2C O

O O CH2OH
O HO HO
S+X C OH HO
S+X
HOH2C O
HO
O OH
O
OH HO
O CH2OH
S−C −X
HOH2C OH HO O
O HO O
Supported Liquid Membrane for Enantioselective OH
OH HO
Separation, Fig. 1 Concept of transportation in SLM O O CH2OH
O
CH2OH

Supported Liquid Membrane for Enantioselective

O O
O O
O O
O O
Supported Liquid Membrane for Enantioselective
Separation, Fig. 2 An example of chiral crown ether
toward amino acids (Shinbo et al. 1993). Cyclo-
dextrins are used as chiral carriers in aqueous
SLM (Armstrong and Jin 1987). The molecular
structure of b-cyclodextrin is shown in Fig. 3.
The improvement of membrane stability is the
key factor for the industrial application of SLM
process (Kocherginsky et al. 2007).
Separation, Fig. 3 b-Cyclodextrin
References
Armstrong DW, Jin HL (1987) Enrichment of enantio-
mers and other isomers with aqueous liquid mem-
branes containing cyclodextrin carriers. Anal Chem
59:2237–2241
Higuchi A, Tamai M, Ko Y, Tagawa Y, Wu Y, Freeman B,
Bing J, Chang Y, Ling Q (2010) Polymeric membranes
for chiral separation of pharmaceuticals and
chemicals. Polym Rev 50:113–143
Kocherginsky NM, Yang Q, Seelam L (2007) Recent
advances in supported liquid membrane technology.
Sep Purif Technol 53:171–177
Shinbo T, Yamaguchi T, Yanagishita H, Sakaki K,
Kitamoto D, Sugiura M (1993) Supported liquid mem-
branes for enantioselective transport of amino acid
mediated by chiral crown ether -effect of membrane
solvent on transport rate and membrane stability.
J Membr Sci 84:241–248
Xie R, Chu L, Deng J (2008) Membranes and membrane
processes for chiral resolution. Chem Soc Rev
37:1243–1263
P
Palladium-Based Membrane
(Palladium Alloy Membrane)
Ekain Fernandez1, Fausto Gallucci2 and David A.
Pacheco Tanaka1
1
Energy and Environment, TECNALIA,
Donostia-San Sebastian, Gipuzkoa, Spain
2
Chemical Process Intensification, Department of
Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
Palladium-based membranes have received a
growing interest for the separation and purifica-
tion of hydrogen from various resources (Paglieri
and Way 2002; Yun and Oyama 2011; Gallucci
et al. 2013). In addition, palladium membranes
can be used as a palladium-based membrane
reactor where the separation process is coupled
with catalytic reactions. Palladium-based mem-
branes have advantages of high hydrogen flux
and exclusive permselectivity for hydrogen due
to the unique permeation mechanism as shown in
Fig. 1.
General Aspects
The developments in Pd and Pd alloys have been
carried out for a long time (Buxbaum 1999;
Grashoff et al. 1983; Holleck 1970). The most
important problem associated with the use of pure
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1031-3
Pd membranes is the hydrogen embrittlement
phenomenon. Operation with hydrogen at a tem-
perature below 300
C and a pressure below
2 MPa leads to the nucleation of the b-hydride
phase from the a-phase resulting in severe lattice
strains. In this case a pure palladium membrane
becomes brittle after a few a,b cycles (Hsieh
1989). Another important problem is the palla-
dium surface poisoning, which can be more sig-
nificant for thin metal membranes, by sulfur
compounds (Edlund and Pledger 1994), CO
(Amandusson et al. 2000), H2O (Li et al. 2000),
chlorine, carbon, unsaturated hydrocarbons,
etc. In order to avoid hydrogen embrittlement
and poisoning and reduce membrane cost, palla-
dium can be alloyed with other metallic elements
such as Ag, Cu, Fe, Ni, Pt, and Y (Bryden and
Ying 2002; Qiao et al. 2010; Uemiya et al. 2007),
or the palladium grains can be used in nanometer
sized (Pacheco Tanaka et al. 2006).
Palladium Alloys
Among binary palladium alloys, Pd-Ag, Pd-Cu,
Pd-Au, Pd-Ce, and Pd-Y exhibit higher perme-
abilities in comparison to pure Pd, according to
Knapton that tested 25 mm thick alloys (Knapton
1977). Pd90Y10 has hydrogen permeability 3.8
times higher than pure Pd at 350
C.
Some interesting palladium alloys to avoid
embrittlement are Pd77-Ag23 and Pd70-Pt30
(weight%) alloys since their critical temperature
2 Palladium-Based Membrane (Palladium Alloy Membrane)
Palladium-Based
Membrane (Palladium
Alloy Membrane),
Fig. 1 Solution-diffusion
H H
mechanism of hydrogen
permeation through a
palladium-based
membrane (Yun and
Oyama 2011)
(Tc) for formation of the b-phase is around room
temperature (Paglieri and Way 2002). Besides,
Pd-Cu alloys do not show embrittlement even at
low temperatures (Kulpatripanja et al. 2005).
Pd-Cu, Pd-Au, Pd-Pt, Pd-Rh, and Pd-Ru
alloys have been used for increasing the tolerance
to sulfur (Paglieri and Way 2002; Morreale
et al. 2004; Way et al. 2008). According to
McKinley, a Pd60Au40 (mass%) is superior to a
Pd60Cu40 (mass%) concerning poisoning by sul-
fur (McKinley and Nitro 1967). According to
Morreale et al., face-centered cubic (fcc) Pd-Cu
showed a decline of 0–10 % permeability when
exposed to 1,000 ppm of sulfur, and body-
centered cubic (bcc) Pd-Cu showed a decline of
99 % at the same sulfur content stream (Morreale
et al. 2004). Thus, the final structure of the palla-
dium alloy is an important issue. In general, the
sulfides of Pt, Ir, Rh, and Ru are much less stable
than those of the Pd, and thus these elements
show better tolerance to poisoning by sulfur.
Currently, novel Pd-based ternary alloy mem-
branes are being studied (Peters et al. 2011,
2013).
Unsupported and Supported
Membranes
Unsupported Pd-based membranes need to be
thick self-standing films (>50 mm thick) in
order to have a minimum mechanical stability.
The main drawback of these membranes is their
low hydrogen permeance. Moreover, in the case
of using an expensive membrane material, the
H2
a) External diffusion
b) Dissociation
H H
H H H H c) Dissolution
d) Internal diffusion
H H H H
e) Association
H H2 H2 H
f) Desorption
g) External diffusion
H2
cost of the whole membrane will be sharply
increased by increasing the membrane thickness.
Thus, there is a threshold between membrane
mechanical stability and membrane thickness
(and thus flux and costs). For this reason it is
foreseen that the first industrially available mem-
branes will be supported membranes. Supported
membranes consist of a thin selective film depos-
ited onto a support that provides mechanical sta-
bility. Thus, the hydrogen permeance of the
membrane will be higher so that less membrane
area is required and the whole membrane cost
will be lower than that for unsupported mem-
branes. However, in the total membrane cost,
the cost of the support also becomes important.
Especially when very thin film membranes are
selected, the support pore size should be much
lower and the surface much smoother, so that its
cost will increase. There are mainly two types of
porous support materials: metallic and
ceramic. Ceramic supports typically have better
surface quality providing membranes with thin-
ner selective layers. However, they are more
fragile. Metallic supports are more robust than
ceramic, but the commercial ones, mainly tubu-
lar, have lower surface qualities. Some research
groups are developing hollow fiber supports
(both ceramic and metallic) in order to increase
the surface area to volume ratio and also improve
the surface quality (Luiten-Olieman et al. 2012).
In the case of the Pd-based membrane, support is
metallic and is used at temperatures above the
Tamman temperature of one of the metallic parts,
common situation for high-temperature
reforming reactions; it is necessary to position
Palladium-Based Membrane (Palladium Alloy Membrane) 3

an intermetallic diffusion barrier layer between

the metallic support and the metallic selective
layer. In this case the materials used as barrier
layer are ZrO2 (Tarditi et al. 2013), YSZ (Sanz
et al. 2011), TiO2 (Li et al. 2008), CeO2 (Qiao
et al. 2010), and Al2O3 (Dardas et al. 2009).

Palladium Membrane Preparation

Common Pd-based layer deposition technologies

include physical vapor deposition (PVD, includ-
ing magnetron sputtering, thermal evaporation,
or pulsed-laser evaporation), chemical vapor
deposition (CVD or MOCVD), electroless plat-
ing (ELP), electroplating, and diffusion welding
(Iniotakis et al. 1987). Each technology has its
strengths and weaknesses; therefore, there is a
trend of tailoring the deposition technology to
the features of the support in order to obtain a
suitable composite membrane. The most widely
used preparation technology for dense metal
layers is ELP due to its ability of covering sup-
ports with complex geometries, the simplicity of
the required equipment, and its low cost (absence
of electrodes or electrical source) (Mallory and
Hajdu 1990). On the other hand, PVD magnetron
sputtering is a very attractive deposition technol-
ogy because it could provide thinner uniform
layers (down to only few nanometers), much
lower than the thickness achieved with the ELP
technique, with a controlled microstructure and
composition across of these coatings. Other
important advantage of PVD versus ELP is its
environmental friendly operation, without pro-
ducing waste liquids from chemical baths
(Klette 2005).
Membrane Commercialization
There are various companies working in the com-
mercialization of palladium-based membranes as
reported by Gallucci et al. (2013); Figure 2 shows
Pd-based tubular membranes manufactured by
CRI/Criterion. As an example of industrial appli-
cation and membrane scale-up, three commercial
membranes from MRT, ECN, and NGK have
Palladium-Based Membrane (Palladium Alloy Mem-
brane), Fig. 2 Palladium-based commercial tubular
membranes manufactured by CRI/Criterion (http://www.
cricatalyst.com/)
been used in membrane reactors for methane
steam reforming in a pilot plant for 20 m3/h of
hydrogen at Tecnimont KT (Italy) (Palo
et al. 2012); the membranes showed good perfor-
mance over 1,300 h of testing and 70 cycles of
start-up and shutdown with no signs of membrane
degradation regarding hydrogen regarding hydro-
gen permeation properties.
References
Amandusson H, Ekedahl LG, Dannetun H (2000) The
effect of CO and O2 on hydrogen permeation through
palladium membrane. Appl Surf Sci 153:259–267
Bryden KJ, Ying JY (2002) Nanostructured palladium-
iron membranes for hydrogen separation and mem-
brane hydrogenation reactions. J Membr Sci
203:29–42
Buxbaum RE (1999) Composite metal membrane for
hydrogen extraction. US Patent 5215729
Dardas Z, She Y, Vanderspurt TH, Yamanis J, Walker
C (2009) Composite palladium membrane having
long-term stability for hydrogen separation. US Patent
0000480A1
4 Palladium-Based Membrane (Palladium Alloy Membrane)
Edlund DJ, Pledger WA (1994) Catalytic platinum-based
membrane reactor for removal of H2S from gas natural
streams. J Membr Sci 84:111–119
Gallucci F, Fernandez E, Corengia P, Van Sint Annaland
M (2013) Recent advances on membrane and mem-
brane reactors for hydrogen production. Chem Eng Sci
92:40–66
Grashoff GJ, Pilkington CE, Corti CW (1983) The purifi-
cation of hydrogen: a review of the technology empha-
sizing the current status of palladium membrane
diffusion. Report 27(4):157–169
Holleck GL (1970) Diffusion and solubility of hydrogen in
palladium and palladium-silver alloys. J Phys Chem
74(3):503
Hsieh HP (1989) Inorganic membrane reactors – a review.
AIChE Symp Ser 85:53–67
Iniotakis N, Von Der Decken CB, Fedders H,
Froehling W, Semetz F (1987) Hydrogen permeation
membrane. US Patent 4699637
Klette H (2005) Thin Pd-Ag foil prepared by PVD,
supported on porous SS. Membr Technol 5:7
Knapton AG (1977) Palladium alloys for hydrogen diffu-
sion membranes. Platin Met Rev 21(2):44–50
Kulpatripanja A, Alptekin GO, Falconer JL, Way JD
(2005) Pd and Pd–Cu membranes: inhibition of H2
permeation by H2S. J Membr Sci 254:49–62
Li A, Ling W, Hughes R (2000) The effect of carbon
monoxide and steam on the hydrogen permeability of
a Pd/stainless steel membrane. J Membr Sci
165:135–141
Li X, Liu TM, Fan YQ, Xu NP (2008) Preparation of
composite palladium-silver alloy membranes by
photocatalytic deposition. Thin Solid Films
516:7282–7285
Luiten-Olieman MW, Raaijmakers MJT, Winnubst L, Bor
TC, Wessling M, Nijmeijer A, Benes NE
(2012) Towards a generic method for inorganic porous
hollow fibers preparation with shrinkage-controlled
small radial dimensions, applied to Al2O3 Ni, SiC,
stainless steel, and YSZ. J Membr Sci
407–408:155–163
Mallory O, Hajdu JB (1990) Electroless plating: funda-
mentals and applications. American Electroplaters and
Surface Finishers Society, Orlando. ISBN
9780815512776
McKinley DL, Nitro WV (1967) Metal alloy for hydrogen
separation and purification. US Patent 3350845
Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
Cugini AV, Enick RM (2004) Effect of hydrogen-
sulfide on the hydrogen permeance of palladium-
copper alloys at elevated temperatures. J Membr Sci
241:219–224
Pacheco Tanaka DA, Llosa Tanco MA, Nagase T,
Okazaki J, Wakui Y, Mizukami F, Suzuki TM
(2006) Fabrication of hydrogen permeable composite
membranes packed with palladium nanoparticles. Adv
Mater 18:630–632
Paglieri SN, Way JD (2002) Innovations in palladium
membrane research. Sep Purif Rev 31:1–169
Palo E, Iaquaniello G, Cucchiella B, Salladini A (2012)
Membrane module design: a general introduction in Pd
membrane technology scale-up workshop
Peters TA, Kaleta T, Stange M, Bredesen R (2011) Devel-
opment of thin binary and ternary Pd-based alloy
membranes for use in hydrogen production. J Membr
Sci 383:124–134
Peters TA, Kaleta T, Stange M, Bredesen R (2013) Devel-
opment of ternary Pd-Ag-TM alloy membranes with
improved sulphur tolerance. J Membr Sci
429:448–458
Qiao A, Zhang K, Tian Y, Xie L, Luo H, Lin YS, Li
Y (2010) Hydrogen separation through palladium-
copper membranes on porous stainless steel with
sol-gel derived ceria as diffusion barrier. Fuel
89:1274–1279
Sanz R, Calles JA, Alique D, Furones L, Ordoñez S,
Marín P, Corengia P, Fernandez E (2011) Preparation,
testing and modelling of hydrogen selective Pd/YSZ/
SS composite membrane. Int J Hydrogen Energy
36:15783–15793
Tarditi A, Gerboni C, Cornaglia L (2013) PdAu mem-
brane supported on top of vacuum-assisted ZrO2-
modified porous stainless steel substrates. J Membr
Sci 428:1–10
Uemiya S, Endo T, Yoshiie R, Katoh W, Kojima T (2007)
Fabrication of thin palladium-silver alloy film by using
electroplating technique. Mater Trans 48:1119–1123
Way JD, Lusk M, Thoen P (2008) Sulfur-resistant com-
posite metal membranes. US Patent 2008/0038567
Yun S, Oyama ST (2011) Correlations in palladium mem-
branes for hydrogen separation: a review. J Membr Sci
375:28–45
P
Palladium-Based Membrane Reactor steam reforming reactions, H2 yield and CO2
1 2
Ekain Fernandez and Gallucci Fausto
1
Energy and Environment, TECNALIA,
Donostia-San Sebastian, Gipuzkoa, Spain
2
Chemical Process Intensification, Department of
Chemical Engineering and Chemistry,
Eindhoven University of Technology,
Eindhoven, The Netherlands
In palladium-based membrane reactor a hydrogen
separation process using palladium-based mem-
branes is coupled with catalytic reactions. It has
received a growing interest in recent years
(Gallucci et al. 2011; De Falco et al. 2011;
Gallucci et al. 2013). Membrane reactors are
mainly used to carry out the reactions limited by
the equilibrium conversion such as water gas shift
(WGS) and so on. In fact, in a membrane reactor
the separation capability of a membrane is utilized
to improve the performance of a catalytic system.
General Aspects
There are two main generic approaches in
Pd-based membrane reactors: selective hydrogen
separation (extractor) and selective hydrogen
addition (distributor), as shown in Fig. 1.
The extractor-type membrane reactor facili-
tates the in situ removal of hydrogen in the case
of using palladium membranes. For example, for
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1032-3
product selectivity in traditional reactors are lim-
ited by thermodynamics. By selective removal of
H2 from the reaction side, the thermodynamic
equilibrium restrictions can be overcome follow-
ing the Le Chatelier’s principle. Due to the shift
effect, both high H2 yields and high CO2 selec-
tivities can be achieved. Besides, this effect
allows operation at milder reaction conditions in
terms of temperature and pressure (Zaman and
Chakma 1994). The distributor-type membrane
reactor may use the Pd-based membrane to feed
the hydrogen distributively in order to control the
contact within reactants. For example, this reac-
tor type can be used for Fischer–Tropsch synthe-
sis reaction (Rohde et al. 2005).
In general, with respect to the traditional reac-
tors, membrane reactors are able to:
• Combine chemical reaction and hydrogen sep-
aration in only one system reducing the capital
cost
• Enhance the conversion of equilibrium limited
reactions
• Achieve higher conversions than traditional
reactors operating at the same membrane reac-
tor conditions or the same conditions, but
operating at milder conditions
• Improve yield and selectivity
2 Palladium-Based Membrane Reactor

Palladium-Based
Membrane Reactor,
Fig. 1 Two approaches in
membrane reactors: (a)
extractor and (b) distributor
(Julbe et al. 2001)

Palladium-Based a
Membrane Reactor,
Fig. 2 Packed-bed tubular
membrane reactor
configurations: (a) catalyst FEED RETENTATE
in tube and (b) catalyst in
shell (Gallucci et al. 2013)

Membrane Catalyst Hydrogen

b FEED

Hydrogen

Membrane
Catalyst
RETENTATE

Hydrogen Production by Pd-Based infinite perm-selectivity to H2. The most com-

Membrane Reactors
In the late 60s, Prof. Gryaznov proposed the use of
Pd-based membrane reactor for dehydrogenation
reactions (Gryaznov et al. 1970). Since then, dense
Pd-based membranes and microporous silica
membranes were studied for hydrogen production
by membrane reactors. Pd-based membranes for
H2 production overcome all the other candidate
materials due to the very high permeability and
monly studied reactions using Pd membrane reac-
tor have been: methane steam reforming (Chen
et al. 2008), methane dry reforming (Gallucci
et al. 2008), partial oxidation of methane (Basile
and Paturzo 2001; Cheng et al. 2009), and water
gas shift reaction (Galuszka et al. 2012). Besides,
reforming reactions using other sources were also
studied such as, steam reforming of ethanol and
methanol (Gallucci et al. 2007).
Palladium-Based Membrane Reactor
Membrane Reactor Configurations
Different types of membrane reactors for hydrogen
production have been proposed in the literature.
Most of the previous work has been performed in
packed-bed membrane reactors (PBMR); how-
ever, there is an increasing interest in novel con-
figurations such as fluidized-bed membrane
reactors (FBMR) and micromembrane reactors
(MMR) especially because better heat manage-
ment and decreased mass transfer limitations can
be obtained in these reactor configurations.
The PBMR configuration is the first and most
studied configuration for hydrogen production in
membrane reactors. This is because, the first stud-
ies on membrane reactors focused on the effect of
Palladium-Based
Membrane Reactor,
Fig. 3 Schematic
representation of a
fluidized-bed membrane
reactor for selective
removal of hydrogen is
presented (Adris
et al. 1994)
3
the hydrogen permeation through membranes on
the reaction system. Thus, it was straightforward
to compare two packed-bed reactors (avoiding the
complication of complex fluid dynamics such as in
fluidized bed) in one of which a membrane was
used. In a PBMR, the catalyst is confined in fixed-
bed configuration and in contact with a Pd-based
membrane. The most used PBMR configuration is
the tubular one where the catalyst may be placed
either in the membrane tube or in the shell side as
shown in Fig. 2.
The FBMR configuration consists of a bundle
of hydrogen selective membranes immersed in a
catalytic bed operated in the bubbling or turbu-
lent regime (see Fig. 3). Compared to PBMR
configuration, the use of FBMR reduces the
Exhaust
Hydrogen
Membrane
tubes
Heat
exchangers
Reactants
4 Palladium-Based Membrane Reactor

Palladium-Based
Feed Retentate
Membrane Reactor,
Fig. 4 Schematic Feed
representation of the Channel housing
microchannel reactor
configuration used by
Bredesen for Pd-based Membrane
membrane tests (Mejdell Retentate
et al. 2009) Perforated plate
Copper gasket
Apertures

Permeate housing

Sweep Permeate

bed-to-wall mass transfer limitations but also
allows operating the reactor at a virtually isother-
mal condition (due to the movement of catalyst).
The MMR configuration is interesting due to:
(i) improved mass and heat transfer owing to the
reduction of the scale length in the
microchannels; (ii) removal of mass transfer lim-
itations (concentration polarization); and (iii)
high degree of process intensification by integrat-
ing different process steps in a small-scale
device. (Gallucci et al. 2013). The microchannel
reactor configuration proposed by Bredesen and
coworkers is presented in Fig. 4.
References
Adris AM, Grace JR, Lim CJ, Elnashaie SS (1994) Fluid-
ized bed reaction system for steam/hydrocarbon gas
reforming to produce hydrogen. US Patent 5,326,550
Basile A, Paturzo L (2001) An experimental study of
multilayered composite palladium membrane reactors
for partial oxidation of methane to syngas. Catal Today
67:55–64
Chen Y, Wang Y, Xu H, Xiong G (2008) Efficient pro-
duction of hydrogen from natural gas steam reforming
in palladium membrane reactor. Appl catal B Environ
80:283–294
Cheng YS, Peña MA, Yeung KL (2009) Hydrogen pro-
duction from partial oxidation of methane in a mem-
brane reactor. J Taiwan Inst Chem Eng 40:281–288
De Falco M, Marrelli L, Iaquaniello G (2011) Membrane
reactors for hydrogen production processes. Springer,
London
Gallucci F, Basile A, Tosti S, Iulianelli A, Drioli E (2007)
Methanol and ethanol steam reforming in membrane
reactors: an experimental study. Int J Hydrogen Eng
32:1201–1210
Gallucci F, Tosti S, Basile A (2008) Pd-Ag tubular mem-
brane reactors for methane dry reforming: a reactive
method for CO2 consumption and H2 production.
J Membr Sci 317:96–105
Gallucci F, Basile A, Hai FI (2011) Introduction – a review
of membrane reactors. In: Basile A, Gallucci F (eds)
Membranes for membrane reactors: preparation, opti-
mization and selection. Wiley, West Sussex, pp 1–61
Gallucci F, Fernandez E, Corengia P, Van Sint Annaland
M (2013) Recent advances on membrane and mem-
brane reactors for hydrogen production. Chem Eng Sci
92:40–66
Galuszka J, Giddings T, Iaquaniello G (2012) Membrane
assisted WGSR – experimental study and reactor
modelling. Chem Eng J 213:363–370
Gryaznov VM, Polyakova VP, Savitskii EM, Frades L,
Khrapova EV, Khuares E, Shkola GV (1970) Influence
of the nature and amount of the second component of
binary-palladium alloys on their catalytic activity with
respect to the dehydrogenation of cyclohexane. Bull
Acad Sci USSR Div Chem Sci 19(11):2368–2371
Julbe A, Farrusseng D, Guizard C (2001) Porous ceramic
membranes for catalytic reactors – overview and new
ideas. J Membr Sci 181:3–20
Mejdell AL, Jøndahl M, Peters TA, Bredesen R, Venvik
HJ (2009) Experimental investigation of a
microchannel membrane configuration with a 1.4 mm
Pd/Ag 23 wt% membrane – effects of flow and pres-
sure. J Membr Sci 327(1–2):6–10
Rohde MP, Unruh D, Schaub G (2005) Membrane appli-
cation in fischer-tropsch synthesis reactors – overview
of concepts. Catal Today 106:143–148
Zaman J, Chakma A (1994) Inorganic membrane reactors.
J Membr Sci 1994:1–28
I
Isotherm Palladium Phase Diagram
Ekain Fernandez
Energy and Environment, TECNALIA,
Donostia-San Sebastian, Gipuzkoa, Spain
Isotherm palladium phase diagram represents
the palladium–hydrogen system as a function of
pressure, temperature, and H/Pd concentration as
shown in Fig. 1.
The isotherm palladium diagram is used to
show the nature of one of the biggest problems
of pure palladium membranes: hydrogen embrit-
tlement. As shown in Fig. 1, the absorption of
hydrogen below its critical point of 571 K
(298  C) and 2 MPa produces two different
phases (a and b), both of which retain the pure
palladium face-centered cubic (fcc) lattice but
with the crystal unit cell lattice parameter
increasing from 0.3890 nm for hydrogen-free
palladium to 0.3895 nm for the a-phase and up
to 0.410 nm for the b-phase at room temperature
(Lewis 1967; Ohira et al. 1996). The a-phase is
obtained at low H/Pd atomic ratios and becomes
the dominant phase at high temperature. The
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1033-1
b-phase is formed at high H/Pd atomic ratios
and coexists with the a-phase at low temperature
(Fig. 1). The hydrogen vapor pressure is constant
in the region of phase coexistence and is bounded
by an envelope defining amax and bmin, the com-
positions of maximum and minimum H/Pd ratio
for pure palladium (Yun and Oyama 2011). The
change in volume accompanying the phase trans-
formation can give rise to strain and, conse-
quently, after a few cycles to a metal lattice
distortion (Shu et al. 1991), and micro-failures
inside the metallic bulk are induced.
The alloying of palladium with other metals,
lowering the coexistence temperature of the two
crystalline phases, reduces the internal strength
generated and avoids micro-failure formation
inside the alloy bulk. Silver is the most used
metal for avoiding hydrogen embrittlement phe-
nomenon in Pd–alloy membranes. The critical
temperature for the formation of b-phase of
Pd–Ag alloy with a composition of 77 and
23 (%wt) is around room temperature (Paglieri
and Way 2002).
2 Isotherm Palladium Phase Diagram

Isotherm Palladium
Phase Diagram,
Fig. 1 Pressure–
concentration–temperature
phase diagram of the
palladium–hydrogen
system (Lewis 1967)

References Paglieri SN, Way JD (2002) Innovations in palladium

Lewis FA (1967) Palladium hydrogen system. Academic,
New York
Ohira K, Sakamoto Y, Flanagan TB (1996) Thermody-
namic properties for solution of hydrogen in Pd-Ag-Ni
ternary alloys. J Alloys Compd 236:42–49
membrane research. Sep Purif Rev 31:1–169
Shu J, Grandjean BPA, Van Neste A, Kaliaguine S (1991)
Catalytic palladium-based membrane reactors: a
review. Can J Chem Eng 69:1036–1060
Yun S, Oyama ST (2011) Correlations in palladium mem-
branes for hydrogen separation: a review. J Membr Sci
375:28–45
H
Heteropolyacids
Ubavka B. Mioc
Faculty of physical chemistry, University of
Belgrade, Belgrade, Serbia
The basic structural unit in heteropolyacids
(HPAs) is the Keggin’s cluster (find “Keggin’s
structure”). Groups are distributed in a three-
dimensional lattice and are interconnected by
hydrogen-bonded water molecules or some
other proton species (OH , H2O, H3O+, H5O2+)
forming the secondary structure of Keggin’s
anion. Water molecules fill channels in solid
HPAs, and next interactions, OH . . .H2O,
H2O. . .H2O and H3O+. . .H2O, are identified.
Empirical RO. . .O distances, between 294 and
263 nm, correspond to weak and medium hydro-
gen bonds.
Three best-known acids have been investigated:
H3PMo12O40  29H2O (MoPA), H3PW12O40
 29H2O (WPA), and H4SiW12O40  30H2O
(WSiA). All three acids are isostructural. Among
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1034-3
HPAs 12-tungstophosphoric acid hydrates, charac-
terized by strong acidity, are classified into
“superacids” (Okuhara et al. 2004). From mother
solutions HPAs crystallize with high number of
water molecules, 29–30, forming quasi liquid
state. Acids are very sensitive to ambient condi-
tions: relative humidity and temperature, and lose
very easily water molecules and change to lower
hydrates, Eq. 1 and Fig. 1. On the other hand,
dehydrated acids are very hygroscopic.
Therefore it is interesting and necessary to see
how these compounds change in process of cal-
cination/dehydration and to determine structural
phase transition and temperature regions of their
stabilities, Fig. 2. Investigations have to be
multidisciplinary and different physicochemical
methods have to be used. Thermal analysis
(TGA, DTA), XRPD, IR, and Raman spectros-
copy are recommended for the beginning (Pope
and Mi€uller 1994; Mioč et al. 1990, 1994, 2005).
Thanks to such investigations besides the phase
transition to different crystal hydrates: 29, 21,
14, and 6 hydrates, dehydrated phase,
WPA-0, at about 230  C, was defined as cubic
2 Heteropolyacids
phase. It was postulated that Keggin’s anions of
WPA-0 phase are stabilized by protons – “free
protons.” At higher temperatures, about 400  C
(the broad peak) was defined as Tg anomaly on
20-31°C 31-35°C
WPA-29, cubic WPA-21, orthorhombic
175-230°C 230-580°C
0-WPA, cubic 0-WPA/D-WPA, cubic
It was evident that these water molecules are
formed from protons and few oxygen atoms
from host lattice in endothermic process, which
is simultaneous with water dehydration. Nowa-
days, this water is called protonated (Janik
et al. 2004). Metastable (D-phase–denuded
phase) is stable up to 604  C, for WPA, when
structural phase transformation to phosphate
a is formed after the loss of “constitutional” water
14-29 H2O
a H5O2+ 6 H2O
a H+
0.2 H2O
a 0 H2O
Heteropolyacids, Fig. 1 Schematic survey of different
steps of hydration of HPAs
DTA curves. It corresponds to exothermic trans-
formation which is followed by the mass loss
(TGA) corresponding to about 0.5–0.3 water
molecules.
42-60°C 60-175°C
WPA-14, triclinic WPA-6, cubic
(1)
580-604°C 604-1000°C
D-WPA, cubic PWB
tungsten bronzes (PWB) happen (Mioč
et al. 1994, 2005). All WPA phases were indexed
and corresponding unit cell dimension calcu-
lated. Some of them for the first time: WPA-14
as triclinic. All phases from WPA-6 up to struc-
tural phase transformation are cubic. Phosphate
tungsten bronzes (PWB) have also been obtained
and defined for the first time using HPAs as
precursor (Mioč et al. 1994). Fournier noted
also the same large peak for WPA and identified
it as a new Q phase. He claims that a new Q phase
(Fournier et al. 1992).
These investigations have been followed by
IR and Raman spectroscopic study in situ, in
temperature range from temperature of liquid
nitrogen 195 to 220  C, and with 18O-labeled
compounds. On the basis of the obtained spectra,
few proton species were identified (H5O2+, H3O+,
H2O, and OH groups): terminal OH groups of
Keggin’s anions at about 3,550; OH groups
from water molecules, due to the most frequent
interaction H2O. . .H2O at about 3,490; and OH
bands belonging to H3O+. . .H2O, the strongest
interaction at about 3,292 and 3,225 and
3,140 cm 1; bands in the region 2,250–2,050
were assigned to n3 and/or n4 of H3O+ and water
libration modes. Dioxonium ion was identified
also, thanks to the band n4 at 1,720 and n2 at
about 1,220 cm 1. Special attention in the pro-
cess of calcination/dehydration was paid to the
intensity changes of bands n4(H3O+) at 1,720 and
Heteropolyacids 3

Heteropolyacids, a 100 12
Fig. 2 DTA and TGA
curves of WPA-29 in 10
98

Endo.← DT →Exo.
different temperature 8
regions. Scanning rates 96

(wt %)
6
were 1, 5, and 10  C/min

(mV )
94 4
2
92
0
90 –2
10 20 30 40 50 60 70 80 90 100
t (°C)

b 99.5 4
3

Endo.← DT →Exo.
98.5 2
1
97.5
(wt %)

(mV )
–1
96.5 –2
–3
95.5 –4
–5
94.5 –6

0 100 200 300 400 500 600 700

t (°C)

c 100 25
98 20

Endo.← DT →Exo.
96
15
(wt %)

94

(mV )
10
92
5
90
0
88
86 –5
0 200 400 600 800 1000
t (°C)
DTA and TGA curves of 29-WPA
at temperatures up to 1000 C

n2(H2O) at 1,610 cm 1 (Mioč et al. 1990, 1994,
2005).
Protonic entities and their dynamic equilib-
rium influence the host structure too. Identifica-
tion of proton species and following of its
dynamic equilibrium is also very important for
understanding catalytic (formation of Brønsted
acid centers) and conductive processes (defining
charge carriers, conductivity dependence of
temperature, frequency, and so on) as character-
istics of these compounds.
References
Fournier M, Feumi-Jantou C, Rabia C, Herve G, Launay
S (1992) Polyoxometalates catalyst materials: X-ray
thermal stability study of phosphorus-containing
heteropolyacids H3+xPM12 xVxO40 13-14H2O
(M = Mo,W; x = 0–1). J Mater Chem 2:971–978
4 Heteropolyacids
Janik MJ, Davis RJ, Neurock M (2004) A first principles
analysis of the location and affinity of protons in the
secondary structure of phosphotungstic acid. J Phys
Chem B 108:12292–12300
Mioč U, Colomban P, Novak A (1990) Infrared and
Raman study of some heteropolyacid hydrates. J Mol
Struct 218:123–128
Mioč UB, Dimitrijević RŽ, Davidović M, Nedić ZP,
Mitrović MM, Colomban P (1994) Thermally induced
phase transformations of 12-tungstophosphoric acid
29-hydrate: synthesis and characterization of
PW8O26-type bronzes. J Mater Sci 29:3705–3718
Mioč UB, Todorović MR, Davidović M, Colomban P,
Holclajtner-Antunović I (2005) Heteropoly
compounds-from proton conductors to biomedical
agents. Solid State Ion 176:3005–3017
Okuhara T, Nishimura T, Watanabe H, Misono M (2004)
Insoluble heteropoly compounds as highly active cat-
alysts for liquid-phase reaction. J Mol Catal
74:247–256
Pope MT, M€ uller A (eds) (1994) Polyoxometalate: from
platonic solids to anti-retroviral activity. Kluwer,
Dordrecht
M
Multielectron Redox Catalysts
U. B. Mioč1, Z. D. Mojović2 and
D. M. Jovanović2
1
Faculty of Physical Chemistry, University of
Belgrade, Belgrade, Serbia
2
Institute of Chemistry, Technology and
Metallurgy (I.Ch.T.M.), Center of Catalysis and
Chemical Engineering, University of Belgrade,
Belgrade, Republic of Serbia
Multielectron redox reactions play a key role in
many biological and synthetic catalytic pro-
cesses. Multielectron redox processes require
the use of a catalyst able to store several redox
equivalents. A redox catalyst is a substance
which can accept or donate several electrons
such that each electron is added or removed at
approximately the same potential. When fully
charged, the catalyst should be capable of driving
a multielectron redox reaction in a process with a
few intermediate steps (Fendler and Bolton
1986).
Multielectron redox catalysts function through
redox potential leveling (Huynh and Meyer
2007). Redox potential leveling is a process
where proton-coupled electron transfer leads to
the accumulation of multiple oxidizing equiva-
lents over a low range of potential (Wang
et al. 2010). The additional demand on the cata-
lyst is that it must accumulate and use multiple
oxidative equivalents at high redox potentials and
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1035-1
carry out a difficult, multielectron reaction or
reactions without reacting with itself or its
surroundings.
The ability of heteropoly acids (HPAs) and
their conjugate anions (polyoxometalates) to per-
form fast reversible multielectron redox transfor-
mations under rather mild conditions prompted
interest in the systems as electrocatalysts for var-
ious inert redox reactions including hydrogen
evolution and oxygen reduction. It has been rec-
ognized that the partially reduced heteropo-
lyanions of W and Mo provide highly reactive
mixed-valence redox centers. However, nearly
all multielectron transfer in polyoxometalates
systems is driven by either adding strong reduc-
ing and oxidizing reagents into solution or
through electrochemical redox reactions
(Takashima et al. 2012).
Polyoxometalates can undergo fast and revers-
ible multielectron redox reactions. Electron
transfer occurs between mixed-valence transition
metal sites according to the electron self-
exchange or electron hopping mechanism. This
model is operative during partial
electroreduction, i.e., injection of up to four elec-
trons to a Keggin-type heteropoly structure of
molybdenum and tungsten. Further reduction of
heteropolytungstate or molybdate is irreversible
and leads to the formation of so-called
heteropolybrown species in which such distinct
ionic sites as WVI and WIV or MoVI and MoIV can
coexist (Bard et al. 2008).
2 Multielectron Redox Catalysts

The heteropolyanions undergo several rapid PMo12 O40 3
þ 2e
þ 2Hþ ¼ H2 PMo12 O40 3

one- and two-electron reversible reductions to
produce the so-called “heteropoly blue” and fur- H 2 PMo12 O40 3
þ 2e
þ 2H þ
ther irreversible multielectron reductions with
concomitant decomposition. The electrons are ¼ H 4 PMo12 O40 3
pH ¼ 1
accepted by the addenda ions of the heteropo-
lyanions. If the addenda ions are all identical, H 4 PMo12 O40 3
þ 2e
þ 2Hþ
the electrons are delocalized on the addenda ion ¼ H 6 PMo12 O40 3

oxide framework at room temperature by rapid
electron hopping (intramolecular electron trans-
Dawson-type heteropolyanions undergo several
fer). The reduction increases the negative charge
reversible one-electron reductions in organic
density at the heteropolyanions and thus their
and aqueous solvents if no protonation accom-
basicity. As a consequence, the reduction can be
panies the reductions.
accompanied by protonation depending on the
pKa of the produced oxometalates (Sadakane
P2 W 18 O62 6
þ e
¼ P2 W 18 O62 7

and Steckhan 1998).
Keggin-type heteropolyanions can accept a
limited number of electrons without decomposi- P2 W 18 O62 7
þ e
¼ P2 W 18 O62 8
0 < pH < 3
tion, and in some cases the reduced compounds
have been isolated. P2 W 18 O62 8
þ 2e
þ 2Hþ ¼ H2 P2 W 18 O62 8

PW 12 O40 3
þ e
¼ PW 12 O40 4
H 2 P2 W 18 O62 8
þ 2e
þ 2Hþ ¼ H4 P2 W 18 O62 8

PW 12 O40 4
þ e
¼ PW 12 O40 5
0 < pH < 3 P2 W 18 O62 8
þ e
¼ P2 W 18 O62 9

PW 12 O40 5
þ 2e
þ H þ ¼ HPW 12 O40 6
P2 W 18 O62 9
þ e
¼ P2 W 18 O62 10
0 < pH < 8:2

With increasing pH, the third reversible
two-electron wave moves to a more negative
potential and splits into two reversible
one-electron reduction waves at pH 4:


PW 12 O40 5

þ e ¼ PW 12 O40 6


ous solutions is considerable dependent on pH
PW 12 O40 6

þ e ¼ PW 12 O40 7

For phosphopolyoxomolybdate, it is difficult to
obtain well-defined redox waves in cyclic
voltammetry in aqueous electrolytes due to the
easy hydrolysis of PMo12O403
. However, it is
stabilized by addition of comparatively large
amounts of organic solvents. The reduction
potentials depend on pH as a result of protonation
(Sadakane and Steckhan 1998; Gómez-Romero
and Casañ-Pastor 1996).
P2 W 18 O62 10
þ 2e
þ 2Hþ ¼ H2 P2 W 18 O62 10

P2 W 18 O62 10
þ e
¼ P2 W 18 O62 11

P2 W 18 O62 11
þ e
¼ P2 W 18 O62 12
8:2 < pH
The stability of tungstophosphoric acid in aque-
with regard to the dominant species present in
the solution (Holclajtner-Antunović et al. 2008).
Many factors influence the equilibrium, primarily
pH and HPA concentration, while the perfor-
mance of different analytical techniques used
for speciation should be taken in account as
well. Tungstophosphoric acid decomposes first
to components of the Dawson series, while the
total decomposition of the Keggin anion to phos-
phate and tungstate occurs at pH >7.5.
It should be noted that, besides the ability to
perform multielectron redox transformations,
Multielectron Redox Catalysts
HPAs also have a very strong Brönsted acidity
approaching superacid region. Their acid-base
and redox properties can be varied over a wide
range by changing the chemical composition
(Damjanović et al. 2005). HPAs catalyze a wide
variety of reactions in homogeneous liquid phase.
Being stronger acids, HPAs will have signifi-
cantly higher catalytic activity than mineral
acids. HPA catalysis lacks side reactions such as
sulfonation, chlorination, nitration, etc., which
occur with mineral acids (Kozhevnikov 1998).
References
Bard AJ, Inzelt G, Scholz F (eds) (2008) Electrochemical
dictionary, 2nd edn. Springer, Berlin
Damjanović L, Rakić V, Mioč UB, Auroux A (2005)
Influence of cations on active sites of the alkaline
earth salts of 12-tungstophosphoric acid:microcalori-
metric study. Thermochim Acta 434:81–87
Fendler J, Bolton J (1986) Panel discussion on sensitiza-
tion and immobilization of catalysts on various sup-
ports. Homog Heterog Photocatal NATO ASI Ser
174:699–701
3
Gómez-Romero P, Casañ -Pastor N (1996) Photoredox
chemistry in oxide clusters. Photochromic and redox
properties of polyoxometalates in connection with
analog solid state colloidal systems. J Phys Chem
100:12448–12454
Holclajtner-Antunović I, Bajuk-Bogdanović D,
Todorović MR, Mioč UB, Zakarevska J, Uskokovi-
ć-Marković S (2008) Spectroscopic study of stability
and molecular species of 12-tungstophosphoric acid in
aqueous solution. Can J Chem 86:996–1004
Huynh MHV, Meyer TJ (2007) Proton-coupled electron
transfer. Chem Rev 107:5004–5064
Kozhevnikov IV (1998) Catalysis by heteropoly acids and
multicomponent polyoxometalates in liquid-phase
reactions. Chem Rev 98:171–198
Sadakane M, Steckhan E (1998) Electrochemical proper-
ties of polyoxometalates as electrocatalysts. Chem
Rev 98:219–237
Takashima T, Yamaguchi A, Hashimoto K, Nakamura
R (2012) Multielectron-transfer reactions at single Cu
(II) centers embedded in polyoxotungstates driven by
photo-induced metal-to-metal charge transfer from
anchored Ce(III) to framework W(VI). Chem
Commun 48:2964–2966
Wang T, Brudvig GW, Batista VS (2010) Study of proton
coupled electron transfer in a biomimetic dimanganese
water oxidation catalyst with terminal water ligands.
J Chem Theory Comput 6:2395–2401
O
Organic Dehydration
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Water/organic-selective membranes are effective
for the dehydration of water/organic mixtures.
The dehydrated organic solvents can be useful
as industrial reaction solvents, washing solvents,
and analytical solvents.
In Fig. 1, the permeation and separation char-
acteristics for an aqueous dimethyl sulfoxide
(DMSO) solution through a dense chitosan
(Chito) membrane by TDEV (see
“▶ Temperature-Difference Controlled
Evapomeation”) are shown. In this figure, the
feed was an aqueous solution of 50 wt.%
dimethyl sulfoxide, the temperature of the feed
solution was kept constant at 40  C, and the
temperature of the membrane surroundings was
lowered to less than the temperature of the feed
solution (Uragami and Shinomiya 1992). Both
the total permeation rate and the separation factor
increased with dropping temperature of the mem-
brane surroundings. This increase in the total
permeation rate may be due to the increase in
the solubility of the vapor in the membrane with
decreasing temperature of the membrane sur-
roundings, according to Henry’s law. The
increase of the separation factor, i.e., the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1036-1
improvement of the H2O/DMSO selectivity, can
be explained by the illustration shown in Fig. 2.
When the dimethyl sulfoxide and water mole-
cules which had vaporized from the feed mixture
come close to the membrane surroundings, the
dimethyl sulfoxide vapor aggregates much easier
than the water vapor (because the freezing points
of dimethyl sulfoxide and water are 18.4  C and
0  C, respectively) and tends to liquefy as the
temperature of the surrounding membrane
becomes lower. This aggregation of the dimethyl
sulfoxide molecules is responsible for the
increase in the H2O/DMSO selectivity for water
through the Chito membrane. The increase in the
separation factor with the TDEV method, in
which the temperature of the membrane sur-
roundings is lower than the temperature of the
feed solution, can be attributed to the degree of
aggregation of the DMSO molecule, which is
significantly governed by the temperature of the
membrane surroundings. The high H2O/DMSO
selectivity of Chito membrane for an aqueous
solution dimethyl sulfoxide in TDEV is signifi-
cantly enhanced by both the high affinity for
water of the Chito membrane and the decrease
in the solubility selectivity for dimethyl sulfoxide
molecules into the Chito membrane, based on
their aggregation on the membrane surroundings
(Uragami and Shinomiya 1992; Uragami 2008).
The mechanism of permeation and separation of
a dimethyl sulfoxide/water mixture through a
dense Chito membrane during TDEV in Fig. 2
is effective for understanding that of an ethanol/
2 Organic Dehydration

Organic Dehydration, 0.2 500

Fig. 1 Effects of the
temperature of the

Separtion factor ; aH2O/DMSO

Permation rate (kg/m2hr)
membrane surroundings on 400
the characteristics of
permeation and separation
300
for an aqueous solution of
50 wt.% dimethyl sulfoxide 0.1
(DMSO) through the Chito 200
membrane in TDEV. Feed
temperature: 40  C
100

0 0
0 10 20 30 40
Temperature of membrane surroundings (˚C)

To vacuum permeation rate and separation factor for H2O/

Membrane
Lower
temperature
Aqueous solution CH3COOH Higher
temperature
o: H2O :CH3COOH
or (CH3)2SO
Organic Dehydration, Fig. 2 Tentative separation
mechanism for aqueous dimethyl sulfoxide solution
through a Chito membrane in TDEV
water mixture through a dense PDMS membrane
during TDEV (Uragami 2008).
The characteristics of permeation and separa-
tion of acetic acid/water mixtures through 85/15
(v/v) PVA/malic acid (MA) membranes were
investigated by EV (see “▶ Evapomeation”) and
TDEV. The permeation rates increased, but sep-
aration factors for H2O/CH3COOH selectivity
decreased with increasing permeation tempera-
ture during EV. When the temperature of feed
liquid was kept constant and the temperature of
the membrane surrounding was dropped, the
CH3COOH selectivity were significantly
influenced by the temperature of membrane sur-
roundings. The increase in the acetic acid con-
centration in the feed vapor mixture decreased
the permeation rate and increased the separation
factor for H2O/CH3COOH selectivity except
40 wt.% acetic acid content. The best separation
factors were 800 in the EV and 860 in the TDEV
for 90 wt.% acetic acid. The separation index of
TDEV was higher than that of EV for an
azeotropic mixture of acetic acid/water. TDEV
in the separation of acetic acid/water mixtures
through the PVA/MA membranes was more
effective than EV (Isiklan and Sanli 2005).
Graft-copolymer membranes grafted 4-vinyl
pyridine, acrylonitrile, and hydroxylmethyl
methacrylate onto poly(vinyl alcohol) and also
were applied to the dehydration of acetic acid in
EV and TDEV, and those membranes showed
high dehydration performance (Asman and
Sanli 2006; Al-Ghezawi and Sanli 2006).
Water/alcohol-selective membranes are effec-
tive for the following scenario. For example,
when an aqueous solution of dilute ethanol
(about 10 wt.%) produced by the
bio-fermentation is concentrated by distillation,
since an aqueous solution of 96.5 wt.% ethanol is
an azeotropic mixture, ethanol cannot be concen-
trated anymore by distillation, and consequently,
ethanol is concentrated by azeotropic distillation
with the addition of benzene. If membranes that
can preferentially permeate only water at 3.5 wt.
 Organic Dehydration
12000
Separation factor, aH2O/EtOH
10000
8000
6000
4000
2000
0 0
0.0 0.5 1.0 1.5
Molar ratio
(−COO−Na+/−N(CH3)3 +CI−)
Organic Dehydration, Fig. 3 Permeation and separa-
tion characteristics for an azeotropic mixture of ethanol/
water through q-Chito/PEO acid 4000 polyion complex/
PES composite membranes during EV as a function of the
molar ratio between the carboxylate groups in PEO acid
4000 and the ammonium groups in q-Chito at 40  C
% in an azeotropic mixture of aqueous ethanol
solution can be developed, significant energy
savings would be achieved. The permeation and
separation mechanisms in PV, EV, and TDEV
through dense membranes consist of the dissolu-
tion of the permeants into the membrane, the
diffusion of the permeants in the membrane, and
the evaporation of the permeants from the mem-
brane. Therefore, the separation of permeants in
the membrane separation techniques depends on
the differences in the solubility and diffusivity of
the permeants in the feed mixture. When the
structure of water/alcohol- and water/organic
liquid-selective membranes is domically
designed, hydrophilic materials can be
recommended as membrane materials. There-
fore, an increase in the solubility of water mole-
cules into the membrane during the solution
process can be expected. In order to raise the
affinity of membranes for water molecules, mem-
branes with dissociation groups introduced into
their structure are used for dehydration from
organic solvents.
The dehydration of an ethanol/water azeo-
trope during EV using polyion complex cross-
linked chitosan composite (q-Chito-PEO acid
PIC/PES composite) membranes, constructed
3
10 from quaternized chitosan (q-Chito) and polyeth-
ylene oxydiglycilic acid (PEO acid) on a porous
Permeation rate (10−2 kg/m2 hr)
polyethersulfone (PES) support, was investigated
8
(Uragami and Yamada 1999, 2003). Both the
6
q-Chito/PES composite and the q-Chito-PEO
acid polyion complex/PES composite mem-
branes showed high H2O/EtOH selectivity for
4
an ethanol/water azeotrope. Both the permeation
rate and the H2O/EtOH selectivity were enhanced
2
by increasing the degree of quaternization of the
chitosan molecule, because the affinity of the
q-Chito/PES composite membranes for water
2.0
was increased by introducing a quaternized
ammonium group into the chitosan molecule.
Q-Chito-PEO acid PIC/PES composite mem-
branes prepared from an equimolar ratio of car-
boxylate groups in the PEO acid versus
quaternized ammonium groups in the q-Chito
showed the best separation factor for H2O/EtOH
selectivity without lowering the permeation rate,
as shown in Fig. 3. With an increasing molecular
weight of PEO acid, the separation factor for
H2O/EtOH selectivity increased, but the perme-
ation rate almost did not change. The separation
factor for aqueous solutions of 1- and 2-propanol
was also maximized at an equimolar ratio of
carboxylate groups and ammonium groups and
was greater than for an ethanol/water azeotrope.
References
Al-Ghezawi N, Sanli O (2006) Permeation and separation
characteristics of acetic acid-water mixtures by
pervaporation through acrylonitrile and hydroxy
ethyl methacrylate grafted poly(vinyl alcohol) mem-
brane. Sep Sci Technol 41:2913
Asman G, Sanli O (2006) Separation characteristics of
acetic acid-water mixtures using poly(vinyl alcohol-
g-4-vinyl pyridine) membranes by pervaporation and
temperature difference evapomeation techniques.
J Appl Polym Sci 100:1385, 199
Isiklan N, Sanli O (2005) Permeation and separation char-
acteristics of acetic acid-water mixtures through poly
(vinyl alcohol)/malic acid membranes by
evapomeation and temperature difference controlled
evapomeation. Sep Sci Technol 40:1083
Uragami T (2008) Structural design of polymer mem-
branes for concentration of bio-ethanol. Polym
J 40:485
Uragami T, Shinomiya H (1992) Concentration of aque-
ous dimethyl sulfoxide solutions through a chitosan
4 Organic Dehydration

membrane by permeation with a temperature differ-
ence. J Membr Sci 74:183
Uragami T, Yamada H (1999) Removal of volatile organic
compounds from dilute aqueous solutions by
pervaporation. Netw Polym 20:203
Uragami T, Yamada H (2003) Dehydration from alcohols
by polyion complex cross-linked chitosan composite
membranes during evapomeation. Biomacro-
molecules 4:137
P

Pervaporation for Chloroform DMS content of more than about 40 and 70 mol%,
Separation respectively. It is noticeable that the benzene and
chloroform permselectivity and the normalized
Tadashi Uragami permeation rates for the graft copolymer mem-
Organization for Research and Development of branes changed remarkably at the same DMS
Innovative Science and Technology (ORDIST), content. These results suggest that the PMMA-
Kansai University, Suita, Osaka, Japan g-PDMS and PEMA-g-PDMS membrane struc-
ture changed at the corresponding DMS content.
On the other hand, the PBMA-g-PDMS mem-
Chloroform/water-selective membranes are brane showed a gradual increase in chloroform
effective for the removal of chloroform in permselectivity and normalized permeation rate
water. These membranes can be contributed to with increasing DMS content. From the above
the environmental problem. results, it was found that the structural change in
Removal of chloroform in an aqueous chloro- the PBMA-g-PDMS membrane with variations in
form solution through the poly DMS content was quite different from that of the
(methylmethacrylate)-poly(dimethylsiloxane) PMMA-g-PDMS and PEMA-g-PDMS mem-
(PMMA-g-PDMS), poly(ethylmethacrylate)- branes (Uragami et al. 2001).
PDMS (PEMA-g-PDMS), and poly(n- The permeation and separation characteristics
butylmethacrylate)-PDMS (PBMA-g-PDMS) of chloroform from water by PV through cross-
graft copolymer membranes was investigated by linked PDMS membranes prepared from
pervaporation (PV). PDMSDMMA and divinyl compounds, such as
Figure 1 shows the results of PV for an aque- EGDM, DVB, DVS, and DVF, were studied
ous solution of 0.02 wt.% chloroform through the (Ohshima et al. 2005). Those membranes showed
graft copolymer membranes. The chloroform high chloroform selectivity and permeability.
permselectivity of PMMA-g-PDMS and PEMA- Both chloroform/water selectivity and perme-
g-PDMS membranes increased dramatically at a ability were affected significantly by the divinyl

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1037-1
2 Pervaporation for Chloroform Separation

4 compound. Furthermore cross-linked

PDMSDMMA membranes showed the highest
chloroform/water selectivity. The chloroform/
Normalized permeation rate

3 water selectivity was mainly governed by the

solubility rather than the diffusion selectivity.
(10−6kg m/m2 hr)

With increasing downstream pressure, the chlo-

2 roform/water selectivity of all cross-linked
PDMSDMMA membranes increased, but the
permeability decreased. A PDMSDMMA-DVF
1
membrane exhibited a normalized permeation
rate of 1.9  10 5 kgm (m2h) 1 It and a separa-
tion factor for chloroform/water of 4,850, yield-
ing a separation index of 9,110.
0
100
PV experiments were carried out using poly
(vinylidene fluoride) (PVF2) flat-sheet mem-
branes with different thickness for chloroform/
Chloroform in permeate (wt%)

80 water mixtures (Khayet and Matsuura 2004). In

Table 1 the permeation rates for chloroform and
60
water and the separation factor, aCH3Cl/H2O, are
listed. With increasing membrane thickness, the
separation factor for the chloroform/water
40 increased, and the permeation rates for water
and chloroform decreased. In fact, the selectivity
20
of the PVF2 membranes is associated not only
with the surface characteristics but also with the
diffusion through the membrane bulk structure.
0
0 20 40 60 80 100
DMS content (mol%)

Pervaporation for Chloroform Separation,

Fig. 1 Effect of the DMS content on the chloroform
concentration in the permeate and normalized permeation
rate for an aqueous solution of 0.02 wt.% chloroform
through the PMMA-g-PDMS (○), PEMA-g-PDMS (●),
and PBMA-g-PDMS (□) membranes by pervaporation

Pervaporation for Chloroform Separation, Table 1 Permeation separation characteristics for chloroform/water
mixture during PV (Khayet and Matsuura 2004)
Membrane Permeation rate for water Permeation rate for chloroform Separation factor
thickness (mm) (10 4kgm 2s 1) (10 5kgm 2s 1) aCH3Cl/H2O
38.81 1.69 2.47 146.02
49.77 1.28 1.81 141.69
59.70 1.17 1.91 163.15
83.15 0.87 1.40 160.47
110.77 0.66 1.14 173.32
Initial chloroform concentration 1 kg/m3, feed temperature 25  C, reduced pressure 1,666.5 Pa
Pervaporation for Chloroform Separation
References
Khayet M, Matsuura T (2004) Pervaporation and vacuum
membrane distillation processes: modeling and exper-
iments. AIChE J 50:1697
Ohshima T, Kogami Y, Miyata T, Uragami T (2005)
Pervaporation characteristics of cross-linked poly
(dimethylsiloxane) membranes for removal of various
3
volatile organic compounds from water. J Membr Sci
260:156
Uragami T, Yamada H, Miyata T (2001) Removal of
dilute volatile organic compounds in water through
graft copolymer membranes consisting of poly
(alkylmethacrylate) and poly(dimethylsiloxane) by
pervaporation and their membrane morphology.
J Membr Sci 187:255
R
Removal of Dissolved VOCs from
Aqueous Solutions (Pervaporation
Application)
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Organic liquid/water selective membranes are
effective for the removal of organics in water
and recovery of organic solvents from water.
These membranes can contribute to the environ-
mental problem and effective use of organic
solvents.
The removal of volatile organic compounds
(VOCs) such as benzene and chloroform from
aqueous benzene and chloroform solutions
using poly(methyl methacrylate)-poly
(dimethylsiloxane) (PMMA-g-PDMS), poly
(ethyl methacrylate)-PDMS (PEMA-g-PDMS),
and poly(n-butyl methacrylate)-PDMS (PBMA-
g-PDMS) graft copolymer membranes was inves-
tigated by pervaporation (PV). When aqueous
solutions of dilute VOCs were permeated through
the PMMA-g-PDMS and PEMA-g-PDMS mem-
branes, these membranes were Bz/H2O- and
CHCl3/H2O selective. The permeation and sep-
aration characteristics of the PMMA-g-PDMS
and PEMA-g-PDMS membranes changed drasti-
cally at a DMS content of about 40 mol% and
70 mol%, respectively, as shown in Fig. 1.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1038-3
The permeation rate and VOC/water selectivity
of the PBMA-g-PDMS membranes, however,
increased gradually with increasing DMS con-
tent, unlike those of PMMA-g-PDMS and
PEMA-g-PDMS membranes. Furthermore,
TEM observations revealed that the PMMA-
g-PDMS and PEMA-g-PDMS membranes had
microphase-separated structures, consisting of a
PDMS phase and a poly(alkyl methacrylate)
phase. On the other hand, the PBMA-g-PDMS
membrane was homogeneous. It was found that
the permeability and selectivity of these graft
copolymer membranes for treatment of aqueous
VOC solutions by PV were significantly related
to a PDMS continuous layer in the phase-
separated structure (Uragami et al. 1999, 2001a).
Hydrophobically surface-modified mem-
branes were prepared by adding a fluorine-
containing graft copolymer to a microphase-
separated membrane consisting of PDMS and
PMMA to improve organic component selectiv-
ity. Contact angle measurements and X-ray pho-
toelectron spectroscopy (XPS) revealed that the
addition of a fluorine-containing copolymer pro-
duced a hydrophobic surface at the air side of the
membrane due to surface localization of the fluo-
rinated copolymer. It was apparent from TEM
that adding a fluorine-containing copolymer of
less than small amount did not affect the mor-
phology of the microphase-separated membrane.
However, adding a fluorine-containing copoly-
mer over a certain amount resulted in a morpho-
logical change, from a continuous PDMS phase
2 Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application)
4 100
Normalized pemeation rate
3
(10 −6kg m/m2 h)
2
1
0 0
0 20 40 60
DMS content (mol%)
Removal of Dissolved VOCs from Aqueous Solutions
(Pervaporation Application), Fig. 1 Effects of the
DMS content on the benzene concentration in the perme-
ate and normalized permeate for an aqueous solution of
to a discontinuous PDMS phase. The addition of
a small amount of fluorine-containing copolymer
to the microphase-separated membranes
enhanced both their permeability and Bz/Chx
selectivity for a dilute aqueous solution of ben-
zene during PV because of their hydrophobic
surfaces and microphase-separated structures.
Specifically, the microphase-separated mem-
brane with a small amount of fluorine-containing
copolymer concentrated an aqueous solution
from 0.05 to 70 wt.% benzene and, therefore,
removed the benzene from water very effectively
(Miyata et al. 2001).
PMMA-g-PDMS and PMMA-b-PDMS mem-
branes containing tert-butylcalix[4]arene
(CA) (CA/PMMA-g-PDMS and CA/PMMA-
b-PDMS) were applied to the removal of benzene
from a dilute aqueous solution of benzene by PV
(Uragami et al. 2006). When an aqueous solution
of 0.05 wt.% benzene was permeated through
CA/PMMA-g-PDMS and CA/PMMA-b-PDMS
membranes, these membranes showed high
Bz/Chx selectivity. Both the permeability and
Bz/H2O selectivity of the CA/PMMA-g-PDMS
and CA/PMMA-b-PDMS membranes were
enhanced by increasing the CA content, due to
the affinity of CA for benzene. The permeability
80
Renzene in permeate (wt%)
60
40
20
80 100 0 20 40 60 80 100
DMS content (mol%)
0.05 wt.% benzene through PMMA-g-PDMS (○), PEMA-
g-PDMS (●), and PBMA-g-PDMS (□) membranes
during PV
and Bz/H2O selectivity of CA/PMMA-b-PDMS
membranes were much greater than those of
CA/PMMA-g-PDMS membranes. TEM observa-
tions revealed that both the CA/PMMA-g-PDMS
and CA/PMMA-b-PDMS membranes had
microphase-separated structures consisting of a
PMMA phase and a PDMS phase-containing
CA. The microphase-separated structure of the
latter membranes was much clearer than that of
the former and was lamellar. The distribution of
CA in the microphase-separated structure of the
CA/PMMA-g-PDMS and CA/PMMA-b-PDMS
membranes was analyzed by differential scan-
ning calorimetry (DSC), and CA was distributed
in a PDMS continuous layer in microphase-
separated structure (Uragami et al. 2001b, 2006).
It was found that a continuous PDMS layer in
PMMA-g-PDMS and PMMA-b-PDMS mem-
branes plays an important role for the removal
of VOCs from water. For the purpose of
constructing the membrane matrix from PDMS
component mainly, polydimethylsiloxane
dimethylmethacrylate macromonomer
(PDMSDMMA) was selected as a membrane
material. The effects of cross-linkers of the
cross-linked PDMS membranes derived from
PDMSDMMA and divinyl compounds were
Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application) 3

Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application), Table 1 Performance for
Bz/H2O of various membranes containing PDMS component
asep. asorp. adiff.
Bz/ Bz/ Bz/
Various PDMS membranesa H2O H2O H2O NPRb PSIc Refs
PMMA 53 422 0.13 0.29 16 Uragami et al. (2001a)
PMMA-g-PDMSd 620 739 0.86 0.13 226 Uragami et al. (2006)
CA/PMMA-g-PDMSe 1,772 1,267 1.40 0.71 1,240 Uragami et al. (2006)
PFA-g-PDMS/PMMA- 4,492 0.64 2,879 Miyata et al. (2001)
g-PDMSf
PDMSDMMA-DVBg 3,171 1,436 2.21 1.46 4,629 Uragami and Ohshima
(2003)
PDMSDMMA-DVSh 2,886 1,270 2.46 1.96 5,656 Uragami and Ohshima
(2003)
PDMSDMMA-DVFi 4,316 1,804 2.49 1.72 7,423 Ohshima et al. (2005)
CA/PDMSDMMA-DVBj 4,021 1,689 2.18 1.75 7,037 Ohshima et al. (2005)
CA/PDMSDMMA-DVSk 3,866 1,620 2.39 1.97 7,616 Ohshima et al. (2005)
CA/PDMSDMMA-DVFl 5,027 1,998 2.52 1.86 9,350 Ohshima et al. (2005)
a
PV experimental conditions: feed solution, an aqueous solution of 0.05 wt.% benzene; permeation temperature, 40  C;
pressure of permeation side, 1.33 Pa
b
Normalized permeation rate [10 5 mkg(m2h) 1]
c
PV separation index (NPR  asep. Bz/H2O)
d
PDMS content 74 mol%
e
PDMS content 74 mol%; CA content 40 mol%
f
PDMS content 74 mol%; PFA-g-PDMS content 1.2 wt.%
g
DVB content 80 mol%
h
DVS content 90 mol%
i
DVF content 90 mol%
j
DVB content 80 mol%; CA content 0.5 wt.%
k
DVS content 90 mol%; CA content 0.5 wt.%
l
DVF content; CA content

investigated, on the PV characteristics of the membrane performance during PV, of a

removal of benzene from an aqueous solution of
dilute benzene. When an aqueous solution of
0.05 wt.% benzene was permeated through the
cross-linked PDMSDMMA membranes, they
showed high Bz/H2O selectivity. Both the per-
meability and Bz/H2O selectivity of the mem-
branes were enhanced with increasing divinyl
compound content as the cross-linker and were
significantly influenced by the kind of divinyl
compound. PDMSDMMA membranes cross-
linked with divinyl siloxane (DVS) showed very
high membrane performance during PV. The best
normalized permeation rate, separation factor for
Bz/H2O selectivity, and PV separation index
(PSI) (Huang and Rhim 1991) which is the prod-
uct of the permeation rate and the separation
factor and can be used as a measure of the
PDMSDMMA-DVS membrane, were 1.96 
10 5 mkg (m2h)-1, 98, and 192, respectively
(Uragami et al. 2003). When divinyl perfluoro-
n-hexane (DVF), which is much more hydropho-
bic, was employed as a cross-linker of
PDMSDMMA, the best normalized permeation
rate, separation factor for Bz/H2O selectivity,
and PSI of a PDMSDMMA-DVF membrane
were 1.72  10 5 mkg(m2h) 1, 4,316, and
7,423, respectively (Ohshima et al. 2005a).
In Table 1, the permeation and separation
characteristics of various polymer membranes
consisting of the PDMS components are com-
pared under the same PV condition: feed solu-
tion, an aqueous solution of 0.05 wt.% benzene;
permeation temperature, 40 C; and pressure of
permeation side, 1.33 Pa. As can be seen in
4 Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application)
Table 1, both the normalized permeation rate and
the Bz/H2O selectivity of each of the CA/
PDMSDMMA-DVB, CA/PDMSDMMA-DVS,
and CA/PDMSDMMA-DVF membranes were
improved as compared to each of the
PDMSDMMA-DVB, PDMSDMMA-DVS, and
PDMSDMMA-DVF membranes. Although the
separation factors of the CA/PDMSDMMA-
DVB and CA/PDMSDMMA-DVS membranes
were lower than that of the PFA-g-PDMS/
PMMA-g-PDMS membranes, the PSI of the for-
mer membranes was much greater than that of the
latter one. In Table 1, it was found that the addi-
tion of CA into the cross-linked PDMSDMMA
membranes cross-linked with a suitable cross-
linker is significantly effective to obtain higher
permeation and separation characteristics. A CA/
PDMSDMMA-DVF membrane with DVF of
90 mol% and CA of 0.4 wt.% showed the best
membrane performance, i.e., the normalized per-
meation rate, separation factor for Bz/H2O selec-
tivity, and PSI were 1.86  10 5mkg(m2h) 1,
5,027, and 9,350, respectively.
The air stripping removal of VOCs such as
toluene and phenol from water by microporous
polypropylene (PP) hollow fibers was studied.
The VOC stream passed through the lumen
side of the module, while air (stripping gas) flowed
across the shell side. Experiments were performed
at different liquid flow rates (8–16 cm3min 1), gas
flow rates (60–180 cm3min 1), feed VOC concen-
trations (100–1,000 ppm), and temperatures
(24–35  C). The removal was more effective
when feed VOC level and liquid or gas flow rate
increased. The applicability of a mass transfer
model that considers diffusion in the liquid layer,
membrane, and gas layer under steady state was
checked. Unlike phenol with a very small dimen-
sionless Henry’s law constant (equilibrium gas
concentration divided by liquid concentration)
and a relatively low amount of sorption on PP
fibers, the measured overall mass transfer coeffi-
cients for toluene reasonably agreed with those
predicted from the model. The large deviation
observed for phenol indicated unsteady state
nature, likely due to its small concentration
difference between air and liquid phase/fiber
matrix (Juang et al. 2005).
References
Huang RYM, Rhim JW (1991) Separation characteristics
of pervaporation membrane separation processes. In:
Huang RYM (ed) Pervaporation membrane separation
processes, Membrane science technology series 1.
Elsevier, Amsterdam, pp 111–180, Chapter 3
Juang RS, Lin SH, Yang MC (2005) Mass transfer analy-
sis on air stripping of VOCs from water in microporous
hollow fibers. J Memb Sci 255:79
Miyata T, Yamada H, Uragami T (2001) Surface modifi-
cation of microphase-separated membranes by
fluorine-containing polymer additive and removal of
dilute benzene in water through these membranes.
Macromolecules 34:8026
Ohshima T, Miyata T, Uragami T (2005a) Cross-linked
smart polydimethylsiloxane membranes for removal
of volatile organic compounds from water. J Mol
Struct 739:47
Ohshima T, Miyata T, Uragami T (2005b) Selective
removal of dilute benzene from water by various
cross-linked poly(dimethylsiloxane) membranes
containing tertbutylcalix [4] arene. Macromol Chem
Phys 206:2521
Uragami T, Ohshima T (2003) Removal of benzene from
an aqueous solution of dilute benzene by various cross-
linked poly(dimethylsiloxane) membranes during
pervaporation. Macromolecules 36:9430
Uragami T, Yamada H, Miyata T (1999) Removal of
volatile organic compounds from dilute aqueous solu-
tions by pervaporation. Trans Mater Res Soc Jpn
24:165
Uragami T, Yamada H, Miyata T (2001a) Removal of
dilute volatile organic compounds (VOCs) in water
through graft copolymer membranes consisting of
poly(alkylmethacrylate) and poly(dimethylsiloxane)
by pervaporation and their membrane morphology.
J Memb Sci 187:255
Uragami T, Meotoiwa T, Miyata T (2001b) Effects of the
addition of calixarene to microphase-separated mem-
branes for the removal of volatile organic compounds
from dilute aqueous solutions. Macromolecules
34:6806
Uragami T, Meotoiwa T, Miyata T (2003) Effects of
morphology of multicomponent polymer membranes
containing calixarene on permselective removal of
benzene from a dilute aqueous solution of benzene.
Macromolecules 36:2041
Uragami T, Yamada H, Miyata T (2006) Effects of
fluorine-containing graft- and block-copolymer addi-
tives on removal characteristics of dilute benzene in
water by microphase-separated membranes modified
with these additives. Macromolecules 39:1890
D
Dissolved Oxygen (DO) in Water by
Membrane Operations, Removal of
V. V. Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Dissolved oxygen (DO) is one of the principal
components which should be removed for the
production of ultrapure water. Even though con-
centration of DO in water is very low
(approximately 8 ppm under ambient condi-
tions), DO leads to oxidation of dissolved com-
ponents and materials, for example, boiler piping
in (nuclear) power plants. In such systems, the
desired DO concentration in the boiler feed water
is 7–10 ppb. Therefore, DO removal from water
presents a challenging problem for various indus-
tries such as production of semiconductors,
power plants, pharmaceuticals, and biotechnol-
ogy. In the production of semiconductors, stan-
dard DO level in ultrapure water is the most
stringent (below 1 ppb). Removal of DO from
water by membrane technology can be accom-
plished by using gas-liquid membrane contactors
and membrane reactors.
Gas-liquid membrane contactors generally
incorporate a porous hollow fiber membrane for
direct contacting of two immiscible phases,
namely, a gas and a liquid, for the purpose of
absorption or stripping without dispersion of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1039-4
one phase into another. The DO removal from
water on a membrane contactor requires genera-
tion of a driving force for oxygen transmembrane
transfer, and this process demands reduction in
oxygen concentration in a gas phase. This goal
can be accomplished in one of three ways: (1) by
applying vacuum to the water, (2) by supplying
an appropriate sweep gas to the gas side, and
(3) by a combination of the first two where a
small flow of sweep gas is used to improve sep-
aration driving force but the gas side is still
maintained under vacuum (Sengupta
et al. 1998). In industrial (commercial) Liqui-
Cel ® gas-liquid membrane contactors, polypro-
pylene porous hollow fiber membranes are used.
These membrane contactors offer a serious alter-
native to the traditional two-stage vacuum
degassing towers in the high-purity water treat-
ment systems in the semiconductor industry.
DO removal from water can be performed on a
membrane-UV reactor because DO can react
with hydrogen to yield water under the action of
UV irradiation with a wavelength of 185 nm. This
reaction requires dissolution of hydrogen in
water, and this process is provided by gas-liquid
membrane contactors based on hollow fiber
membranes which are permeable for hydrogen
and UV irradiation (Li and Tan 2001).
Most efficient existing methods for deep
removal of DO from water are based on the
principle of oxygen reduction by hydrogen on a
palladium catalyst which yields water. The
existing catalytic processes for water
2 Dissolved Oxygen (DO) in Water by Membrane Operations, Removal of
deoxygenation via hydrogenation reaction
involve two stages: (1) absorption of hydrogen
in water and (2) passage through a fixed-bed
catalytic reactor. In contrast to existing processes,
the DO removal on a catalytic membrane reactor
can be accomplished in one stage. There are two
configurations of catalytic membrane reactors.
The first design of the membrane reactor is
based on a polypropylene porous hollow fiber
membrane module packed with a palladium cat-
alyst, namely, spherical beds of palladium-
deposited granules of anion-exchange resin in
the void space of the shell side (Li et al. 1995).
An alternative design of a catalytic membrane
reactor provides water deoxygenation by cata-
lytic membranes, namely, by palladium-loaded
hollow fibers (Volkov et al. 2009). Water and
hydrogen are supplied into a shell side of the
reactor and into a fiber lumen, respectively.
Hence, DO removal is accomplished by chemical
reaction between dissolved oxygen and dissolved
hydrogen in the presence of the palladium-based
catalyst. Using a catalytic membrane reactor,
concentration of DO in water of ten parts per
billion (ppb) and lower is feasible.
References
Li K, Tan X (2001) Development of membrane-UV reac-
tor for dissolved oxygen removal from water. Chem
Eng Sci 56(17):5073–5083
Li K, Chua I, Ng WJ, Teo WK (1995) Removal of
dissolved oxygen in ultrapure water production using
a membrane reactor. Chem Eng Sci 50(22):3547–3556
Sengupta A, Peterson PA, Miller BD, Schneider J, Fulk
CW (1998) Large-scale application of membrane
contactors for gas transfer from or to ultrapure water.
Sep Purif Technol 14:189–200
Volkov VV, Petrova IV, Lebedeva VI, Plyasova LM,
Rudina NA, van Erkel J, van der Vaart R,
Tereshchenko GF (2009) Catalytic nanoclusters of
palladium on the surface of polypropylene hollow
fiber membranes: removal of dissolved oxygen from
water. In: Starov VM (ed) Nanoscience: colloidal and
interfacial aspects. Taylor & Francis Group, New
York, pp 1173–1188
H
H2 Permeation Through Pd-Based
Membranes
V. V. Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Palladium is known to be one of the most effec-
tive metals for hydrogen adsorption, dissociation,
and recombination even though the permeability
of this metal is by an order of magnitude lower
than that of refractory metals such as tantalum,
vanadium, and niobium.
In 1863, Sainte-Claire Deville and Troost dis-
covered that hydrogen is able to permeate
through palladium; later, in 1866, Graham
found that palladium can absorb huge amounts
of hydrogen (several times with respect to its
initial volume) at room temperature. The
palladium-based membrane technology for
hydrogen production has come into life in the
late 1950s. In the 1960s, pioneering studies by
Gryaznov led to the development of a break-
through membrane reactor when palladium-
based membranes were used for hydrogen supply
or withdrawal from the reaction zone, thus pro-
viding improved yield and high catalyst effec-
tiveness (Pagliery and Way 2002).
Hydrogen permeation through solid palladium
proceeds via the solution–diffusion mechanism,
and this mechanism involves the following steps:
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1040-2
(a) diffusion of molecular hydrogen to the surface
of the palladium-based membrane, (b) a revers-
ible dissociative adsorption on the palladium sur-
face, (c) dissolution of atomic hydrogen in the
bulk metal, (d) diffusion of atomic hydrogen
through the bulk metal, (e) association of hydro-
gen atom on the palladium surface, (f) desorption
of molecular hydrogen from the surface, and
(g) diffusion of molecular hydrogen away from
the surface (Yun and Oyama 2011). On the pal-
ladium surfaces, the dissociative adsorption of
hydrogen molecules proceeds with a low or zero
activation energy barrier. This is the first step in
bulk absorption toward the formation of metal
hydrides.
Generally, hydrogen permeation is described
by the following equation:
J ¼ Pðpn h  pn l Þ=L;
where J is the hydrogen flux, P is the permeability
coefficient, L is the thickness of the palladium
layer, ph and pl are the partial pressures of hydro-
gen on the high-pressure (feed) side and the
low-pressure (permeate) side, respectively, and
n is the pressure exponent. This exponent gener-
ally ranges from 0.5 to 1 depending on the rate-
controlling step [steps (a–g)]. According to
Sievert’s law, when the rate-controlling step is
the bulk diffusion through the palladium layer
[step (c)], the n value is equal to 0.5 because the
diffusion rate is proportional to the concentration
of hydrogen atoms on the opposite sides of the
2 H2 Permeation Through Pd-Based Membranes
metal surface and this hydrogen concentration is
proportional to the square root of the hydrogen
pressure. When mass transport to or from the
surface (a, g) or dissociative adsorption (b) or
associative desorption (e) becomes rate-
controlling steps, the expected value of n is
1 because these processes depend linearly on the
concentration of molecular hydrogen. In the case
of the Pd-based composite membranes with thick
(>5 mm) Pd layers, the n values are higher than
0.5, and this fact can be explained by defects or
pinholes through which substantial amounts of
hydrogen can permeate. This process proceeds
via the Knudsen or Poiseuille flow mechanisms,
and the corresponding exponents are higher than
0.5.
In the case of binary palladium alloys, hydro-
gen permeation is generally proportional to the
average bond distance of the alloys. Permeability
is the product of diffusivity and solubility. In the
case of Pd–Ag alloys, hydrogen solubility
increases with increasing Ag content up to
20–40 wt.%; hydrogen diffusivity decreases
with increasing Ag content. Concomitant
changes in solubility and diffusivity lead to
higher hydrogen permeability (1.7 times higher)
as compared with that of pure Pd at 23 wt.% of Ag
and at 623K (Ma et al. 2003).
References
Ma YH, Mardilovich IP, Engwal EE (2003) Thin compos-
ite palladium and palladium/alloy membranes for
hydrogen separation. Ann N Y Acad Sci 984:346–360
Paglieri SN, Way JD (2002) Innovations in palladium
membrane research. Sep Purif Rev 31:1–169
Yun S, Oyama ST (2011) Correlations in palladium mem-
branes for hydrogen separation: a review. J Membr Sci
375:28–45
H
Hydrogen Removal by Membranes
V. V. Volkov
A.V.Topchiev Institute of Petrochemical
SynthesisRussian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Pure hydrogen is known to be a valuable indus-
trial material, and its annual consumption comes
to billions of cubic meters. Over 90 % of hydro-
gen is generated from fossil fuel sources (mainly,
steam reforming of natural gas) and the other
10 % is produced by water electrolysis. Hydrogen
is widely used in diverse large-scale processes in
metallurgical, chemical, petrochemical, pharma-
ceutical, and textile industries for the production
of a wide range of products – from semiconduc-
tors and steel alloys to vitamins and raw chemical
materials such as ammonia, methanol, and hydro-
gen peroxide. Recently, hydrogen has attracted a
keen attention as an alternative energy carrier for
the solution of environmental problems
(so-called concept of “hydrogen economy”). In
contrast to fossil fuels, hydrogen combustion
does not generate carbon dioxide but only water
vapors. Large-scale hydrogen production
requires significant capital investments for sepa-
ration and purification processes; thus, the cost of
hydrogen markedly increases. Conventional
technologies for hydrogen separation include sol-
vent absorption, pressure swing adsorption
(PSA), fractional/cryogenic distillation, and
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1041-1
membrane separation. Membrane separation
seems to be the most promising method because
of its low energy consumption, continuous oper-
ation, low investment costs, and easy operation
(Ockwig and Nenoff 2007).
Among all basic large-scale applications of
polymer membranes, hydrogen recovery is the
most important. In the 1970s, commercial suc-
cess of hydrogen-selective hollow-fiber mem-
brane systems for the in-process recycling of
hydrogen from ammonia purge gases has trig-
gered large-scale application of the membrane
gas separation. This technology has been
extended to other situations for recovery of
hydrogen from gas mixtures (H2/CO or H2/CH4
ratio adjustment for syngas production) and has
been successfully competing with cryogenic dis-
tillation and PSA processes. In the petrochemical
industry, hydrogen recovery from refinery
streams is an emerging field for membrane sepa-
ration; it is a key approach to meet the increased
demand of hydrogen (for hydrotreating, hydro-
cracking, or hydrodesulfurization processes)
owing to new environmental regulations
(Bernardo et al. 2009).
The main liability of hydrogen-selective
membranes is that recompression of the perme-
ated hydrogen is usually required. Therefore, an
alternative method involves contaminate prefer-
ential permeation, and this method is treated as a
new approach for hydrogen purification, primar-
ily by using the carbon-based membranes. For
example, hydrogen production by natural gas
2 Hydrogen Removal by Membranes
steam reforming yields a gaseous mixture
containing hydrogen and also carbon dioxide
and carbon monoxide. Solubility-controlled
membranes (e.g., carbon-based membranes) are
preferentially permeable for big-sized gas mole-
cules (e.g., CO2) in relation to hydrogen. This
peculiarity offers evident economic advantages
that maintaining/collecting hydrogen in the
retentate at nearly bulk feed pressure mitigates
the demands for costly hydrogen recompression
steps, even though a CO2 compression step is
required (Ockwig and Nenoff 2007).
Hydrogen-separating membranes made of pal-
ladium alloys have been developed over the past
50 years into a technology that in some instances
is used in practice. In an early work in the United
States and in the former Soviet Union, relatively
thick-walled tubes were used. This design has
been advanced for ultra-purification of hydrogen
and for its application in the semiconductor
manufacturing processes and in the hydrogen
generators for remote or small-scale usage. Cur-
rent research topics in this area are concerned
with membrane reactors for hydrogen gas supply
for fuel cells or for the chemical process industry.
Palladium-alloy diffusers present a key compo-
nent for the recovery of hydrogen radioisotopes
which are used and produced by the nuclear fis-
sion in the fusion reactors. Hydrogen recovery
from waste gases or purge streams (e.g.,
hydrotreater off-gas) presents a potentially large
application of the palladium-based membrane
technology. Coal gasification or natural gas
reforming coupled to a palladium membrane
reactor can offer an alternative huge source of
hydrogen. Production of pure hydrogen for its
use in fuel cells also seems to be another impor-
tant mission of the palladium-based membrane
reactor (Paglieri and Way 2002).
References
Bernardo P, Drioli E, Golemme G (2009) Membrane gas
separation: a review/state of the art. Ind Eng Chem Res
48:4638–4663
Ockwig NW, Nenoff TM (2007) Membranes for hydrogen
separation. Chem Rev 107:4078–4110
Paglieri SN, Way JD (2002) Innovations in palladium
membrane research. Sep Purif Rev 31:1–169
H
Hydrogen Selective Membranes
V. V. Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
As compared with other known fuels, hydrogen is
abundantly available in the universe and pos-
sesses the highest energy content per weight
unit. Moreover, in contrast to fossil fuels, the
use of hydrogen as an energy source yields
water as the only by-product. Hence, in recent
years, the demand for hydrogen energy and pro-
duction has been growing. Membrane separation
process offers an attractive alternative to mature
technologies such as pressure swing adsorption
(PSA) and cryogenic distillation.
Hydrogen selective membranes are designed
such that hydrogen concentration increases in the
permeate. Based on the materials used, hydrogen
selective membranes can be classified into four
types: (i) polymer (organic), (ii) metallic, (iii)
carbon, and (iv) ceramic. Metallic, carbon, and
ceramic membranes are referred to as inorganic
membranes. Depending on the type of the raw
material, inorganic membranes can be classified
into two groups: metal membranes and ceramic
membranes. In addition, they could be divided
into porous (microporous) and nonporous (dense)
membranes (Adhikari and Fernando 2006).
Microporous inorganic membranes include
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1042-2
carbon and ceramic (amorphous or crystalline)
membranes, and their separation characteristics
are governed by the molecular sieving transport
mechanism. Usually, dense inorganic mem-
branes are based on a metal or on a polycrystal-
line ceramic. In these dense membranes, the
fundamental operating mechanism involves the
conduction of free electrons and the presence of
specific catalytic surfaces in order to dissociate
H2 on the raw feed stream side and reassociate
both protons and electrons on the product side. In
such systems, hydrogen selectivity is typically
very high because their dense structure prevents
the transport of larger atoms and molecules (e.g.,
CO, CO2, O2, N2, etc.). This high selectivity pro-
vides the production of high-purity hydrogen
(Ockwig and Nenoff 2007).
Historically, hydrogen separation is accom-
plished on the Pd-based membranes because
they catalyze surface dissociation/reassociation
processes and they are highly permeable to
hydrogen. Palladium and Pd-alloy membranes
can produce hydrogen gas on the ppb impurity
levels. Since the late 1950s, small-scale Pd-based
membrane modules have produced high-purity
hydrogen at remote sites and for industrial, labo-
ratory, or military purposes. There are various
types of metallic membrane materials for hydro-
gen separation: (i) pure metals (Pd, V, Ta, Nb,
and Ti); (ii) binary alloys of Pd such as Pd-Cu,
Pd-Ag, Pd-Y, and also Pd-based alloys with Ni,
Au, Ce, and Fe; (iii) complex alloys (Pd alloyed
with three to five other metals); (iv) amorphous
2 Hydrogen Selective Membranes
alloys (typically Group IV and Group V metals);
and (v) coated metals such as Pd on Ta, V, etc.
(Adhikari and Fernando 2006). Dense ceramic
membranes (e.g., perovskite, bismuth oxide, and
solid electrolyte) have been developed and com-
mercialized. Dense inorganic membranes are
generally designed as a thin film on a porous
inorganic support.
To overcome the relatively low permeance
and high cost of dense metallic membranes,
researchers are exploring the utility of high-
permeance, less costly, and less selective micro-
porous inorganic (silica or carbon or zeolite)
membranes. The structure of these membranes
presents a network of interconnected micropores
with a diameter of ~0.5 nm. In general, micropo-
rous silicas show the highest hydrogen selectiv-
ities, and they exhibit the best H2/N2 selectivity
which exceeds 10,000 for the membranes pre-
pared by chemical vapor deposition (Ritter and
Ebner 2007).
Since the 1970s, gas separation polymer mem-
branes have been used industrially for hydrogen
separation from gaseous mixtures in the United
States (Ockwig and Nenoff 2007) and in the
former Soviet Union (Yampolskii and Volkov
1991). Membranes made of glassy polymers
(i.e., polymers with glass transition temperatures
above the operating temperature) are used for
removing hydrogen from gas mixtures. Examples
of membrane materials for commercial polymer
membranes include polyimide and polysulfone
(asymmetric hollow fiber membranes) or polyvi-
nyl trimethylsilane and cellulose acetate
(asymmetric flat membranes). Such polymer
membranes operate according to the solution-
diffusion mechanism.
In general, hydrogen selectivity is low, mod-
erate, and very high for polymeric, microporous
inorganic, and metallic membranes, respectively.
Polymeric membranes primarily operate at tem-
peratures below 373 K, whereas carbon, silica,
and dense ceramic membranes can function at
higher temperatures (773–1,173 K). Metallic
membranes can be used at ~573–873 K.
References
Adhikari S, Fernando S (2006) Hydrogen membrane sep-
aration techniques. Ind Eng Chem Res 45:875–888
Ockwig NW, Nenoff TM (2007) Membranes for hydrogen
separation. Chem Rev 107:4078–4110
Ritter JA, Ebner AD (2007) State-of-the-art adsorption
and membrane separation processes for hydrogen pro-
duction in the chemical and petrochemical industries.
Sep Sci Technol 42:1123–1193
Yampolskii YP, Volkov VV (1991) Studies in gas perme-
ability and membrane gas separation in the Soviet
Union. J Membr Sci 64:191–228
H
Hydrogenation Contactors
and Reactors
V. V Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Among all known catalysts for hydrogenation,
metals of platinum family (Pt, Pd, Ni) are
known to be most efficient and advantageous.
Palladium catalysts for selective hydrogenation
hold the unique position. Palladium and its alloys
show an excellent potential to dissolve huge
amounts of hydrogen, and as membrane mate-
rials, dense palladium and palladium alloy mem-
branes are permeable only for hydrogen.
Pioneering studies by Gryaznov and his
coworkers have encouraged the use of palladium
and palladium alloy membranes in catalytic
membrane reactors, including fundamental stud-
ies on selective hydrogenation of various unsatu-
rated hydrocarbons, for example, acetylene,
1,3-pentadiene, and cyclopentadiene. The gen-
eral concept can be formulated as follows: hydro-
gen is supplied to one side of the Pd-based
catalytic membrane, and then it diffuses selec-
tively through the membrane and approaches the
other side of the membrane in its highly reactive
form. Fundamental concepts on membrane catal-
ysis and catalytic membrane reactors have been
advanced in the 1960s, and the phenomenon of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1043-1
conjugating of chemical reactions with the evo-
lution (dehydrogenation reaction) and consump-
tion (hydrogenation reaction) of hydrogen on
palladium membranes has been discovered in
1964 (Gryaznov et al. 2003). This concept is
illustrated in Fig. 1.
Early studies in this direction have been
focused on the use of relatively thick nonporous
Pd or Pd-alloy membranes. Their thickness can
be reduced by preparation of composite mem-
branes on porous or nonporous supports.
A critically new step providing reduced con-
sumption of expensive noble metals is concerned
with the development of catalytic membranes
based on the metal–polymer composites. In this
case, nonporous polymer matrix, for example,
silicon rubber, is loaded with palladium
nanoparticles (Gryaznov et al. 2003).
Pd-based catalytic nanoparticles can be
immobilized on the surface of porous inorganic
or polymeric membranes, thus providing a new
type of catalytic membrane reactor, called cata-
lytic contactor. According to the proposed classi-
fication (Miachon and Dalmon 2004), depending
on the mode of supply of reagents, two types of
catalytic contactors exist: an interfacial contactor
and a flow-through contactor. In this case, a key
point is concerned with localization of reactants
in the very volume where the catalyst is
deposited.
The typical example of hydrogenation on an
interfacial catalytic contactor is related to
removal of dissolved oxygen (DO) from water
2 Hydrogenation Contactors and Reactors
Substrate
Liquid
Palladium
‹H›
alloy
Gas
H2 or R-H2
Hydrogenation Contactors and Reactors,
Fig. 1 Principle of a dense and self-supporting palladium
alloy membrane (a thin-walled tube or a foil) for liquid
phase hydrogenation. Hydrogen or hydrogen-containing
source R–H2 is supplied to the gas side; a to-be-
hydrogenated substrate is supplied to the liquid side.
Dehydrogenation of R–H2 occurs on the gas-side surface
(Volkov et al. 2011). Hydrogen and
DO-containing water are supplied to the opposite
sides of a hydrophobic porous catalytic mem-
brane. In this case, membrane material should
be non-wettable for water (hydrophobic) in
order to provide liquid-free pores and high-rate
hydrogen transmembrane mass transfer. The Pd
catalyst is placed onto the water-contacting mem-
brane surface. Water deoxygenation by catalytic
membranes, including palladium-loaded hollow
fibers, is accomplished by the chemical reaction
between dissolved oxygen and hydrogen in the
presence of the palladium catalyst.
In a flow-through contactor, reactants are
forced to flow through a porous catalytic mem-
brane, i.e., through the Pd-loaded pores. This
enables to control and rule residence time of
reacting species in the active zone of the catalytic
membrane.
ΔH < 0
Hydrogenated products
q
~ 50 – 100 μm
R (opt.)
ΔH > 0
and this process is endothermic; both reactions are accom-
panied by hydrogen transfer. Due to excellent thermal
conductivity of the membrane, the heat released by hydro-
genation can be utilized to facilitate endothermic dehy-
drogenation (autothermic operation) (Dittmeyer
et al. 2004)
References
Dittmeyer R, Svajda K, Reif M (2004) A review of cata-
lytic membrane layers for gas/liquid reactions. Top
Catal 29(1–2):3–27
Gryaznov VM, Ermilova MM, Orekhova NV,
Tereschenko GF (2003) Reactors with metal and
metal-containing membranes. In: Cybulski A, Moulijn
JA (eds) Structured catalysts and reactors, 2nd edn.
Taylor & Francis, New York, pp 579–614
Miachon S, Dalmon J-A (2004) Catalysis in membrane
reactors: what about the catalyst. Top Catal 29:59–65
Volkov VV, Petrova IV, Lebedeva VI, Roldughin VI,
Tereshchenko GF (2011) Palladium-loaded polymeric
membranes for hydrogenation in catalytic membrane
reactors. In: Basile A, Gallucci F (eds) Membranes for
membrane reactors: preparation, optimization and
selection. Wiley, New York, pp 531–548
P
Palladium-Loaded Hollow Fibers: rate, and it provides a nearly dense palladium
Application in Water Deoxygenation layer with thickness of 2–3 mm.
V. V. Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Palladium nanoparticles can be deposited on a
hydrophobic porous polypropylene hollow fiber
membrane, which preserves its hydrophobic
nature (Lebedeva et al. 2006). Prior to the depo-
sition of palladium onto the membrane surface,
hollow fibers should be cleaned with surfactants
and organic solvents. Then, their outer surface is
etched either by strong inorganic acids or by
strong inorganic bases. The next step includes
electroless deposition of palladium by one of
the two following methods: (1) reduction of pal-
ladium tetraaminochloride by hydrazine hydrate
(initial membranes are Accurel Q3/2 and Accurel
S6/2) and (2) reduction of palladium chloride or
palladium acetate by methanol (Accurel Q3/2,
Celgard X50) (Volkov et al. 2009). According
to the computational analysis of the SEM images,
surface porosity of the initial membranes (both
Accurel Q3/2 and Celgard X50) slightly
increases after pretreatment. All palladium
appears to be localized on the outer surface of
the hollow fiber membranes. The deposition
method (1) is characterized by a high deposition
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1044-2
The slow wet-chemical deposition method
includes the use of aliphatic alcohols (e.g., meth-
anol) which serve as a reducing agent and as a
solvent for palladium salts, and this process
makes it possible to provide deposition of well-
distributed fine palladium nanoparticles. In this
case, loading of palladium is well below 20 mg/
cm2, and dimensions of nanoparticles tend to
decrease with decreasing level of loading. The
EDX and EXAFS observations reveal no other
palladium-containing phases (e.g., oxides) and
crystallinity of metallic palladium is proved by
the XRD analysis. Dimensions of primary parti-
cles in their free state and in aggregates are esti-
mated by the methods of X-ray analysis and SEM
observations. Dimensions of primary palladium
particles range from 10 to 40 nm, and dimensions
of their aggregates vary from 200 nm to tens of
microns.
Palladium nanoclusters can catalyze DO
hydrogenation, thus providing water deoxygen-
ation by catalytic membranes, even though the
loading of palladium is as low as 5 mg/cm2. The
estimated surface porosity is (12  1) %, (17 
2) %, and (17  3) % for initial Celgard X50,
pretreated membrane, and Pd-loaded membrane
(5.4 mg/cm2 Pd), respectively. For the sample
containing 39 mg/cm2 of Pd, surface porosity
cannot be estimated by the computer-aided SEM
image processing because the deposited palla-
dium totally occupies the entire structure of
2 Palladium-Loaded Hollow Fibers: Application in Water Deoxygenation
porous membranes. Palladium can be deposited
either onto individual hollow fiber membranes or
onto the surface of membranes within a mem-
brane module. Hence, commercially available
membrane module (Liqui-Cel ®) can be coated
integrally as delivered, without any disassembly.
Reduction of DO down to its concentration of
10 parts per billion (ppb) and lower is feasible
using catalytic membrane reactors based on
palladium-loaded porous hollow fibers.
References
Lebedeva VI, Gryaznov VM, Petrova IV, Volkov VV,
Tereshchenko GF, Shkol’nikov EI, Plyasova LM,
Kochubey DI, van der Vaart R, van Soest-
Verecammen ELJ (2006) Porous Pd-containing
polypropylene membranes for catalytic water deoxy-
genation. Kinet Catal 47:867–872
Volkov VV, Petrova IV, Lebedeva VI, Plyasova LM,
Rudina NA, van Erkel J, van der Vaart R,
Tereshchenko GF (2009) Catalytic nanoclusters of
palladium on the surface of polypropylene hollow
fiber membranes: removal of dissolved oxygen from
water. In: Starov VM (ed) Nanoscience: colloidal and
interfacial aspects. Taylor & Francis Group, New
York, pp 1173–1188
W
Water Deoxygenation by Catalytic
Membranes
V. V. Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
The process of catalytic removal of dissolved
oxygen (DO) from water presents an encouraging
example for the industrial application of palla-
dium catalysts supported on ion-exchange resins.
Noteworthy is that the existing catalytic pro-
cesses for deoxygenation of water via hydroge-
nation reaction involve two stages: (1) absorption
of hydrogen in water and (2) passage of water
containing dissolved hydrogen and DO through a
fixed-bed catalytic reactor.
Catalytic membranes, i.e., palladium-loaded
hollow fibers, can be prepared by deposition of
palladium nanoparticles onto an outer surface of
the hydrophobic porous polypropylene
(PP) hollow fiber membranes and allow the DO
removal from water in one stage (van der Vaart
et al. 2001).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1045-2
The principle of DO removal using a catalytic
membrane is illustrated in Fig. 1. The hydropho-
bic porous catalytic membrane serves three key
functions: (1) a well-defined and easily controlled
location of a hydrogen–water interface, (2) acces-
sibility of a catalyst for reagents (hydrogen and
oxygen), and (3) high overall mass transfer coef-
ficient. DO-containing water flows over the outer
surface of the Pd-loaded hydrophobic hollow
fiber membrane, whereas hydrogen, as a reducing
agent, is supplied into the lumen side of hollow
fibers and approaches the working surface of a
catalyst through the pores of the membranes. Due
to the catalytic activation of hydrogen adsorbed
on the palladium surface, a heterogeneous reac-
tion of DO reduction takes place. Consequently,
this design allows good access of both the gas
phase and liquid phase reactants to the catalyst
placed on the outer membrane surface, and this
system is well suited for hydrogenation reactions
in aqueous media. Moreover, the reaction pro-
ceeds at room temperature. The process of water
deoxygenation based on catalytic membranes is
capable of achieving residual oxygen concentra-
tion below 10 ppb.
2 Water Deoxygenation by Catalytic Membranes

References
H2O
van der Vaart R, Hafkamp B, Koele PJ, Querreveld M,
Jansen AE, Volkov VV, Lebedeva VI, Gryaznov VM
(2001) Oxygen removal from water by two innovative
membrane techniques. Ultrapure Water 18:27–32
Volkov VV, Lebedeva VI, Petrova IV, Bobyl AV,
H2 Konnikov SG, Roldughin VI, van Erkel J,
Tereshchenko GF (2011) Adlayers of palladium parti-
cles and their aggregates on porous polypropylene
hollow fiber membranes as hydrogenization contrac-
tors/reactors. Adv Colloid Interface 164:144–155
2

Water Deoxygenation by Catalytic Membranes,

Fig. 1 A scheme illustrating the process of DO removal
from water using a Pd-loaded porous hollow fiber mem-
brane: 1 deposited Pd, 2 polypropylene porous support
(Volkov et al. 2011)
S
SPS/PES Asymmetric Blend
Nanofiltration Membrane
Yuzhong Zhang
School of Material Science and Engineering,
Tianjin Polytechnic University, Tianjin, China
An SPS/PES asymmetric blend nanofiltration
(NF) membrane is a novel semipermeable mem-
brane used in nanofiltration process, such as
water treatment for drinking water production,
desalination, concentration, and purification and
pharmaceutical and chemical industries.
SPS/PES asymmetric blend nanofiltration mem-
branes are developed in 2011 by Senuo Filtration
Technology (Tianjin) Co., Ltd (Chen et al. 2011).
A nanofiltration membrane is a type of
pressure-driven membrane with properties in
between reverse osmosis (RO) and ultrafiltration
(UF) membranes, with a membrane pore size
between 0.5 and 2 nm, nominal molecular weight
cutoffs from 200 to 1000 Da, and operating pres-
sures between 5 and 40 bar (Hilal et al. 2004).
Most nanofiltration membranes are composite
membranes produced via sophisticated fabrica-
tion processes, such as coating or interfacial poly-
merization, where the top selective layer and
bottom porous substrate of the membrane can be
independently modified and optimized (Lau et al.
2012; Mulder 2009). The fabrication processes
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1049-6
for composite membrane in general involve var-
ious preparation conditions, making the entire
process very labor intensive.
Asymmetric blend nanofiltration membranes
are made by non-solvent-induced phase separa-
tion, which is a single-step process. Non-solvent-
induced phase separation technology is a rela-
tively simple preparation technique compared to
composite membrane fabrication technology.
And also, the blending technique has the advan-
tage of combining the positive features of each
component while being very simple.
SPS/PES asymmetric blend nanofiltration
membranes are fabricated by blending
polyethersulfone (PES) with sulfonated
polysulfone (SPS) as membrane material. PES
is one of the important polymer materials in
membrane fabrication, due to its excellent
mechanical strength and thermal and chemical
stability. PES also allows easy manufacturing of
membranes, with reproducible properties and
controllable size of pores down to several decade
nanometers. Polyethersulfone repeating unit is
shown in Fig. 1.
PES is also an inherently hydrophobic poly-
mer. A wide range of evidence shows that mem-
brane with adequate hydrophilicity can prevent
deposition of many solutes such as protein, which
can increase resistance to fouling. However,
hydrophobicity of PES has limited its application
in NF membrane preparations. Introducing
2 SPS/PES Asymmetric Blend Nanofiltration Membrane

sulfonic groups to membrane is an efficient way
to improve the hydrophilicity of PES membrane,
which can be carried out through the introduction
of sulfonic groups directly into PES or by blend-
ing with another sulfonated material, such as
sulfonated polysulfones (SPSs). Sulfonated
polysulfone (repeating unit shown in Fig. 2)
with hydrophilic group, sulfonic group, has ade-
quate hydrophilicity. The high hydrophilicity can
improve the water flux and pollution resistibility.
But sulfonated polysulfones possess weak
strength, which will cause bad stability for oper-
ation. The miscibility of PES with SPS is better
enough. Sulfonated polysulfone can be induced
to increase hydrophilicity of the PES
nanofiltration membrane.
Besides increasing hydrophilicity, sulfonated
polysulfone offers another advantage, negative
O shown in Fig. 3. Blending of PES with SPS in
O S
O n
SPS/PES Asymmetric Blend Nanofiltration Mem-
brane, Fig. 1 Polyethersulfone repeating unit
charge. Membranes with fixed charges are
predicted to exclude solutes or colloids bearing
the same sign of charge and to decrease mem-
brane fouling. SPS/PES asymmetric blend
nanofiltration membranes with functional group,
sulfonic group, can gain negative charges and
give them great selectivity with respect to ions
or charged molecules.
SPS/PES asymmetric blend nanofiltration
membranes are primarily characterized by pure
water flux, rejection, and hydrophilicity.
An SPS/PES asymmetric blend nanofiltration
membrane is a combination of good hydrophilic-
ity and mechanical strength, which can improve
the water flux, antipollution ability, and stability
of blend membrane. The negative charge due to
sulfonic group leads to a high selectivity over
ions or molecules with positive charges.
The SPS/PES asymmetric blend nanofiltration
membrane has the asymmetric morphology, as
the casting dope leads to interesting asymmetric
structure. There are fingerlike macropores and
spongelike pores in SPS/PES membranes.
A dense layer supported on a porous layer, as
shown in Fig. 4.

SPS/PES Asymmetric SO3H

Blend Nanofiltration CH3 O
Membrane,
Fig. 2 Sulfonated O C O S
polysulfone repeating unit
CH3 O n

SPS/PES Asymmetric Blend Nanofiltration Membrane, Fig. 3 Typical cross section morphology of SPS/PES
asymmetric blend nanofiltration membrane
SPS/PES Asymmetric Blend Nanofiltration Membrane 3

References

Chen YH, Ma F, Li DW, Li Ran (2011) A preparation

method for PES/SPS asymmetric blend nanofiltration
membrane. China Patent CN101979132A
Hilal N, AL-Zoubi H, Darwish NA, Mohammad AW, Abu
Arabi M (2004) A comprehensive review of
nanofiltration membranes: treatment, pretreatment,
modelling, and atomic force microscopy. Desalination
170:281–308
Lau WJ, Ismail AF, Misdan N, Kassim MA
(2012) A recent progress in thin film composite mem-
brane: a review. Desalination 287:190–199
Mulder M (2009) Basic principles of membrane technol-
ogy. Kluwer, London
SPS/PES Asymmetric Blend Nanofiltration Mem-
brane, Fig. 4 Typical morphology of the top surface
M
Microscale Modeling
and Membranes
Vasilis Burganos and Eugene Skouras
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology,
Hellas, Patras, Hellas
Microscale modeling refers to the modeling of
membrane processes at a resolution level where
fundamental phenomena can be described with
minimum assumptions using first principles.
Modeling tools at the microscopic level usually
encompass molecular dynamics (MD) and/or
Monte Carlo (MC) techniques, which incorporate
many degrees of freedom for the detailed analysis
of transport, sorption, reaction, and other process
phenomena in membranes. Because of the tre-
mendous significance of the internal structure of
membranes on their performance, especially in
separation or preferential transport applications
(e.g., fuel cells and membrane reactors), models
of the membrane structure at the microscopic
level have been developed. In polymeric, “rub-
bery” membranes, models of gas transport in
their interior are mainly based on free volume
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1050-2
concepts. In the free volume approaches, the con-
centration dependence of the penetrant diffusiv-
ity is described by considering the average spaces
between chains (Flory 1969). Such models com-
monly relate the mutual diffusion coefficients for
a gas/polymer system to the free volume of the
system. Significant efforts have been made to
explain the mechanisms of gas transport in poly-
mers by means of molecular theories. Molecular
theories attempt to analyze the diffusion process
in terms of specific postulated motions of the
polymer chain relative to each other and the
motion of penetrant molecules. In order to move
into the polymer matrix, the gas molecule pushes
the polymer chain and jumps into a new position
(Pace and Datyner 1979). Αt around the glass
transition temperature and below, thermal fluctu-
ations of the polymer configurations are limited
and penetrants are assumed to jump between
cavities with a motion that is likely to entail a
significant activation energy barrier (Crank and
Park 1968). Simulations in glassy polymers have
been attempted with the help of a dual-mode
sorption model and some free volume model
description. Attempts have also been made to
explain gas diffusion in polymers by various
molecular mechanisms and models that involve
2 Microscale Modeling and Membranes
Microscale Modeling and Membranes,
Fig. 1 Atomistic reconstruction of SiO2 (Accelrys Mate-
rial Studio)
the calculation of the energy for an assumed
specific simplified polymer conformation after
an energy-activated jump of the penetrant. Most
models are leading to the concept of available
free volume as diffusing channels (Kotelyanskii
and Theodorou 2004). In fact, the mechanism of
gas separation by dense, nonporous membranes
is different from that by porous ones, since diffu-
sion occurs via a solution-diffusion mechanism;
the permeants dissolve in the membrane material
and then diffuse through the membrane down a
concentration or chemical potential gradient.
Separation between the different permeants is
achieved due to differences in the amount of
material diffusing through the membranes. The
microstructure of membranes, both polymeric
and inorganic, used in gas separation is usually
reconstructed at the atomistic level, to study the
interaction effect of solute or diffusing molecules
with the membrane material. The reconstruction
of inorganic membrane structures at the molecu-
lar scale is usually realized using MD and MC
techniques. Initially, the atoms of the membrane
materials are positioned at predefined bulk lattice
sites, taken from literature, experimental data, or
diffraction techniques. The interatomic potential
energy of the configuration is dynamically calcu-
lated using some force field description. The
force field approach involves an analytical
expression that gives the energy of a molecular
system in terms of the positions of all its atoms.
Both intramolecular (short) and non-bonded
(long) atomic interactions are usually taken into
account. These data are obtained using either
empirical or quantum mechanical
(QM) calculations. Using a force field, useful
quantities such as momenta, interaction energies,
conformational energy barriers, and free energies
can be estimated. The atomistic structure is the
basis for MD and MC calculations to probe the
locations, conformations, and motions of mole-
cules, predicting the actual supply of sorbates to
the active sites of membrane (Allen and Tildesley
1987). Mesoscopic and macroscopic membrane
process parameters, such as permeabilities, diffu-
sivities, sorption isotherms, reaction and decay
coefficients, as well as (perm)selectivities, used
in mesoscopic simulations derived from kinetic
theory, Fickian, or Stefan-Maxwell (dusty gas)
approaches, can then be derived based on proper
integration of their microscopic origins (Figs. 1
and 2).
Microscale Modeling and Membranes 3

Microscale Modeling
and Membranes,
Fig. 2 FAU structure with
equilibrated Na+ cations
(Accelrys Material Studio)

References Flory PJ (1969) Statistical mechanics of chain molecules.

Allen MP, Tildesley DJ (1987) Computer simulation of
liquids. Clarendon, Oxford
Crank J, Park GS (1968) Diffusion in polymer. Academic,
NY
Wiley, NY
Kotelyanskii MJ, Theodorou DN (2004) Simulation
methods for polymers. Marcel Dekker, NY
Pace RJ, Datyner A (1979) Statistical mechanical model
for diffusion of simple penetrants in polymers. 1. The-
ory. J Polym Sci Part B: Polym Phys 17(3):437–451
M
Mesoscopic Transport Simulation
Vasilis Burganos
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology,
Hellas, Patras, Hellas
Mesoscopic transport simulation is a type of con-
ceptual or computational simulation of transport
phenomena at the mesoscopic scale. The latter is
defined as an intermediate scale between the
microscopic scale, which considers molecular
configurational details, and macroscopic scale,
at which certain types of inhomogeneities or fluc-
tuations have been averaged out. In the area of
porous media, mesoscopic simulation of trans-
port phenomena may refer to the pore scale itself,
that is, to the scale of a few hundreds of pores or
grains or to the scale at which a pore neighbor-
hood is viewed as a thermodynamic point in
space. In the former case, the characteristic
length of a mesoscopic transport simulator is
significantly larger than the atomic dimensions,
and, as such, it contains or refers to a large num-
ber of molecules of the transported species. As a
result, local values of system properties, like den-
sity, pressure, temperature, etc., can be defined in
a consistent yet statistical manner. In the latter
case, a continuum formulation is used to employ
spatial averages over length scales much larger
than the typical pore or grain scale. The concept
of the thermodynamic point or of a representative
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1051-2
volume element (RVE) has contributed critically
in this direction, sidestepping the need for
treating spatial heterogeneities at smaller scales.
These are reflected in pore-scale simulations,
which are utilized to offer effective values for
constitutive parameters that are functions of the
local conditions and local structure (Bear 1972).
In the context of transport phenomena in mem-
branes, mesoscopic simulations of diffusion,
flow, two-phase flow, dispersion, and ionic trans-
port are typical examples of simulations that are
performed with reference to finite samples of the
membrane material. Once a mesoscopic descrip-
tion of the membrane sample is available, trans-
port simulations can lead to the determination of
transport coefficients at that scale.
The mesoscopic description of the membrane
material may involve a pore model to represent
the void space of the membrane, a fiber or grain
model to represent the solid phase, or a digitized
model of the structure following three-
dimensional reconstruction. Different types of
numerical tools and simulation techniques have
been developed for the solution of problems
involving transport phenomena at this scale.
Notable examples include the classical numerical
solvers for the direct solution of the transport
equations complemented by appropriate bound-
ary conditions at the faces of the working domain
and at the interface between void and solid or,
more generally, between the various phases that
comprise the membrane. Typical examples of
such equations include the diffusion equation,
2 Mesoscopic Transport Simulation
Mesoscopic Transport
Simulation,
Fig. 1 Representative
element of porous medium
the heat conduction equation, the Stokes or
Navier–Stokes equations for flow problems, the
convection–diffusion equation, etc. Another cat-
egory involves the simulation of the motion of a
number of molecule deputies that carry, in an
efficient manner, the properties of the actual
fluid molecules that are obviously too many to
follow individually. Such methods include the
direct simulation Monte Carlo (Bird 1963, 1976,
1994), the dissipative particle dynamics
(Hoogerbrugge and Koelman 1992;
Moeendarbary et al. 2009), the lattice gas method
(Frisch et al. 1986; Wolfram 1986, Rothman and
Keller 1988), and the lattice Boltzmann method
(Benzi et al. 1992; Chen et al. 1992), which,
rather than the fluid molecules themselves, fol-
low the evolution of their probability density
function across the lattice. The lattice Boltzmann
method is a mesoscopic method that originated
from the classical statistical physics and is based
on simplified kinetic equations. A rigorous math-
ematical analysis that starts from the lattice
Boltzmann equation has been shown to recover
mesoscopic continuity and momentum equations
using well-defined features of propagation–-
collision dynamics. Thanks to the explicit rela-
tion with details of the geometry and physics of
the problem, complex boundaries and various
Representative element of porous medium
physicochemical phenomena can be treated.
Single- and two-phase flow phenomena with or
without phase transition can be studied in the
context of membrane separations, including gas
separation, filtration, membrane distillation,
membrane emulsification, etc. (Fig. 1).
References
Bear J (1972) Dynamics of fluids in porous media. Amer-
ican Elsevier, New York
Benzi R, Succi S, Vergassola M (1992) The lattice
Boltzmann-equation – theory and applications. Phys
Rep 222:145–197
Bird GA (1963) Approach to translational equilibrium in a
rigid sphere gas. Phys Fluids 6:1518–1519
Bird GA (1976) Molecular gas dynamics. Clarendon,
Oxford
Bird GA (1994) Molecular gas dynamics and the direct
simulation of gas flows. Claredon, Oxford
Chen S, Wang Z, Shan X, Doolen G (1992) Lattice
Boltzmann computational fluid-dynamics in 3 dimen-
sions. J Stat Phys 68:379–400
Frisch U, Hasslacher B, Pomeau Y (1986) Lattice-gas
automata for the Navier–Stokes equation. Phys Rev
Lett 56:1505–1508
Hoogerbrugge PJ, Koelman JMVA (1992) Simulating
microscopic hydrodynamic phenomena with dissipa-
tive particle dynamics. Europhys Lett 19:155–160
Moeendarbary E, Ng T, Zangeneh M (2009) Dissipative
particle dynamics: introduction, methodology and
Mesoscopic Transport Simulation 3

complex fluid applications – a review. Int J Appl Mech Wolfram S (1986) Theory and applications of cellular
1:737–763 automata. World Scientific, Singapore
Rothman D, Keller JM (1988) Immiscible cellular-
automaton fluids. J Stat Phys 52:1119–1127
D
Digitized Structure Model
Vasilis Burganos
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology -
Hellas, FORTH/ICE-HT, Patras, Hellas
Digital Reconstruction
It is a procedure to represent the internal structure
of materials in digital form, usually, binary, in
three dimensions using data from microphoto-
graphs or other sources of spatial correlation
data. It has contributed significantly to the visual
comprehension of the internal configuration of
porous materials, human tissues, and composite
materials. In the case of porous materials, like
porous membranes, catalyst supports, rocks,
etc., a binary representation in three dimensions
assigns the value of 0 (or 1) to the voxels that lie
in the void space and the value of 1 (or 0) to the
voxels in the complementary space (solid)
(Torquato 2002, 2010). In this way, one obtains
a fully three-dimensional array of flags (0 or 1)
that defines in a discretized form the pore space
inside the material. This array can then be utilized
in simulations of sorption and transport phenom-
ena (Gelb 2009), typically, diffusion, flow,
two-phase flow, and dispersion that are of utmost
importance in the design and modeling of mem-
brane materials and membrane separation pro-
cesses. Raw data for the initiation of the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1053-2
reconstruction procedure can be obtained in var-
ious ways. Physical serial sectioning along planes
that are normal to a fixed direction has repeatedly
been used using special microtomes or surface
grinders following impregnation of the void
phase with some suitable substance (resin,
Wood’s metal, etc.). Digitization of the photo-
graphs of each and every section of the material
provides a set of two-dimensional arrays to be
combined in a deterministic fashion into a three-
dimensional array that discretizes the working
sample of the medium. Computer tomography
provides the same type of information in an auto-
mated or semiautomated manner and enjoys tre-
mendous use in medicine and some types of
porous media, most typically in hydrocarbon res-
ervoirs. More recently, stochastic techniques are
attracting the increasing interest of investigators
in this area inasmuch as they require a single
section only rather than a whole series of sec-
tions. Provided that the sample is sufficiently
isotropic and homogeneous, one can extract valu-
able geometric and topological data from the
section and reconstruct in three dimensions a
discretized form of the material that respects the
features that characterize the two-dimensional
image of the section (Quiblier 1984; Adler
1992). Such features include various moments
of the correlation function, typically porosity
and autocorrelation function, but also higher-
order moments or lineal-length distribution,
chord-length distribution, etc. The latter is
succeeded by the simulated annealing technique

Digitized Structure
Model, Fig. 1 Stochastic
reconstruction of porous
material using the
fractional Brownian motion
method, showing
individual volume elements
(Kirkpatrick et al. 1983) that, theoretically, is
capable of reproducing three-dimensional
descriptions of materials from an arbitrary num-
ber of moments of the correlation function at the
expense, of course, of heavy requirements in
computational time. A simpler procedure that
has proven efficient for several types of porous
membranes including asymmetric ones is the
so-called fractional Brownian motion technique
that respects the first two moments of the corre-
lation function and, in addition, offers an inter-
weaving option that allows three-dimensional
reconstruction (Fig. 1) at much greater scale
than the correlation length of the structure
(Kikkinides and Burganos 2000). For materials
that have evolved from powders through some
agglomeration or sintering process, ballistic or
random placement methods can be used that
allow mass transfer between coalescing particles
at a controlled fashion so as to reproduce the
actual grain-size distribution and porosity or
solid fraction. Reconstruction of fiber-type mate-
rials can proceed in a similar manner. In the case
of porous membranes that contain nanoscale
Digitized Structure Model
pores, scattering techniques can be used that
offer in an implicit manner the autocorrelation
function, thus sidestepping the stage of micros-
copy and the subsequent phase of image analysis
for the extraction of two-dimensional features.
References
Adler PM (1992) Porous media- geometry and transports.
Butterworth-Heinemann, Stoneham
Gelb LD (2009) Modeling amorphous porous materials
and confined fluids. MRS Bull 34:592–601
Kikkinides ES, Burganos VN (2000) Permeation proper-
ties of three-dimensional self-affine reconstructions of
porous materials. Phys Rev E 62:6906–6915
Kirkpatrick S, Gelatt CD, Vecchi MP (1983) Optimization
by simulated annealing. Science 220:671–680
Quiblier JA (1984) A new 3-dimensional modeling tech-
nique for studying porous-media. J Colloid Interface
Sci 98:84–102
Torquato S (2002) Random heterogeneous
materials – microstructure and macroscopic proper-
ties. Springer-Verlag, New York
Torquato S (2010) Optimal design of heterogeneous mate-
rials. Annu Rev Mater Res 40:101–129
P
Pore Model
Vasilis Burganos
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology, Patras,
Hellas
A model that involves a set or a network of pores
to represent the void phase in the interior of
porous materials. It is used in the context of
pore structure characterization and as a structural
basis for the prediction of transport properties.
Traditionally used pore model types are the par-
allel pore model (Wheeler 1955), the random
pore model (Wakao and Smith 1962) or dual
porosity model, the cavity-neck model (Conner
et al. 1983), and numerous variations. Because of
the explicit representation of the void space that
is offered by a pore model, major topological and
geometrical features of the pore structure can be
revealed or identified. The former relate mainly
to pore connectivity as quantified by quantities
like coordination number, genus per unit volume,
etc., whereas the latter include pore shape, pore
volume, pore size distribution, internal surface
area per unit of volume, pore roughness,
etc. These features can be extracted from individ-
ual or combined experimental techniques that can
be divided into static (mercury porosimetry, gas
adsorption/desorption, calorimetry, nuclear mag-
netic resonance, radiation scattering, wave prop-
agation, etc.) and dynamic (liquid displacement,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1055-2
fluid flow). In fact, pore models play an important
role in the physically meaningful and explicit
interpretation of the data that are produced by
these techniques. Once a pore model is set up,
investigations of transport phenomena in the inte-
rior of porous materials in a direct manner are
greatly facilitated for the prediction of effective
transport properties and for the identification of
underlying mechanisms. Notable examples are
diffusion of single species and multicomponent
mixtures, single and multiphase flow, heat and
ion conduction, convective diffusion and conduc-
tion, transport in catalytic or non-catalytic fluid-
solid reaction systems accompanied by pore
structure evolution, etc. In the presence of chem-
ical reaction, as, for instance, in membrane reac-
tors, access to and removal from the reaction
front of reactants and products are affected sig-
nificantly by the pore structure features, and the
use of a pore model that is temporally changing is
highly appreciated. The study of wetting phe-
nomena is also greatly facilitated by the employ-
ment of pore models both for the purpose of
structure characterization and for the theoretical
modeling of capillary phenomena during immis-
cible and miscible displacement in porous media
with the objective to predict percolation and
breakthrough conditions. Thanks to this direct
usefulness of pore models in the identification
of structural features and in the prediction of
transport properties and the fact that membrane
separation is based on selective transport, pore
models enjoy strong utilization in membrane
2 Pore Model
Pore Model, Fig. 1 Pore segment identification process
to produce a cavity-neck model
science and engineering. More specifically, pore
models are used for the understanding of the role
of the membrane pore structure in the target sep-
aration process, for the elucidation of the rela-
tionship between structure and transport, and for
the design of new or modified membranes for
specific separations. Pore models are a major
design component in numerous membrane pro-
cesses, including, most notably, gas separation,
ultrafiltration, microfiltration, pervaporation,
membrane contactors, membrane distillation,
etc. Flux equations at the individual pore scale
and at the pore network scale have been devel-
oped (Maxwell-Stefan equations, dusty gas
equations) that describe the relationship between
driving forces and resulting fluxes of the different
species (Jackson 1977). The former include gra-
dients of species concentration, partial pressure,
chemical potential, pressure, temperature,
etc. For pore networks that can be characterized
adequately by a constant or a mean coordination
number, effective medium treatments are avail-
able that homogenize the transport property of a
distributed pore size network and with the help of
the smooth field approximation can offer an
excellent estimate of the overall transport of the
pore structure (Burganos and Sotirchos 1987). In
the case of variable connectivity of the pore net-
work, standard network solutions are available in
the form of numerical algorithms that practically
express the continuity condition at pore intersec-
tions (Fig. 1).
References
Burganos VN, Sotirchos SV (1987) Diffusion in pore
networks. Effective medium theory and smooth field
approximation. AIChE J 33:1678–1689
Conner WC, Lane AM, Ng KM, Goldblatt M (1983) Mea-
surement of the morphology of high surface area
solids: porosimetry of agglomerated particles. J Catal
83:336–345
Jackson R (1977) Transport in porous catalysts. Elsevier,
New York
Wakao N, Smith JM (1962) Diffusion in catalyst pellets.
Chem Eng Sci 17:825–834
Wheeler A (1955) Catalysis, vol II. Reinhold, New York,
pp 105–106
F
Fiber Models
Vasilis Burganos
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology,
Hellas, Patras, Hellas
A fiber model is a model that uses straight or
curved fibers, either finite in length or infinitely
long, to represent the solid phase in a porous
material or a reinforcement component in a com-
posite material. Fiber models are the appropriate
choice for modeling fibrous media, woven or
nonwoven, typically synthetic but occasionally
also natural ones. Typical examples include the
representation of membranes and porous media
for fuel cells (Mathias et al. 2003), filters for the
separation or sieving of particulate matter, or
filters for the exclusion of bubbles in diverse
applications of microfluidics. There is a recent
rapid growth of interest in the utilization of fiber
models for the description of the structure of gas
diffusion layers in fuel cells but also of modern
textiles and fabrics for specialized applications
(Thiedmann et al. 2009; Gaiselmann et al. 2012).
The typical features that characterize a fiber
model include the diameter and length of the
fiber, the number or length density per unit vol-
ume, the solid fraction, the shape of the fibers,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1056-2
and the elastic properties of the fibers that deter-
mine the macroscopic mechanical properties of
the material. Carbon cloth, electrospun polyacry-
lonitrile, and polyester are common examples of
fibrous materials that can be represented by fiber
models. To convert to a pore model, various
attempts have been made to infer some effective
pore sizes from the fiber model, usually with the
help of inscribed spheres among neighboring
fiber segments. Skeletonization of a fiber model
is often part of the analysis routine to facilitate the
comprehension of the fiber cluster articulation
and the eventual determination of the topology
of the system. Useful concepts from straight-line
path statistics or randomness of secant distribu-
tion through convex bodies (Coleman 1969) are
incorporated in this type of models. The fibers
can be hollow or solid, randomly oriented or
ordered to arbitrary degree, and either charged
or neutral depending on the application. Fiber
models of membrane materials and, more gener-
ally, fibrous media lend themselves to the numer-
ical simulation of transport phenomena through
their structure, usually diffusion, single or,
two-phase flow, dispersion, particle attraction
and deposition, combined phase transition and
flow, heat conduction, electrical conduction, and
light transmission (Torquato 2002; Tomadakis
and Sotirchos 1993).
2 Fiber Models
References
Coleman R (1969) Random paths through convex bodies.
J Appl Probab 6:430–441
Gaiselmann G, Thiedmann R, Manke I, Lehnert W,
Schmidt V (2012) Stochastic 3D modeling of fiber-
based materials. Comput Mater Sci 59:75–86
Mathias MF, Roth J, Fleming J, Lehnert W (2003)
Diffusion media materials and characterisation.
In: Vielstich W, Lamm A (eds) Handbook of fuel
cells, volume III, chapter 42, 517–537, J. Wiley &
Sons, London
Thiedmann R, Hartnig C, Manke I, Schmidt V, Lehnert
W (2009) Local structural characteristics of pore space
in GDLs of PEM fuel cells based on geometric 3D
graphs. J Electrochem Soc 156:B1339–B1347
Tomadakis MM, Sotirchos SV (1993) Ordinary and tran-
sition regime diffusion in random fiber structures.
AIChE J 39:397–412
Torquato S (2002) Random heterogeneous materials –
microstructure and macroscopic properties. Springer-
Verlag, New York
G
Grain Models
Vasilis Burganos and Eugene Skouras
Institute of Chemical Engineering Sciences,
Foundation for Research and Technology,
Hellas, Patras, Hellas
Grain models involve a set of grain-shaped
objects to represent the solid phase in the interior
of porous materials. Model representation of the
structure of porous membranes is very important
for visualizing and understanding the structure of
amorphous, porous, and random membrane
materials and can be implemented, among other
ways, by deterministic or stochastic modeling of
the outcome of the actual fabrication process
(e.g., random assembly or sequential deposition
of particles) with or without reference to the
detailed physics of the process (Preparata and
Shamos 1985). Typically, such reconstructions
involve some random packing, optionally com-
bined with ballistic deposition of hard or soft
spheres, disks, or ellipsoids of prolate or oblate
geometry (Rogers 1964). This stage is usually
followed by simulation of grain sintering as the
result of thermal or viscous sintering. In the
majority of packing procedures, random sequen-
tial deposition of overlapping or non-overlapping
particles takes place (Jaeger and Nagel 1992).
The particles position themselves either ran-
domly or under the influence of some unidirec-
tional force (ballistic) or, alternatively, toward
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1057-2
some fixed center of attraction (Finney 1970).
Ballistic random sphere packs are usually driven
by gravity and are considered to be more repre-
sentative of the compaction process. Ballistic
deposition and central attraction methods provide
packings with similar structural properties in
terms of the autocorrelation function. Depending
on the type of fabrication process as well as on the
characteristic dimensions of the grains, other
forces, either local/short ranged (van der Waals,
double layer, hydrodynamic) or long ranged
(electrostatic, electromagnetic), can also be
taken into account during simulations. One, two,
or three points of contact can be assumed to
discontinue the downhill motion of the particle.
In energy-based models, downhill motion of a
particle continues until a position of local energy
minimum is reached that is considered stable.
Such a procedure can be systematically followed
through the use of a steepest descent method
followed by a conjugate gradient algorithm
(Conway and Sloane 1993). Procedures based
on Monte Carlo or similar statistical methods
have also been implemented, where each time a
number of test grains are inserted, but only
selected displacements are allowed that lead to
minima of position or energy. Motion and inter-
action of granular particles have also been stud-
ied mechanistically with computational methods,
such as the discrete element method (DEM), also
called a distinct element method (Zhu et al. 2007,
2008), for computing the motion and effect of a
large number of small particles. Although DEM
2 Grain Models
Grain Models,
Fig. 1 Ballistic
reconstruction followed by
partial sintering
is closely related to molecular dynamics, the
method is generally differentiated by its inclusion
of rotational degrees of freedom, as well as
compacted and other complex granular geome-
tries. Grain models have also been used for the
description of micro- or nanoparticle additives,
also called nanofillers (at least one of the parti-
cles’ dimensions is in the nanometer range), into
a polymer membrane to form a polymeric com-
posite membrane or a hybrid, mixed matrix mem-
brane (Sanchez et al. 2005). This is a promising
idea to improve the separation properties of the
neat polymer and produce the so-called
nanobarriers with numerous applications in gas
separation, fuel cells, preservation of sensitive
products, etc. The enhancement of barrier prop-
erties through the addition of inorganic
nanoparticles in polymer matrices can be studied
with the help of grain models and elucidate their
complex dependence on interfacial interactions,
filler shape and orientation with respect to the
transport direction, filler size, distribution of
inter-filler distances, and degree of agglomera-
tion (Fig. 1).
References
Conway JH, Sloane NJA (1993) Sphere packings, lattices,
and groups, 2nd edn. Springer, New York
Finney JL (1970) Random packings and the structure of
simple liquids. I. The geometry of random close pack-
ing, Proc R Soc Lond A-Math Phys Sci 319:479–493
Jaeger HM, Nagel SR (1992) Physics of granular states.
Science 255(5051):1523–1531
Preparata FP, Shamos MI (1985) Computational geome-
try: an introduction. Springer, New York
Rogers CA (1964) Packing and covering. Cambridge Uni-
versity Press, Cambridge
Sanchez C, Julian B, Belleville P, Popall M (2005) Appli-
cations of hybrid organic-inorganic nanocomposites.
J Mater Chem 15:3559–3592
Zhu HP, Zhou ZY, Yang RY, Yu AB (2007) Discrete
particle simulation of particulate systems: theoretical
developments. Chem Eng Sci 62:3378–3392
Zhu HP, Zhou ZY, Yang RY, Yu AB (2008) Discrete
particle simulation of particulate systems: a review of
major applications and findings. Chem Eng Sci
63(23):5728–5770
A
Amorphous Polymers
and the Amorphous Region
Petr Sysel
Department of Polymers, Institute of Chemical
Technology, Prague, Czech Republic
Polymers consist of the large molecules (polymer
chains). An arrangement of these chains in
the bulk polymer is given by their chemical com-
position, spatial orientation (e.g., an isotactic vs
atactic polypropylene), molecular weight, and
processing conditions (e.g., a cooling rate).
Based on these factors, bulk polymers show an
amorphous or partially crystalline
(semicrystalline) phase state. In the amorphous
state, an ordering of the (entangled) polymer
chains is random. The amorphous polymer does
not include a long-range order, but it is charac-
terized by the existence of some regularity on a
short-range order. As a consequence of it, an
X-ray diffraction provides a diffuse ring only
(a set of discrete rings is typical for well-ordered
structures). If the amorphous polymer is exposed
to a gradually increased temperature, it passes
from a glass (hard and rigid) to a rubber (soft
and flexible) and finally to a molten consistency.
Boundaries between the glass/rubber and rubber/
molten consistency are given by a glass transition
temperature (Tg) and flow temperature, respec-
tively (see a thermomechanical curve of an amor-
phous polymer, Fig. 1).
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1059-5
The glass transition temperature of the poly-
mer is also an important indicator of its applica-
tion temperature region (e.g.,
polydimethylsiloxane (Tg = ca 120  C) is rub-
bery and polystyrene (Tg = ca +100  C) is a
glassy polymer at room temperature).
A character of the main backbone (flexible/
rigid), its substitution (small vs bulk substitu-
ents), and a level of molecular (chain) interac-
tions (e.g., van der Waals forces vs hydrogen
bonds) are important factors influencing the posi-
tion (value) of this transition. A flexibility of the
chains (or segments) of an amorphous polymer is
restricted at temperatures below its Tg. Under
heating, molecular interactions (secondary
forces) are disrupted, and a free volume among
more flexible chains increases (Fig. 2).
An extent of this (segmental) chain motion
and free volume influences a lot of the polymer
properties, e.g., a transport of the different
low-molecular-weight media through the mem-
branes made of these polymers (Strathmann
2011). For example, a nonporous (dense)
membrane made of a rubbery polysiloxane
[( Si(R)2-O-)n, where R is often CH3] shows a
much higher gas permeation (and also diffusivity)
in comparison with those made of common
glassy polymers at room temperature (Pandey
2001; Bernardo et al. 2009). But their selectivity
is traditionally low (Robeson 2008).
Some polymers (e.g., polyethylene, polyam-
ides) include both amorphous and crystalline
fractions, and they are called semicrystalline
2 Amorphous Polymers and the Amorphous Region

deformation

glassy state rubbery state plastic state

glass transition flow temperature

temperature
temperature

Amorphous Polymers and the Amorphous Region, Fig. 1 Thermomechanical curve of an amorphous polymer

Amorphous Polymers
and the Amorphous
Region,
Fig. 2 Temperature specific
dependence of the specific volume
volume of an amorphous
polymer

glass transition
temperature

temperature

ones. Chains of such polymers may be organized
in spherulites having a well-ordered lamellar
structure (i.e., a folded chain) with an incorpo-
rated disordered amorphous fraction (Fig. 3).
Amorphous polymers are usually transparent;
semicrystalline ones are opaque. A segmental
mobility of the amorphous regions in
semicrystalline polymers varies from that of the
amorphous polymer. These regions are affected
by the presence of crystalline phase, and this
phenomenon influences also transport character-
istics of the penetrating media. Traditionally, the
“more dense” crystalline phase decreases a chain
mobility and prolongs a transport trajectory of
Amorphous Polymers and the Amorphous Region
Amorphous Polymers
and the Amorphous
Region, Fig. 3 Schematic
arrangement of the
spherulite
penetrating media, and – as a consequence of
this – their permeability decreases (Pandey
2001). Nevertheless, some exceptions were also
found, e.g., an increase of gas permeability in a
polylactide membrane with its increasing crystal-
linity (Colomines et al. 2010).
References
Bernardo P, Drioli E, Golemme G (2009) Membrane gas
separation. Ind Eng Chem Res 48:4638–4663
3
amorphous region
lamellar structure
Colomines G, Ducruet V, Courgneau C, Guinault A,
Domenek S (2010) Barrier properties of poly(lactic
acid) and its morphological changes induced by
aroma compound sorption. Polym Int 59:818–826
Pandey P, Chauhan RS (2001) Membranes for gas sepa-
ration. Prog Polym Sci 26:853–893
Robeson LM (2008) The upper bound revisited. J Membr
Sci 320:390–400
Strathmann H (2011) Introduction to membrane science
and technology. Wiley-VCH, Weinheim
D
Density Functional Theory Modeling
of Membrane Systems
Giorgio De Luca
Institute on Membrane Technology ITM-CNR,
University of Calabria, Rende (CS), Italy
Density functional theory is a new methodology
in the frame of quantum mechanics (ab initio).
The assessment of material features depending on
the electron interactions or electron density
polarization necessarily needs the use of quantum
mechanics. Large molecular systems cannot be
described with accurate quantum mechanical
approaches, such as correlated Hartree-Fock
(Szabo and Ostlund 1994), due to the huge com-
putational time required by these. Instead, the
density functional theory (Parr and Yang 1989)
allows to get results with similar precision in
relatively shorter computational time. Thus,
density functional theory is a powerful tool to
investigate large chemical systems like the
nanostructures involved in the membrane prepa-
ration. In density functional theory, the total
energy of an electronic system is evaluated
through a total functional which depends on the
electron density of the quantum system, r(r), and
external potential v(r). It is defined as follows:
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1062-1
EDFT ½rðrÞ ¼ Ts ½rðrÞ þ J½rðrÞ þ Exc ½rðrÞ
ð
þ vðrÞrðrÞdr
where Ts[r(r)] is the kinetic energy of an isoelec-
tronic noninteracting system, while J[r(r)]
describes the Coulomb electrostatic energy. The
Exc[r(r)] is the exchange and correlation func-
tional, which takes into account the difference
between the kinetic energies of the isoelectronic
interacting and noninteracting systems in addi-
tion to the difference between the quantum
electron-electron and Coulomb electrostatic
energy. r(r) can be evaluated by the nonlinear
Kohn-Sham equations, defined by means of an
effective potential. The electron density allows to
calculate all the properties of the quantum system
in addition to the total energy. Computational
approaches, based on density functional theory,
are applied in the study of catalysts used in mem-
branes and in the study of noncovalent interac-
tions, such as hydrogen-bonding and London
dispersion interactions (De Luca et al. 2009). In
fact, hydrogen-bonding, electrostatic interactions
and London force are important for membranes at
the basis of fundamental properties such as
molecular adsorption and sorption, recognition,
and self-assembly. Also size, shape, and electro-
static features of supramolecular architectures
can be studied using density functional theory.
All these properties control the selectivity of the
materials, used in membranes, the permission as
well as the antifouling or anti-embrittlement
2 Density Functional Theory Modeling of Membrane Systems
features. Density functional theory studies of the
catalysis in membrane reactors require the defi-
nition of structural models of the catalysts. For
the most part, they are modeled by infinite sur-
faces, slabs, or different types of adsorbed or
absorbed atomic clusters. These studies could be
treated independently from the aforementioned
analysis. However, it is important to emphasize
that the merging of the results obtained by the
different investigations would be advisable. For
example, the kinetic constants characterizing a
reaction path, related to a particular catalyst,
evaluated by the density functional theory,
should be compared with the diffusion coeffi-
cients characterizing the permeability of reagents
and products through the membrane derived by
the adsorption/absorption of different molecules.
References
De Luca G, Gugliuzza A, Drioli E (2009) Competitive
hydrogen-bonding interactions in modified polymer
membranes: a density functional theory investigation.
J Phys Chem B 113:5473–5477
Parr RG, Yang W (1989) Density functional theory of
atoms and molecules. Oxford University Press, New
York
Szabo A, Ostlund NS (1994) Modern quantum chemistry.
Macmillan Publishing CO, New York
E
Ethanol-Water Mixtures: Separation
by Pervaporation
Kew-Ho Lee
Department of Chemical and Biomolecular
Engineering, National Research Laboratory for
Environmental Catalysis, Korea Research
Institute of Chemical Technology (KRICT),
Yuseong-gu, Daejeon, South Korea
Pervaporation is an important membrane process
in chemical industries in which valuables are iso-
lated from the liquid mixture. Liquid and vapor
separation by thermal processes has always been
highly energy intensive, and new separation pro-
cesses taking advantage of mass transfer through
dense membranes have already shown they enable
very significant energy savings as compared to
more classic technologies (Anne et al. 2002).
Membranes can be used for the selective removal
of water from aqueous organic mixtures.
Pervaporation (PV) is a separation process that
involves separation of liquid mixtures, in contact
with a membrane. With feed solution on one side,
permeate is removed as a vapor from the other
side (Brian et al. 2011); pervaporation (PV) is a
very well-known membrane process for the sepa-
ration of liquid and vapor mixtures due to its
energetic aspects (EP 909209A1 1999; EP
944575A1 1999; EP 880400A1 1998).
Pervaporation mostly allows a variety of possible
application areas: dewatering of organic fluids
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1063-1
like alcohols, ketones, ethers, etc. (EP 765682A1
1997); separation of mixtures from narrow boiling
temperatures to constant (azeotrope) boiling tem-
peratures (EP 811420A1 1997); removal of
organic pollutants from water and air streams
(EP 749351A1 1996); separation of fermentation
products; and separation of organic-organic liquid
mixtures (Kujawski 2000). Pervaporation is also
considered as so-called clean technologies, espe-
cially well suited for the treatment and recycling
of volatile organic compounds and pollution pre-
vention (Anne et al. 2002).
Transport mechanism of PV through poly-
meric membranes was studied by many research
groups, and it was explained by the solution-
diffusion model (Binning et al. 1961; Paul and
Paciotti 1975; Lee 1975; Mulder and Smolders
1984; Kataoka et al. 1991a, b). According to the
solution-diffusion model, each component of the
permeation molecules dissolves into the mem-
brane and diffuses through the membrane due to
the concentration gradient (Mikihiro et al. 1998)
(Fig. 1).
Transport through the membrane is driven by
the vapor pressure difference between the feed
solution and the permeate vapor. The vapor pres-
sure difference can be maintained by applying a
vacuum on the permeate side or by cooling the
permeate vapor so that it condenses, thus creating
a partial vacuum. Commercial systems for the
dehydration of concentrated alcohol and other
solutions have been developed since the 1980s,
much of the push coming from interest in the
2 Ethanol-Water Mixtures: Separation by Pervaporation
Ethanol-Water Mixtures:
Separation by
Pervaporation,
Fig. 1 Solution-diffusion
mechanism (Graham 1866)
production of pure ethanol as an alternative liquid
fuel, where PV can be used to dehydrate (Brian
et al. 2011).
Pervaporation Membranes
Polymeric Membranes
For dehydration, where the small molar volume
favors the preferential sorption of water, materials
have to be selected with a higher affinity for water
than for the other component. The polymeric
materials can be broadly classified into three cat-
egories: glassy polymers, rubbery or elastomeric
polymers, and ionic polymers. In general, the
glassy and ionic polymers are more suited for
making water-selective membranes for
dehydration.
For water-selective membranes, the most
important factor responsible for the separation is
the specific interaction between water and the
polymer. To obtain high selectivities, it is neces-
sary to use polymers, which contain specific
groups/active centers, capable of strong interac-
tions with water.
The highest fluxes are those for the hydrophilic
membranes based on cellulose and Nafion and
grafts of hydrophilic poly(vinylpyrrolidone) on
Teflon and polyacrylonitrile. The PVA/TEOS
1. Sorption
Micrivoids
Polymer
2. Diffusion
Microchannels
3. Desorption
membranes are exceptions in that they are hydro-
philic but exhibit low fluxes (Brian et al. 2011)
(Table 1).
The emphasis is on selectivity, postulated to be
determined by selective sorption and selective
diffusion. Selective sorption is governed by the
presence in the membrane of active centers such
as charged sites which are capable of specific
interaction with water, while selective diffusion
is governed by the rigidity and regularity of the
polymer structure and the nature of the polymer
interspace, exemplified by the degree of swelling
and the frequency of the cross-links. The results
for a series of membranes made by grafting neu-
tral or charged polymers onto supporting mem-
branes are reported in (Table 2).
Polysalts, formed from anionic and cationic
polyelectrolytes, would be appropriate for
obtaining both highly permeable and highly selec-
tive membranes (Semenova et al. 1997) (Table 3).
The best performers in terms of flux, which at a
maximum of 5 kg/m2h never achieve high values,
are charged polymers of one type or another,
including polysalts. Anionic and polysalt mem-
branes are superior. For anionic polymers, the
proton form has a significantly higher flux than
the metal or quaternary ammonium salt versions,
owing to the greater free space within the polymer
network (Table 4).
Ethanol-Water Mixtures: Separation by Pervaporation 3

Ethanol-Water Mixtures: Separation by Pervaporation, Table 1 PV dehydration of ethanol through various

polymeric membranes (Brian et al. 2011)
Polymer Feed (wt% water) Temp. ( C) Separation factor Flux (g/m2h)
Regenerated cellulose 50 45 5.0 2060
Cellulose acetate 4 60 5.9 200
Teflon-g-polyvinylpyrrolidone 4 25 2.9 2200
Perfluorinated polymer on PAN support 1.3 50 387 1650
Nafion-H+ 4 70 2.5 5000
Polyacrylonitrile-polyvinylpyrrolidone 4 20 3.2 2200
Poly(maleimide-co-acrylonitrile) 15 15 33 8
Poly(acrylic acid-co-acrylonitrile) 18 15 877 13
Polystyrene 4 40 101 5
Poly(vinyl chloride) 4 40 63 3
Alginic acid 4 40 8.8 48
5 60 13 2800
Chitosan 4 40 2208 4
Chitosan acetate salt 4 40 2556 2
Chitosan/glutaraldehyde 4 40 202 7
PVA/25 % TEOS, annealed at 160  C 15 40 329 5
PVA/25 % TEOS, annealed at 130  C 15 40 893 4

Ethanol-Water Mixtures: Separation by Pervaporation, Table 2 PV dehydration of 20 % aqueous ethanol at 70  C

using graft polymer membrane having different charges (Brian et al. 2011)
Host polymer Grafted polymer Graft site charge Separation factor
Polyvinylidene fluoride 4-Vinylpyridine Neutral 9
Polyvinylidene fluoride N-Vinyl-imidazole Neutral 10
Polyvinyl fluoride N-Vinylmethyl-acetamide Neutral 4
Polyvinyl fluoride N-Vinyl-pyrrolidone Neutral 7
Polyacrylonitrile Acrylic acid Neutral 10
Polyacrylonitrile K+ acrylate Anionic 500
Polyvinyl fluoride K+ acrylate Anionic 156
Polyvinylidene fluoride Quaternized 4-vinylpyridine Cationic 175
Polyvinylidene fluoride Quaternized N-vinylimidazole Cationic 61
Polyvinylidene fluoride 4-Vinylpyridine/BrCH2COOH Zwitterionic 76
Polyvinyl fluoride Vinylimidazole/BrCH2COOH Zwitterionic 63

Hybrid Membranes are several reports showing good separation per-

Many a times, the polymeric membranes may fail
to meet the desired separation requirements. In
such cases, it becomes necessary to add filler
materials such as ceramics and zeolites to improve
the separation properties of the membrane. There
formance for ethanol/water mixture using zeolite
membranes (Kita et al. 1995; Sano et al. 1994).
Kita et al. made NaA-type zeolite membrane by
hydrothermal synthesis. NaA zeolite membrane is
a water-selective membrane, and the PV
4 Ethanol-Water Mixtures: Separation by Pervaporation

Ethanol-Water Mixtures: Separation by Pervaporation, Table 3 PV dehydration of aqueous ethanol with mem-
brane based on various polysalts (Brian et al. 2011)
Feed (wt% Temp. Separation Flux
Polyanion Polycation water) ( C) factor (g/m2h)
Poly(acrylonitrile-co- Poly(acrylonitrile-co-vinyl pyridine) 10 – 5000 400
acrylic acid)
Cellulose-SO3-Na+ Polyethyleneimine 16 50 295 1900
Cellulose-SO3-Na+ PolyDADMAC, linear 16 50 140 3200
Cellulose-SO3-Na+ Same, but branched 16 50 123 4900
Cellulose-SO3-Na+ Poly-N, N-dimethyl-3, 5- 16 50 123 2700
dimethylenepiperidine chloride
Aromatic polyamide Polyethyleneimine 20 60 15 300
sulphonate
Poly(acrylic acid) Chitosan
On polysulphone supporting membrane 5 30 1008 132
No supporting membrane 5 30 2216 33
Na+ polystyrene Polyallylamine HC1 6.2 70 70 230
sulphonate
Na+ CMC Chitosan 10 70 1062 1140
Na+ CMC N-Ethyl-4-vinyl-pyridinium bromide 10 70 782 1320
Anionic PVA Cationic PVA
DS 2.3 % DS 2.9 % 4.6 75 2250 378
DS 5.0 % DS 5.2 % 4.6 75 1910 284

Ethanol-Water Mixtures: Separation by Pervaporation, Table 4 Highest fluxes for PV dehydration of aqueous
ethanol (Brian et al. 2011)
Separation
Membrane polymer Mem. type Feed (wt% water) Temp. ( C) Flux (g/m2h) factor
Nafion-H+ Anionic 4 70 5000 2.5
Cellulose-SO3-Na+ and Polysalt 16 50 4900 125
polyDADMAC, branched
K+ acrylate graft on poly(vinyl Anionic 20 70 4700 156
fluoride)
PEI/PAA on RO membrane Polysalt 10+ 70 4050 1075
Cellulose-SO3-Na+ and Polysalt 16 50 3200 140
polyDADMAC, linear
K+ acrylate graft on PAN Anionic 20 70 3000 500

separation factor of water/ethanol system was
over 10,000 at 348 K. For ethanol permselective
membranes, Sano et al. (1994) prepared polycrys-
talline silicalite membrane by the hydrothermal
synthesis.
The silicalite membrane showed high ethanol
permselectivity, and a separation factor of 58 was
realized at 333 K by PV. Silicalite membranes
seem to have great potential for the ethanol recov-
ery by PV (Table 5).
Ethanol-Water Mixtures: Separation by Pervaporation 5

Ethanol-Water Mixtures: Separation by Pervaporation, Table 5 PV dehydration of ethanol using PVA/inorganic

hybrid membranes (Brian et al. 2011)
Crosslinker Feed (wt% water) Temp. ( C) Separation factor Flux (g/m2h)
TEOS (160  C) 15 40 329 50
TEOS (130  C) 15 40 893 40
PEG blend and TEOS 15 50 300 46
No PEG 15 50 160 500
Poly(acrylic acid) copolymer and TEOS 15 40 250 18
g-Aminopropyl-triethoxysilane 5 50 537 36
Sulphated zirconia 5 50 263 10
10 50 142 105
20 50 86 183
30 50 61 1036

References Kataoka T, Tsuru T, Nakao S, Kimura S (1991b) Mem-

Anne J, Robert C, Pierre LND, Bruno C (2002) Industrial
state-of-the-art of pervaporation and vapour perme-
ation in the western countries. J Membr Sci 206:87–117
Binning RC, Lee RJ, Jennings JF, Martin EC (1961) Sepa-
ration of liquid mixtures by permeation. Ind Eng Chem
53:45
Brian B, Manh H, Zongli X (2011) A review of membrane
selection for the dehydration of aqueous ethanol by
pervaporation. Chem Eng Process 50:227–235
EP 749351A1 (1996) Device for separating mixtures or for
purifying substances by pervaporation
EP 765682A1 (1997) Apparatus for separating liquid
media with two membranes having their primary sides
connected by an intermediate space
EP 811420A1 (1997) Composite membrane for selective
separating organic substances by pervaporation
EP 880400A1 (1998) Composite membrane with a support
membrane made in particular of a microporous material
EP 909209A1 (1999) Pervaporisation and module for car-
rying out said process
EP 944575A1 (1999) Esterification of fermentation-
derived acids via pervaporation
Graham T (1866) On the absorption and dialytic separation
of gases by colloid septa. Philos Mag J Sci 32:401–420
Kataoka T, Tsuru T, Nakao S, Kimura S (1991a) Perme-
ation equations developed for prediction of membrane
performance in pervaporation, vapor permeation and
reverse osmosis based on the solution diffusion
model. J Chem Eng Jpn 24:326
brane transport properties of pervaporation in
ethanolwater system using polyacrylonitrile and cel-
lulose acetate membranes. J Chem Eng Jpn 24:334
Kita H, Horii K, Ohtoshi Y, Tanaka K, Okamoto K (1995)
Synthesis of a zeolite NaA membranefor pervaporation
of water/organic liquid mixtures. J Mater Sci Lett
14:206
Kujawski W (2000) Application of pervaporation and
vapor permeation in environmental protection. Pol
J Environ Stud 91:13–26
Lee CH (1975) Theory of reverse osmosis and some other
membrane permeation operations. J Appl Polym Sci
1983
Mikihiro N, Takeo Y, Sin-ichi N (1998) Ethanol/water
transport through silicalite membranes. J Membr Sci
144:161–171
Mulder MHV, Smolders CA (1984) On the mechanism of
separation of ethanol/water mixtures by pervaporation
I. Calculations of concentration profiles. J Membr Sci
17:289
Paul DR, Paciotti JD (1975) Driving force for hydraulic
and pervaporative transport in homogeneous mem-
branes. J Polym Sci 13:1201
Sano T, Yanagishita H, Kiyozumi Y, Mizukami F, Haraya
K (1994) Separation of ethanol/water mixture by
silicalite membrane on pervaporation. J Membr Sci
95:221
Semenova SI, Ohya H, Soontarapa K (1997) Hydrophilic
membranes for pervaporation: an analytical review.
Desalination 110:251–286
P
Pd–Cu Alloys for Hydrogen
Separations
Kew-Ho Lee
Center for Membranes, Korea Research Institute
of Chemical Technology (KRICT), Yuseong-gu,
Daejeon, South Korea
Pd–Cu alloys have been widely studied as a
hydrogen separation membrane because they do
not show embrittlement even at low temperatures
(Kulprathipanja et al. 2005; Miller et al. 2008).
Studies by Morreale et al. have shown that the
face-centered cubic (fcc) phase is more resistant
to sulfur than the body-centered cubic (bcc) phase
(Morreale et al. 2004). In transient experiments,
the fcc Pd–Cu composition showed a decline of
0–10 % when exposed to 1,000 ppm of sulfur,
while a bcc Pd–Cu composition had a decline of
99 %. Studies by Pomerantz and Ma (Pomerantz
and Ma 2009) confirm these results for Pd–Cu
compositions of 8, 18, and 19 wt.% Cu, with
permeance losses of 80 % at 500  C (773 K).
They further showed that the loss was partially
reversible by hydrogen treatment. A recent study
by Howard and coworkers (O’Brien et al. 2010)
shows that Pd exposed to 1,000 ppm sulfur at
350  C (623 K) corrodes over a period of hours
to form a thick (6.6 mm) PdS4 layer, probably by
an autocatalytic process. In contrast a Pd47Cu53
alloy forms a thin (3 nm) Pd–Cu–S layer.
Although this layer cannot dissociate hydrogen
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1064-1
or is impermeable to hydrogen, it does protect the
bulk from sulfidation and could be removed by a
hydrogen treatment.
The alloying of Cu with Pd increases the resis-
tance for the a to b phase transition in Pd–H
system. Moreover the phase transition in the
Pd–H system is eliminated even at room temper-
ature by adding more than 8 wt.% Cu in Pd
(Karpova and Tverdovskii 1959). McKinley
(McKinley et al. 1969) studied the permeation
characteristics of Pd–Cu alloys with different
compositions. The H2 permeabilities of various
alloys are shown in Table 1. Out of all other
Pd–Cu alloys, the Pd60Cu40 shows the highest
permeability which corresponds to the ordered
b-phase in Pd–Cu system (McKinley and
US. Patent 3, 439, 474 1969). In contrast, it is
reported that Pd47Cu53 (mol%) alloy has the
highest hydrogen permeability at 350  C among
the Pd–Cu alloys (Yuan et al. 2007; Yang
et al. 2007; McKinley et al. 1969; Roa
et al. 2002) and is comparable in its hydrogen
permeability to pure Pd at the same temperature.
The solubility of Pd–Cu (20 % Cu) is five times
smaller than that of pure Pd, which corresponds
to the permeability behavior of that alloy
(Sonwane et al. 2006).
In summary Pd–Cu (particularly Pd60Cu40) is
the most promising composition; has the charac-
teristics of having high hydrogen permeance,
good sulfur resistance, robustness w.r.t. thermal
cycling, and an excellent dimensional stability
(small degree of swelling); is cheaper; eliminates
2 Pd–Cu Alloys for Hydrogen Separations

Pd–Cu Alloys for Hydrogen Separations, McKinley DL (1969) Method for hydrogen separation and
Table 1 Permeabilities of Pd–Cu alloys with different purification, USA
wt.% of Cu at 350  C, 300 psig Miller JB, Morreale BD, Gellman AJ (2008) The effect of
adsorbed sulfur on surface segregation in a polycrys-
wt.% Permeability (Cm3/cm2.s)
talline Pd70Cu30 alloy. Surf Sci 602:1819–1825
90Pd–10Cu 0.69 Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
70Pd–30Cu 0.12 Cugini AV, Enick RM (2004) Effect of hydrogen-
60Pd–40Cu 1.52 sulfide on the hydrogen permeance of palladium-
550Pd–45Cu 0.25 copper alloys at elevated temperatures. J Membr Sci
241:219–224
45Pd–55Cu 0.01
O’Brien CP, Howard BH, Miller JB, Morreale BD,
90Pd–10Cu 0.69 Gellman AJ (2010) Inhibition of hydrogen transport
through Pd and Pd47Cu53 membranes by H2S at
350  C. J Membr Sci 349:380–384
Pomerantz N, Ma YH (2009) Effect of H2S on the perfor-
mance and long-term stability of Pd/Cu membranes.
warping and cracking; and avoids a to b phase Ind Eng Chem Res 48:4030–4039
transition in pure Pd (Gabitto and Tsouris 2009). Roa F, Block MJ, Way JD (2002) The influence of alloy
composition on the H2 flux of composite Pd–Cu mem-
branes. Desalination 147:411–416
Sonwane CG, Wilcox J, Ma YH (2006) Solubility of
References hydrogen in PdAg and PdAu binary alloys using den-
sity functional theory. J Phys Chem
Gabitto JF, Tsouris C (2009) Sulfur poisoning of metal B 110:24549–24558
membranes for hydrogen separation. Int J Chem Eng Yang JY, Nishimura C, Komaki M (2007) Effect of H2S
1:394–411 on hydrogen permeation of Pd60Cu40/V–15Ni com-
Karpova RA, Tverdovskii IP (1959) Sorption of hydrogen posite membrane. J Alloys Compd 446–447
by disperse Pd-Cu alloys. Zhur Fiz Khim 33:1393 Yuan L, Goldbach A, Xu H (2007) Segregation and H2
Kulprathipanja A, Alptekin GO, Falconer JL, Way JD transport rate control in body centered cubic PdCu
(2005) Pd and Pd–Cu membranes: inhibition of H2 membranes. J Phys Chem B 111:10952–10958
permeation by H2S. J Membr Sci 254:49–62
McKinley DL (1969) US. Patent 3,439,474
E
Emulsion
Emma Piacentini
Institute on Membrane Technology. (ITM-CNR),
University of Calabria, Rende CS, Italy
An emulsion consists of two immiscible liquids
(usually oil and water) with one of the liquids
(dispersed phase or internal) dispersed as a form
of spherical droplets in the other (continuous phase
or external) (Israelachvili 1994). Depending upon
the nature of the dispersed phase, the emulsions are
classified as (i) oil-in-water emulsions (O/W)
consisting of oil droplets dispersed in an aqueous
phase and (ii) water-in-oil emulsions (W/O)
consisting of aqueous droplets dispersed in an oil
phase. It is also possible to prepare various types of
multiple emulsions, for example, water-in-oil-in-
water emulsions (W/O/W), in which water droplets
are dispersed within larger oil droplets which are
themselves dispersed in an aqueous phase and
oil-in-water-in-oil emulsions (O/W/O) consisting
of oil droplets dispersed in larger water droplets
which are themselves dispersed in an oil phase.
The preparation of an emulsion is termed
emulsification and the agents used for this pur-
pose are termed emulsifiers. Other agents, such as
emulsion promoters or stabilizers, are often
added to an emulsion to promote the emulsifying
process, for example, by increasing the viscosity
or providing a protective colloid action. The
preparation of emulsions involves breaking up
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1066-1
the internal phase by supplying mechanical or
chemical energy. When an emulsion is formed,
the interface between the phases is considerably
increased as a result of the droplet formation. The
liquid always tends to reduce its surface or inter-
face to a minimum; therefore, an increase in
interface is possible only if energy is supplied.
The work that must be expended on drop division
is:
dA ¼ g dI
where dA is the work to be expended and dI is the
increase in interface. The proportionality factor is
the interfacial tension g between the phases to be
emulsified. Thus, if the interfacial tension
between the two phases is high, considerable
mechanical energy is required for emulsification
unless an emulsifier is added; if the interfacial
tension is low, little mechanical energy is
consumed.
According to the droplet size, emulsions are
classified as follows:
• Macroemulsions: these usually have a size
range of 0.1–5 mm.
• Nanoemulsions: these usually have a size
range of 20–100 nm.
• Micellar emulsions or microemulsions: these
usually have a size range of 5–50 nm.
2 Emulsion
Emulsion, Fig. 1 The
various breakdown
processes in emulsions
No change in droplet size and size distribution
FLOCCULATION
CREAMING
SEDIMENTATION
If the droplet size exhibits a wide statistical
distribution, the emulsion is described as polydis-
perse, in contrast to monodisperse systems with a
uniform droplet size. The ideal particle size
depends on the available methods of preparation
and industrial application in each case. Another
important emulsion property is the ratio of the
volume of the dispersed phase (Vi) to the volume
of the continuous phase or (Ve) is called the phase
volume ratio (F). If F < 0.43 (Vi = 30 % of
total volume), the flow properties of the emulsion
are determined primarily by the continuous
phase. If F > 0.43, the viscosity of the emulsion
generally increases. As F increases, either phase
reversal or cream formation occurs.
Emulsion stability should match its applica-
tion. Thus, for a number of applications, the
emulsion should be stable under very specific
conditions, but it should break after its purpose
has been achieved according to a specific condi-
tion (such as temperature, pH, or salts, or the
like). An emulsion is stable if fusion of the drop-
lets is prevented by a sufficiently high energy
barrier (Tadros 2013). In general, the energy bar-
rier is built up by the film of emulsifier that forms
at the surface of the droplets. Several breakdown
Change in droplet size and size distribution
OSTWALD
RIPENING
EMULSION COALESCENCE
PHASE
INVERSION
processes may occur on storage depending on
particle size distribution and density difference
between the droplets and the medium (Fig. 1).
In sedimentation, the uniform dispersion of
the droplets is disturbed by aggregation, which
leads to settling or creaming of the internal phase.
This process results from external forces usually
gravitational or centrifugal. When such forces
exceed the thermal motion of the droplets
(Brownian motion), a concentration gradient
builds up in the system with the larger droplets
moving faster to the top (if their density is lower
than that of the medium) or to the bottom (if their
density is larger than that of the medium) of the
container. To keep an emulsion stable, such
aggregation must be prevented since droplet
aggregates sediment faster than individual small
droplets. Sedimentation is not always necessarily
accompanied by coalescence. Although the dis-
tribution has been altered, the original dispersion
can be restored by shaking or stirring. Floccula-
tion refers to aggregation of the droplets (without
any change in primary droplet size) into larger
units. It is the result of the van der Waals attrac-
tion that is universal with all disperse systems.
Flocculation occurs when there is no sufficient
Emulsion
repulsion to keep the droplets apart to distances
where the van der Waals attraction is weak. Floc-
culation may be “strong” or “weak,” depending
on the magnitude of the attractive energy
involved. One way to overcome the van der
Waals attraction is by electrostatic stabilization
using ionic surfactants, which results in the for-
mation of electrical double layers that introduce a
repulsive energy that overcomes the attractive
energy. The second and most effective method
of overcoming flocculation is by “steric stabili-
zation” using nonionic surfactants or polymers.
Ostwald ripening (disproportionation) results
from the finite solubility of the liquid phases.
Liquids that are referred to as being immiscible
often have mutual solubilities that are not negli-
gible. With emulsions, which are usually poly-
disperse, the smaller droplets will have larger
solubility when compared with the larger ones
(due to curvature effects). With time, the smaller
droplets disappear and their molecules diffuse to
the bulk and become deposited on the larger
droplets. With time, the droplet size distribution
shifts to larger values. Several methods may be
applied to reduce Ostwald ripening: (i) Addition
of a second dispersed phase component that is
insoluble in the continuous medium. In this case,
partitioning between different droplet sizes
occurs, with the component having low solubility
expected to be concentrated in the smaller drop-
lets. During Ostwald ripening in a
two-component system, equilibrium is
established when the difference in chemical
potential between different size droplets (which
results from curvature effects) is balanced by the
difference in chemical potential resulting from
partitioning of the two components. This effect
reduces further growth of droplets.
(ii) Modification of the interfacial film at emul-
sion interface. By using surfactants that are
strongly adsorbed at the emulsion interface (i.e.,
polymeric surfactants) and that do not desorb
during ripening (by choosing a molecule that is
insoluble in the continuous phase), the rate could
be significantly reduced. In coalescence, the indi-
vidual droplets fuse together. First, the smaller
droplets are absorbed by the larger droplets, and
then increasingly larger drops merge together
3
until two continuous phases are finally formed.
The driving force for coalescence is the surface or
film fluctuations which results in close approach
of the droplets whereby the van der Waals forces
is strong thus preventing their separation. Two
droplets can only coalesce if the intervening layer
of liquid is pierced when they approach each
other. Therefore, coalescence is opposed in two
ways by the emulsifier film surrounding the drop-
lets. First, as in the case of aggregation, the like
charges of the electrical double layer prevent
them from approaching each other. Second, the
buildup of an elastic surface film causes the emul-
sion droplets to bounce off each other when they
collide. Coalescence is always followed by accel-
erated settling or creaming, which destroys the
emulsion completely. The emulsion is then bro-
ken and cannot be reconstituted by shaking or
stirring. The driving force for prevention of coa-
lescence is to produce a stable film that can be
achieved by two mechanisms and their combina-
tion: (i) increased repulsion both electrostatic and
steric and (ii) dampening of the fluctuation. In
general, smaller droplets are less susceptible to
surface fluctuations and hence coalescence is
reduced. This explains the high stability of
nanoemulsions. The phase inversion refers to
the process whereby there will be an exchange
between the disperse phase and the medium. For
example, an O/W emulsion may with time or
change of conditions invert to a W/O emulsion.
In many cases, phase inversion passes through a
transition state whereby multiple emulsions are
produced. Phase inversion of emulsions can be
one of two types: transitional inversion induced
by changing the facers that affect the HLB of the
system, for example, temperature and/or electro-
lyte concentration, and catastrophic inversion,
which is induced by increasing the volume frac-
tion of the disperse phase.
Emulsions have application in several indus-
trial systems such as food emulsion, for example,
mayonnaise, salad creams, deserts, and bever-
ages; personal care and cosmetics, for example,
hand creams, lotions, hair sprays, and sunscreens;
and pharmaceuticals, paints, and bitumen
emulsions.
4 Emulsion

References Tadros T F (2013) Emulsion Formation, Stability, and

Rheology, in Emulsion Formation and Stability (ed
Israelachvili J (1994) The science and applications of T. F. Tadros), Wiley-VCH Verlag GmbH & Co.
emulsions - an overview, Colloids and Surfaces A: KGaA, Weinheim, Germany.
Physicochemical and Engineering Aspects 91: 1–8.
B
Bimetallic Electrocatalyst for Fuel
Cells
Dmitri Bessarabov
Faculty of Engineering, DST HySA
Infrastructure Center of Competence, North-
West University, Potchefstroom, South Africa
General Requirements for Fuel Cells
Most of the known today fuel cell systems (e.g.,
automotive, portable applications, backup power,
etc.) have common requirements that include
reduction in costs, improvement in performance
and durability, increase in tolerance toward
impurities in the feed fuel, etc. (Vielstich
et al. 2003a; Debe 2012).
Pt-based Electrocatalyst: Key
Component
The platinum-based electrocatalyst used in PEM
(proton-exchange membrane, also called poly-
mer electrolyte membrane) fuel cells, PAFC
(phosphoric acid fuel cell), and DMFC (direct
methanol fuel cell) is one of the key components
and directly influences performance, durability,
costs, etc. More specifically, in the PEM fuel cell,
the oxygen reduction reaction (ORR) occurring at
the cathode is known to have slow kinetics, lead-
ing to large cathodic overpotential losses under
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1083-3
typical operating conditions. In the case of spe-
cific application of PEM fuel cells, when hydro-
gen is produced from a reformate, an additional
requirement such as tolerance of the anode
electrocatalyst toward the traces of CO in the
feed fuel stream must also be met. In order to
reduce costs of the fuel cells, an increased mass
activity of the cathode electrocatalyst is required
that would allow a decrease in the amount of the
electrocatalyst in a fuel cell device.
Advanced Electrocatalysts
A search for better ORR electrocatalysts for PEM
fuel cells that meet advance requirements has
resulted in the development of various Pt-based
bimetallic compounds (these can include alloys
or intermetallic systems). It is believed that the
improved performance (i.e., activity enhance-
ment) of bimetallic alloys as electrocatalysts
could be explained by the structural modification
of Pt 5d orbital, coordination number of Pt, and
modification in adsorption of oxygenated species
from the electrolyte to the Pt or the alloying
metal. For example, alloying results in a lattice
contraction, leading to a more favorable Pt-Pt
distance for the dissociative adsorption of oxygen
(Vielstich et al. 2003b; Zhang 2008).
Pt+Cr, Pt+Ni, and Pt+Co bimetallic
electrocatalysts have been demonstrated to show
two- to threefold increase in their activities for
ORR. The activation energy for oxygen reduction
2 Bimetallic Electrocatalyst for Fuel Cells
was also shown to be lower than that in
Pt. However, it is also well recognized that
these bimetallic electrocatalysts are subject to
significant degradation rates (sintering/dissolu-
tion) as well as carbon-support corrosion under
specific voltage cycling conditions that are com-
mon for automotive drive cycles during fuel cell
startup and shutdown.
A lot of efforts have also been made during the
last two decades to improve anode electrocatalyst
in fuel cells that are designed to use hydrogen
obtained by means of reforming other fuels. In
that case an anode electrocatalyst is required for
hydrogen oxidation reaction to take place in the
presence of CO, as well as to improve perfor-
mance of the methanol fuel cells. The focus has
been on the development of bimetallic platinum-
based electrocatalysts to reduce the amount of
adsorbed CO and/or to improve performance of
electrooxidation of CO. Many metals have been
considered for modifying the activity of the plat-
inum catalyst, but only a few of them (Ru, Ir, Sn,
Mo, etc.) lead to improved performances. The
most studied bimetallic electrocatalyst is the fam-
ily of Pt/Ru alloys, which enhance greatly the
rate of oxidation of many alcohols (methanol,
ethanol, etc.).
Current Trends
Research and development in the area of bime-
tallic and ternary electrocatalysts is ongoing. The
trend is to make use of unique nanoscale struc-
tural effects that can be observed in structurally
modified alloys (e.g., de-alloyed Pt-based cata-
lysts) and intermetallic systems to enhance
greatly ORR. These include novel structures
observed in thin film extended surfaces
(Stamenkovic et al. 2007; Debe 2012) as well as
a multilayer Pt-skin surface (Wang et al. 2011,
2012).
References
Debe MK (2012) Electrocatalyst approaches and chal-
lenges for automotive fuel cells. Nature 486:43–51
Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ,
Lucas CA, Wang G, Ross PN, Markovic NM
(2007) Trends in electrocatalysis on extended and
nanoscale Pt-bimetallic alloy surfaces. Nat Mater
6:241–247
Vielstich W, Lamm A, Gasteiger HA (eds) (2003a)
Handbook of fuel cells, vol 1, Fundamentals and sur-
vey of systems. Wiley, New York
Vielstich W, Lamm A, Gasteiger HA (eds) (2003b)
Handbook of fuel cells, vol 2, Electrocatalysis.
Wiley, New York
Wang C, Chi M, Li D, Strmcnik D, van der Vliet D,
Wang G, Komanicky V, Chang K-C, Paulikas AP,
Tripkovic D, Pearson J, More KL, Markovic NM,
Stamenkovic VR (2011) Design and synthesis of
bimetallic electrocatalyst with multilayered Pt-skin
surfaces. J Am Chem Soc 133:14396–14403
Wang C, Markovic N, Stamenkovic VR (2012) Advanced
platinum alloy electrocatalysts for the oxygen reduc-
tion reaction. ACS: Catalysis 2:891–898
Zhang J (ed) (2008) PEM fuel cell electrocatalysts and
catalyst layers. Springer, London
F
Fuel Cell Components
Rajnish Kaur Calay
Energy Technology Research Group, Narvik
University College, Navrik, Norway
All fuel cells essentially consist of two
electrodes – an anode (negative side) and a cath-
ode (positive side) – and an electrolyte to allow
charges to move between the two sides of the fuel
cell. Electrons are drawn from the anode to the
cathode through an external circuit, producing
direct current electricity. On both sides of the
electrolyte and two electrodes (cathode, anode)
are the catalyst layers. A catalyst lowers the acti-
vation energy to undergo a reaction and helps the
reaction to take place at a faster rate. The fuel cell
type is defined based on the nature of the electro-
lyte. The six types are alkaline fuel cell (AFC),
molten carbonate fuel cell (MCFC), phosphoric
acid fuel cell (PAFC), proton exchange mem-
brane or polymer electrolyte membrane (PEM)
fuel cell, and solid oxide fuel cell (SOFC). The
PEM and SOFC have solid electrolyte, while
other three fuel cell types have liquid electrolyte.
In a solid electrolyte fuel cell, for example, a
PEMFC, the catalyst layer is spread either on
the electrolyte (as in PEM or SOFC) or on the
electrode. In addition to these basic components,
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1084-1
other components are gas diffusion layer, electric
connections, current collectors, separator plates,
and seals. In PEM fuel cell bipolar plates made up
of metal or conductive polymer (or carbon com-
posites) have more than one function. Bipolar
plates allow the transfer of electrons from the
anode side of one cell to the cathode side of the
adjacent cell, provide structural rigidity of the
stack, distribute reactant gas to each cell within
a stack, and distribute reactant gas within the cell
in the stack through proprietary flow field topol-
ogy (shape designs). In some cases, heat manage-
ment can be integrated in BPP design which
typically involves a thermally conductive
medium being supplied through the stack to
remove heat from the stack. Thermally conduc-
tive mediums typically can be air, de-ionized
water, or a coolant with high specific heat capac-
ity. Liquid electrolyte fuel cells will have elec-
trodes immersed in the liquid electrolyte and
often benefit from simplified design and also
less expensive catalyst materials. As a result,
liquid fuel cells, such as PAFC and MCFC, are
well-established technologies and have been
widely used for medium-scale (<250 kW) sta-
tionary applications. Table 1 shown below gives
an overview of each type of fuel cell, its electro-
lyte, and the primary catalyst used.
2 Fuel Cell Components

Fuel Cell Components, Table 1 Basic components of different fuel cells

Electrolyte
Fuel cell type Electrolyte type Catalyst
Alkaline Solution of potassium hydroxide KOH Liquid Platinum
Molten carbonate Sodium or magnesium carbonates (CO3) Liquid Nickel
Phosphoric acid Phosphoric acid Liquid Platinum
Polymer Polymer electrolyte membrane Solid Platinum
electrolyte
Solid oxide Ceramic compound of metal (like calcium or zirconium) Solid Nickel
oxides
P

Platinum metals): ruthenium (Ru), rhodium (Rh), palla-

Dmitri Bessarabov
DST National Center of Competence : Hydrogen
Infrastructure (HySA Infrastructure), North-West
University, Faculty of Engineering,
Potchefstroom, South Africa
Platinum
dium (Pd), osmium (Os), iridium (Ir), and plati-
num (Pt). These elements are all transition metals
clustering in the groups of 8, 9, and 10 and
periods 5 and 6 in the periodic table.
Platinum has a melting point of 1,769  C
(Platinum (Pt) 2012) and density of 21.45 g/cm3
at 20  C. It has a face-centered cubic crystal
structure.

Platinum (Pt) is a chemical element with an

Use of Platinum
atomic number of 78 and atomic mass of 195.09
(Platinum (Pt) 2012).
Platinum is used as a catalyst in the chemical
industry (e.g., in sulfuric acid production, petro-
chemistry) and in catalytic converters in the auto-
General Facts
motive industry. It is also used to make electrical
components, corrosion-resistant chemical labora-
Platinum has five naturally occurring stable iso-
tory equipment, and jewelry. Platinum is also
topes and one naturally occurring radioactive iso-
used in many medical applications (electrodes,
tope (Pt 190) that decays with a half-life of
dentistry, as a component for certain types of
6.5  1011 years. There are also a few known
anticancer drugs, etc.). One of the potentially
synthetic isotopes. Platinum is a silver-white
large applications for platinum and platinum-
metallic element. Platinum is a relatively rare
based alloys is its use in fuel cells as a catalyst.
and usually occurs in combination with other
metals including iridium, osmium, or nickel.
South Africa is the dominant supplier of Pt
which accounts for approximately 80 % of the References
world production. The world’s most important
deposits occur in the North West Province of Platinum (Pt) (2012) Encyclopædia Britannica online.
Encyclopædia Britannica Inc. http://www.britannica.
South Africa near Rustenburg and Brits. com/EBchecked/topic/464081/platinum-Pt
Platinum is one of the six metallic elements
forming the so-called PGM (platinum-group
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1085-4
A
Activity Coefficient
Dmitri Bessarabov
DST HySA Infastructure Center of Competence,
North-West University, Faculty of Engineering,
Potchefstroom, South Africa
Chemical Thermodynamics
Depending on a specific area of fundamental
science and technology, the term “activity” may
have a different meaning. For example, in chem-
ical thermodynamics, activity (a) is well known
as a convenient variable to represent data,
obtained experimentally or calculated theoreti-
cally, for the values of chemical potentials of
components in real chemical solutions. For the
i
th component of a mixture, activity ai is
defined as follows: mi ¼ m0i þ RTlnðai Þ , where
mi is the chemical potential of a component and
m0i is the chemical potential of that component in
standard state. R is the gas constant and T is the
thermodynamic temperature. The numerical
value of the activity depends on the choice of a
standard state, as it describes the difference
between an actual chemical potential and a stan-
dard chemical potential.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1086-3
Fuel Cells and Electrocatalysis
In hydrogen fuel cell science and technology,
activity is often referred to as the measure of
efficiency of electrocatalysts. Electrocatalytic
processes in fuel cells occur on the surface of
electrodes, and one of the main challenges is to
explain, predict, and improve electrocatalytic
activity of various electrode materials. In the
area of low temperature PEM (proton exchange
membrane, also called polymer electrolyte mem-
brane) fuel cells, catalytic activity is often used to
compare efficiency of electrocatalysts toward
kinetics of the oxygen reduction reaction (ORR)
occurring at the cathode. ORR is known to have
slow kinetics due to the reaction having multiple
steps and difficulties in breaking the O–O bond,
which leads to a larger cathodic overpotential
(Zhang 2008). In this case, overpotential is
defined as the extra potential over the equilibrium
value that must be applied to cause an electrode
reaction at a certain rate. Thus, an electrocatalyst
with high activity is required to minimize the
overpotential.
According to the Sabatier principle (Bligaard
et al. 2004), a volcano-shaped curve is obtained
when the activity of a catalyst for ORR is plotted
as a function of a variable that relates to the
ability of the electrocatalyst surface to form
chemical bonds with oxygen, reaction intermedi-
ates, and/or products (Nørskov et al. 2004). For
example, it was shown that the catalytic activity
of a single Pt-based electrocatalyst toward ORR
2 Activity Coefficient
depends strongly on such variables as the O2
adsorption energy, the dissociation energy of the
O–O bond, and the binding energy of OH on the
catalyst surface. The electronic structure of the Pt
catalyst (Pt d-band vacancy) and the Pt–Pt
interatomic distance (geometric effect) can
strongly affect these variables. Theoretical calcu-
lations on O2 and OH binding energy on several
metals have predicted that Pt should have the
highest electrocatalytic activity among other
metals with the ORR activity of Pt > Pd > Ir >
Rh, which is in agreement with experimental
results. Calculations have also predicted that
Pt–M (M = Fe, Co, Ni, etc.) bimetallic alloys
should have higher catalytic activity than pure
Pt, which has again been proven by experiments
(Nørskov et al. 2004).
Practical Measurements
Practically, electrocatalytic activity of various
electrocatalysts can be compared by measuring
electrical currents produced at a given
overpotential. The electrocatalyst that generates
higher current at lower overpotential is generally
a better electrocatalyst.
The rotating disk electrode (RDE) technique is
often used to measure ORR activity of
electrocatalysts for hydrogen PEM fuel cell
applications. Typically, current density j is mea-
sured at 0.9 V at the positive voltage sweep at a
certain electrode rotating speed. The measured
current density j is expressed by the following
equation: 1j ¼ j1 þ j1 þ j1 , where jk is kinetic
k d f
current density, jd is hydrodynamic diffusion lim-
iting current density, and jf is film diffusion lim-
iting current density. RDE experiments should be
designed to maximize jf. In that case, 1j ¼ j1 þ j1
k d
and after rearrangement jk ¼ j  jd =ðjd
jÞ.
For ORR the value of jd is normally taken at
0.4 V during RDE experiments.
Once jk is known, activity is often reported in
practical values as mass activity (A/mg Pt) by
normalization to the value of Pt loading of the
sample on the disk electrode.
Another practically important way of
reporting the electrocatalyst activity is to use
area-specific activity. The area-specific activity,
expressed in the following units, uA/cm2 Pt, is
reported by normalization of jk to the electro-
chemical surface area (ECSA) of the catalyst.
References
Bligaard T, Nørskov JK, Dahl S, Matthiesen J,
Christensen CH, Sehested S (2004) The Brønsted–e-
vans–polanyi relation and the volcano curve in hetero-
geneous catalysis. J Catal 224:206–217
Nørskov JK, Rossmeisl J, Logadottir A, Lindqvist L,
Kitchin JR, Bligaard T, Jonsson H (2004) Origin of
the overpotential for oxygen reduction at a fuel-cell
cathode. J Phys Chem B 108:17886–17892
Zhang J (ed) (2008) PEM fuel cell electrocatalysts and
catalyst layers. Springer, London
Further Reading
Vielstich W, Lamm A, Gasteiger HA (eds) (2003) Hand-
book of fuel cells, vol 2, Electrocatalysis. Wiley, New
York
F
Fruit Juice Processing by Integrated
Membrane Operations
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende, CS, Italy
Fruit juice clarification, stabilization,
depectinization, and concentration are typical
steps where membrane processes such as
microfiltration (MF), ultrafiltration (UF), reverse
osmosis (RO), osmotic distillation (OD), and
membrane distillation (MD) can be utilized as
alternative technologies to the conventional
transformation technologies. Particularly, MF
and UF are valid approaches for the clarification
of fruit juices as alternative to the use of fining
agents, such as gelatin, diatomaceous earth, ben-
tonite, and silica sol, which cause problems of
environmental impact due to their disposal
(Echavarria et al. 2011).
Clarified juices coming from MF or UF pro-
cesses can be commercialized or submitted to a
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1088-1
concentration process in order to obtain a product
suitable for the preparation of juices and
beverages.
RO, MD, and OD can be used as concentration
techniques as alternative systems to thermal
evaporation or cryoconcentration (Jiao
et al. 2004).
Integrated membrane operations have been
suggested for replacement of conventional juice
processing unit operations for the clarification
and concentration of different fruit juices as
well as for the recovery of aroma compounds.
A typical example of integrated membrane
system for the clarification and concentration of
fruit juices is depicted in Fig. 1. The fresh juice is
clarified by UF; the clarified juice is
pre-concentrated by RO and then concentrated
by OD. Pervaporation (PV) is used to recover
aroma compounds from the fresh juice.
2 Fruit Juice Processing by Integrated Membrane Operations

pasteurization

pulp

Fresh juice
permeate
(10-11 °Brix)
UF RO

preconcentrated concentrated
juice diluted stripping
stripping solution
(25-26 °Brix) solution

OD

PV concentrated
aromatic compounds juice
(64-65 °Brix)

Fruit Juice Processing by Integrated Membrane Operations, Fig. 1 Integrated membrane process for the
production of concentrated fruit juice

References Jiao B, Cassano A, Drioli E (2004) Recent advances on

membrane processes for the concentration of fruit
Echavarria AP, Torras C, Pagan J, Ibarz A (2011) Fruit juices: a review. J Food Eng 63:303–324
juice processing and membrane technology applica-
tion. Food Eng Rev 3:136–158
R
Recovery of Polyphenols from Olive
Mill Wastewaters by Membrane
Operations
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
Olives contain an appreciable amount of bioac-
tive compounds such as polyphenols with
remarkable health benefits. They are potent anti-
oxidants and exhibit various other physiological
activities including antiinflammatory, antimicro-
bial, antiallergic, anticarcinogenic, and antihy-
pertensive activities (Obied et al. 2005).
The biophenolic fraction of olive oil com-
prises only 1–2 % of the total phenolic content
of the fruits; the remaining 53 % and 45 % are lost
in olive mill wastewaters (OMWs) and the olive
cake, respectively. Typical biophenols occurring
in OMWs are benzoic acid derivatives
(4-hydroxybenzoic, protocatechuic, vanillic
acids), hydroxycinnamic acid derivatives
(ferulic, caffeic acids), tyrosol, homovanillyl
alcohol, hydroxytyrosol, and oleuropein. These
compounds represent a precious resource of
potentially useful chemical substances (after
their direct recovery or chemical transformation)
for cosmetic and pharmaceutical industries and in
food processing and food product conservation.
Several techniques have been proposed indi-
vidually or in integrated forms to recover
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1089-1
phenolic compounds from OMWs including sol-
vent extraction, supercritical fluid extraction, and
chromatographic separation.
Membrane operations such as
microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis (RO),
mostly in sequential form, represent useful tech-
nologies for the recovery, purification, and con-
centration of polyphenols with regard to their
molecular weight cutoff values. They offer sig-
nificant advantages over conventional methodol-
ogies in terms of low energy consumption, no
additive requirements, and no phase change.
Integrated membrane processes based on the
use of these operations permit to obtain purified
water which can be discharged in aquatic systems
according to national regulations or to be used for
irrigation. NF is typically employed for the sep-
aration of most part of phenolic compounds
(Paraskeva et al. 2007).
References
Obied HK, Allen MS, Bedgood DR, Prenzler PD,
Robards K, Stockmann R (2005) Bioactivity and anal-
ysis of biophenols recovered from olive mill waste.
J Agric Food Chem 53:823–837
Paraskeva CA, Papadakis VG, Kanellopoulou DG,
Koutsoukos PG, Angelopoulos KC (2007) Membrane
filtration of olive mill wastewater (OMW) and OMW
fractions exploitation. Water Environ Res 79:421–429
R
Recovery of Polyphenols from Wine
Wastewaters by Membrane
Operations
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
Grape seeds and pomace (a solid material
consisting of skins and grape seeds) are typical
by-products of the winemaking process
containing phenolic compounds.
Grape seeds contain basically (w/w) 40 %
fiber, 16 % essential oil, 11 % protein, 7 % com-
plex phenolic compounds, sugars, minerals, and
other substances (Campos et al. 2008). Grape
skin is a source of anthocyanidins and anthocya-
nins, natural pigments with antioxidant
properties.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1090-1
These phenolic compounds have an extremely
high market value as food additives,
nutraceuticals, and cosmeceuticals, due to their
biological activity (Crespo and Brazinha 2010).
A membrane-based process scheme for the
purification, fractionation, and concentration of
phenolic compounds from wine wastewaters is
depicted in Fig. 1. The purification step devoted
to the removal of undesirable compounds (such
as fats, proteins, and sugars) and microorganisms
is based on the use of ultrafiltration
(UF) membranes.
The use of appropriate nanofiltration
(NF) membranes allows for obtaining fractions
enriched in phenolic compounds. The final con-
centration step with removal of the extracting
solvent (as permeate) is performed by reverse
osmosis (RO).
2 Recovery of Polyphenols from Wine Wastewaters by Membrane Operations

Recovery of Polyphenols microorganisms,

from Wine Wastewaters fats, proteins,
by Membrane sugars
Operations,
Fig. 1 Purification,
fractionation, and
Raw material
concentration of extraction
(pomace, seeds) UF NF
polyphenols from wine
wastewaters by integrated
membrane process
extracting phenolic
solvent RO fractions

food additives,
cosmeceuticals,
nutraceuticals

References extracts from Cabernet Sauvingnon (Vitis vinifera).

Bioresour Technol 99:8413–8420
Campos LMAS, Leimann FV, Pedrosa RC, Ferreira SRS Crespo JG, Brazinha C (2010) Membrane processing:
(2008) Free radical scavenging of grape pomace natural antioxidants from winemaking by-products.
Filtr Sep 47:32–35
O
Olive Mill Wastewater Treatment by
Membrane Operations
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
The extraction of olive oil generates huge quan-
tities of wastes having a great impact on land and
water environments because of their high phyto-
toxicity. Pressure and three-phase centrifugation
systems produce a liquid effluent called olive mill
wastewater (OMW).
Several waste management approaches,
including physicochemical treatments (natural
evaporation, treatment with lime and clay, oxida-
tion), agronomic methods (land spreading), ani-
mal breeding, and biological treatments (both
aerobic and anaerobic) have been proposed to
reduce the polluting load and, consequently, the
final waste disposal. The efficiency of the pro-
cess, the complexity, and the costs involved may
vary remarkably. In addition, different legisla-
tions existing in olive-oil producing countries
play an important role in the selection of appro-
priated technologies.
Pressure-driven membrane operations, includ-
ing microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1091-1
(RO) have been proposed and combined in inte-
grated processes to obtain effluent streams from
OMWs of acceptable quality for safe disposal
into the environment (surface water or soil) for
irrigation or even for recycling and use in the
olive mill. Basically, MF and UF processes are
used for primary treatment purpose, while NF
and RO are used for final treatment (Cassano
et al. 2013; Paraskeva et al. 2007).
Integrated systems based on the use of these
processes permit to obtain a COD reduction of
about 99 %, the recovery of high percentage of
purified water (60–70 %) (permeate of RO mem-
branes), a production of an organic fraction
(retentate of MF and UF membranes) which can
be submitted to anaerobic digestion for the pro-
duction of biogas, the recovery of a phenolic
fraction (retentate of NF and RO membranes) of
potential interest for food, phytotherapic, or cos-
metic applications (Fig. 1).
References
Cassano A, Conidi C, Giorno L, Drioli E (2013) Fraction-
ation of olive mill wastewaters by membrane separa-
tion techniques. J Hazard Mater 248–249:185–193
Paraskeva CA, Papadakis VG, Tsarouchi E,
Kanellopoulou DG, Koutsoukos PG (2007) Membrane
processing for olive mill wastewater fractionation.
Desalination 213:218–229
2 Olive Mill Wastewater Treatment by Membrane Operations

Formulations for food, cosmetic

and phytoterapic industry

anaerobic digestion purification

OMWs
organic fractions phenolic fractions

pretreatment

MF UF NF RO

purified water

Olive Mill Wastewater Treatment by Membrane Operations, Fig. 1 Integrated membrane process for the
treatment of OMWs
O
Olive Wastewater
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende, CS, Italy
Olive oil extraction processes are usually
grouped into press extraction and centrifugation
extraction systems (two-phase and three-phase
centrifugal olive oil extraction).
The extraction of olive oil generates huge
quantities of wastes having a great impact on
land and water environments because of their
high phytotoxicity. Pressure and three-phase cen-
trifugation systems produce a liquid effluent
called olive mill wastewater (OMW) or vegeta-
tion water. Typically, 0.5–1.5 m3 of OMWs per
1,000 kg of olives are produced depending on the
process used. OMWs appear like violet-dark
brown liquids with acid reaction (pH from 3 to
6) containing great quantity of suspended matter,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1092-1
high degree of organic pollution (COD,
40–220 g/L; BOD, 35–110 g/L), high electrical
conductivity, reducing sugars up to 60 % of the
dry substance and polyphenols (0.5–24 g/L)
(Takac and Karakaya 2009).
The organic content is mainly represented by
polyphenols, carbohydrates, polysaccharides,
sugars, nitro compounds, polyalcohols, and oil.
Ultrafiltration (UF) membranes allow to sepa-
rate macromolecules and colloids having molec-
ular weight between 500 and 250,000 Da; they
can be used to remove most parts of COD from
pretreated OMWs producing a permeate stream
which can be submitted to a biological treatment
to comply with law limits relevant to BOD and
COD (Borsani and Ferrando 1996). A scheme of
OMW treatment including a concentration step
via UF is depicted in Fig. 1.
2 Olive Wastewater

Olive Wastewater, OMWs

Fig. 1 Scheme of OMWs
treatment with UF
Neutralization Settled waters
membranes Storage
Sedimentation (35°C)

Biological UF
treatment

discharge in
superficial water

References Takac S, Karakaya A (2009) Recovery of phenolic anti-

oxidants from olive mill wastewater. Rec Pat Chem
Borsani R, Ferrando B (1996) Ultrafiltration plant for Eng 2:230–237
olive vegetation waters by polymeric membrane bat-
teries. Desalination 108:281–286
D
Dynamic Mechanical Analysis
Chi Hoon Park
Gyeongnam National University of Science and
Technology (GNTECH), Jinju-si,
Gyeongsangnam-do, Republic Of Korea
(South Korea)
Dynamic mechanical analysis (DMA) is a tech-
nique to study viscoelastic properties and modu-
lus of elasticity of polymers by measuring the
damping of an oscillatory signal of stress and
strain. DMA results generally describe the varia-
tion of modulus values as a function of tempera-
ture or frequency (e.g., Fig. 1) and are widely
used to detect the transitions such as glass transi-
tion temperature (Tg) or melting of polymer
materials.
Figure 2a shows general schematic diagram of
DMA apparatus; after a sinusoidal force is
applied to the sample as an input signal, the
resulting sinusoidal deflection or deformation is
detected as an output signal, which contains
information about the storage modulus E0 , the
dynamic loss modulus E00 , and the mechanical
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1093-5
loss factor tan d (www.ngb.netzsch.com).
According to the feature or types of sample mate-
rials, there are various modes of deformation as
shown in Fig. 2b (www.ngb.netzsch.com), and
this variety of sample holding method enables
DMA to have wide applications. For membrane
samples, tension mode (fifth mode from the top in
Fig. 2b) is generally adopted.
In the membrane applications, DMA is widely
used for various fields such as fuel cell mem-
branes, bio membranes, gas separation,
pervaporation, etc. Page et al. applied DMA to
investigate the structural characteristic of Nafion
membranes well known as a fuel cell membrane
(Page et al. 2005). In the study, two thermally
reversible transitions of Nafion over room tem-
perature were explained as glass transition by the
short-range segmental motions within a static
electrostatic network below 150  C and the
long-range chain/side-chain motion by thermally
activated destabilization of the electrostatic
network over 240  C. Also, Xie reported that
the perfluorosulfonic acid (PFSA) ionomer mem-
brane showed a wide range of glass transition
from 55  C to 130  C (Fig. 1), and based on
the Tg result, he studied the multi-shape memory
2 Dynamic Mechanical Analysis

Dynamic Mechanical
Analysis, Fig. 1 Dynamic
mechanical analysis
(DMA) curve of
perfluorosulfonic acid
(PFSA) ionomer. tan d is
the ratio between the loss
modulus E00 and the storage
modulus E0 (Xie 2010)
(Reprinted with permission
from Macmillan Publishers
Ltd: Nature 464:267–270,
copyright (2010))

effect of PFSA (Xie 2010). Mano focused on the
advantage of DMA that the test conditions can be
more closely set to the physiological environ-
ments which the biomaterials will be applied to
(Mano 2008). Using chitosan membranes, their
mechanical properties were measured under
low/moderate hydration conditions at different
relative humidity (RH) levels and in completely
wet (immersed) condition. Weng
et al. synthesized intrinsically dopable polyimide
(DPI) membranes containing an amine-capped
aniline trimer (ACAT) having high gas separa-
tion properties, where DMA results reported
higher mechanical and thermal stabilities of the
membranes than those of polyaniline (PANI) and
conventional nondopable polyimide (NDPI)
(Weng et al. 2011). Other examples are as
follows: Budd et al. studied the mechanical sta-
bility of polymer of intrinsic microporosity
(PIM-1) by DMA in the temperature range from
30  C to 450  C for pervaporation application
(Budd et al. 2004); Nagarale et al. synthesized
poly(vinyl alcohol)-SiO2 hybrid membrane by
sol-gel method for a cation-exchange membrane,
and its mechanical stability was measured by
DMA (Nagarale et al. 2004); Gholap
et al. synthesized hydrophobically modified
PVA-g-polyNTBA membranes, where DMA
was used to detect the crystallinity of the mem-
branes as a function of annealing (Gholap
et al. 2004); using DMA, Arjun and Ramesh
studied the mechanical stability of the oxida-
tively stable polycarbonate urethane (PCU)
membranes fabricated by electrospinning method
Dynamic Mechanical Analysis 3

Fig. 2 (continued)
4 Dynamic Mechanical Analysis

Dynamic Mechanical Analysis, Fig. 2 (a) General sample holding method) (www.ngb.netzsch.com)
schematic diagram of dynamic mechanical analysis (Reprinted with permission from NETZSCH-Gerätebau
(DMA) apparatus and (b) modes of deformation (i.e., GmbH)
Dynamic Mechanical Analysis
for biomedical application (Arjun and Ramesh
2012); Ghassemi et al. synthesized poly(arylene
ether)s with pendant perfluoroalkyl sulfonic acid
groups for fuel cell application, where their
a-relaxation temperature was reported around
196  C (Ghassemi et al. 2011); Love investigated
thermal and mechanical transitions for commer-
cially available polymer Li-ion battery separators
(Love 2011).
References
Arjun GN, Ramesh P (2012) Structural characterization,
mechanical properties, and in vitro cytocompatibility
evaluation of fibrous polycarbonate urethane mem-
branes for biomedical applications. J Biomed Mater
Res A Article first published online. doi:10.1002/jbm.
a.34255
Budd PM, Elabas ES, Ghanem BS, Makhseed S,
McKeown NB, Msayib KJ, Tattershall CE, Wang
D (2004) Solution-processed, organophilic membrane
derived from a polymer of intrinsic microporosity.
Adv Mater 16(5):456–459
Dynamic Mechanical Analyzer DMA 242 C. Online
accessible poster. NETZSCH-Gerätebau GmbH.
http://www.netzsch-thermal-analysis.com/download/
Poster_DMA_242C_65.pdf. Accessed 25 Aug 2012
5
Ghassemi H, Schiraldi DA, Zawodzinski TA, Hamrock
S (2011) Poly(arylene ether)s with pendant
perfluoroalkyl sulfonic acid groups as proton-
exchange membrane materials. Macromol Chem
Phys 212(7):673–678
Gholap SG, Jog JP, Badiger MV (2004) Synthesis and
characterization of hydrophobically modified poly
(vinyl alcohol) hydrogel membrane. Polymer
45(17):5863–5873
Love CT (2011) Thermomechanical analysis and durabil-
ity of commercial micro-porous polymer Li-ion bat-
tery separators. J Power Sources 196(5):2905–2912
Mano JF (2008) Viscoelastic properties of chitosan with
different hydration degrees as studied by dynamic
mechanical analysis. Macromol Biosci 8(1):69–76
Nagarale RK, Gohil GS, Shahi VK, Rangarajan R (2004)
Organic–inorganic hybrid membrane: thermally stable
cation-exchange membrane prepared by the Sol–gel
method. Macromolecules 37(26):10023–10030
Page KA, Cable KM, Moore RB (2005) Molecular origins
of the thermal transitions and dynamic mechanical
relaxations in perfluorosulfonate ionomers. Macro-
molecules 38(15):6472–6484
Weng C-J, Jhuo Y-S, Huang K-Y, Feng C-F, Yeh J-M,
Wei Y, Tsai M-H (2011) Mechanically and thermally
enhanced intrinsically dopable polyimide membrane
with advanced gas separation capabilities. Macromol-
ecules 44(15):6067–6076
Xie T (2010) Tunable polymer multi-shape memory
effect. Nature 464:267–270
W
Wide-Angle X-ray Diffraction Pattern material is a PET with a high degree of crystal-
Doriano Lamba
Institute of Crystallography, National Research
Council, Trieste, Italy
According to the Wide-Angle X-ray Diffraction
(WAXD) method, the sample is scanned in a
wide-angle X-ray goniometer, and the scattering
intensity is plotted as a function of the 2y angle.
When X-rays are directed in solids, they will
scatter in predictable patterns based upon the
internal structure of the solid. A crystalline solid
consists of regularly spaced atoms (electrons)
that can be described by imaginary planes. The
distance between these planes is called the
d-spacing. The intensity of the d-space pattern is
directly proportional to the number of electrons
(atoms) that are found in the imaginary planes
(Warren 1990).
Every crystalline solid will have a unique pat-
tern of d-spacings, which represents a fingerprint
for that solid. In fact, solids with the same chem-
ical composition but different phases can be iden-
tified by their pattern of d-spacings.
For semicrystalline isotropic materials, a qual-
itative measure of crystallinity is directly
obtained from the respective WAXD curve.
Figure 1 shows the phenomenon for poly(eth-
ylene terephthalate) (PET) membrane (Stribeck
2007). The curve in bold solid line shows a
WAXD curve with many reflections. The
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1099-1
linity. The thin solid line at the bottom shows a
compressed image of the corresponding scatter-
ing curve from a completely amorphous sample.
Compared to the semicrystalline material it only
shows two very broad peaks – the so-called first
and second order of the amorphous halo.
It is obvious that the semicrystalline material
contains this amorphous feature as well, under-
neath the reflections. In the semicrystalline mate-
rial, the halo is shifted to higher scattering angle.
In fact, the dash-dotted curve is simply an image
of the scattering curve of the amorphous material
stretched in the vertical as well as in the horizon-
tal direction.
The dash-dot-dotted curve shows the instru-
mental background of the goniometer. Identifica-
tion of the observed peaks can be accomplished
by means of data listed in the Polymer Handbook
(Brandrup et al. 2005).
A simple method can be used to describe
changing crystallinity from WAXD data of iso-
tropic materials. It is based on the computation of
areas in Fig. 1. At first, the border between first-
order and second-order amorphous halo is iden-
tified. For PET, this is at 2y  37 (vertical line
in the plot). Then the area, Aam, between the
amorphous halo and the machine background is
integrated. Finally the area, Acr, between the crys-
talline reflections and the amorphous halo is inte-
grated and the crystallinity index Xc,
Xc = Acr/(Aam + Acr), is computed.
2 Wide-Angle X-ray Diffraction Pattern

Wide-Angle X-ray
Diffraction Pattern,
Fig. 1 WAXD curves
from semicrystalline and
amorphous poly(ethylene
terephthalate) (PET).
Separation of the observed
intensity into crystalline,
amorphous, and machine
background (laboratory
goniometer Philips PW
1078, symmetrical-
reflection geometry) (This
figure has been taken from
Stribeck (2007) (Fig. 8.2,
p. 102))

References Stribeck N (2007) X-ray scattering of soft matter. Springer

laboratory manuals in polymer science. Springer, Ber-
Brandrup J, Immergut EH, Grulke EA, Abe A, Bloch DR lin/Heidelberg
(eds) (2005) Polymer handbook, 4th edn. Wiley, Warren BE (1990) X-ray diffraction, Dover books on
New York physics. Dover Publications, New York
W

Wide-Angle X-Ray Scattering (WAXS) sinðyÞ

q ¼ 4p
l
Doriano Lamba
represents the scattering vector and e2sij q is the
2 2

Institute of Crystallography, National Research

Council, Trieste, Italy
Synonyms
Wide-Angle X-ray diffraction (WAXD)
Wide-Angle X-ray Scattering (WAXS) or
Wide-Angle X-ray Diffraction (WAXD) is an
x-ray-diffraction technique that is often used to
determine the crystalline structure of inorganic
and organic polymeric membranes. This tech-
nique specifically refers to the analysis of Bragg
peaks scattered to wide angles (2y >1
), which
by Bragg’s law implies that they are caused by
subnanometer-sized structures.
The Debey’s equation (Guinier 1963)
 
X
N
sin qr ij 2s2 q2
I ð qÞ ¼ fi fj e ij
i, j
qr ij
provides a relationship between interatomic dis-
tances rij and the x-ray scattering factors fi and fj
of the atoms i and j respectively.
Debye–Waller thermal factor.
s2ij is the atomic mean-square displacement.
Thermal motion reduces WAXS intensity.
To derive the equation, it is assumed that the
sample is composed of perfect crystals of finite
dimensions randomly oriented, each consisting of
N atoms that vibrate with harmonic motion.
Wider is the motion, greater is the Debye–Waller
factor.
The Fourier transform of the reduced intensity
I(q) results in a radial distribution and hence pro-
vides information about short and medium range
order in the sample.
Wide-Angle X-ray Scattering is the same
technique as Small-Angle X-ray Scattering
(SAXS): only the distance from sample to the
detector is shorter and thus diffraction maxima
at larger angles are observed. Depending on the
measurement instrument used, it is possible to do
WAXS and SAXS in a single run (Small- and
Wide-Angle X-ray Scattering SWAXS).
At third generation synchrotron radiation
sources, the development of m-sized beams
allows to perform time-resolved mSAXS/m
WAXS experiments on polymeric membranes
during melting, crystallization, and deformation
aiming to visualize and understand the evolution
of nanostructures (Stribeck 2007; Nozue
et al. 2007).

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1101-1
2 Wide-Angle X-Ray Scattering (WAXS)
Wide-Angle X-Ray Scattering (WAXS), Fig. 1 Wide-
angle X-ray scattering from (a) polystyrene, showing a
diffuse halo from an amorphous sample; and (b) highly
Amorphous structures yield scattering halos
(broad peaks) whereas crystalline structures are
characterized by Bragg peaks (Fig. 1). WAXS is
therefore a good monitor of crystallinity in the
sample.
This technique is a time-honored but a some-
what out-of-favor technique for the determina-
tion of degree of crystallinity of inorganic
and/or organic membrane polymeric samples.
The diffraction pattern generated allows to deter-
mine the chemical composition or phase compo-
sition of the membrane film, the texture of the
membrane film (preferred alignment of crystal-
lites), the crystallite size, and presence of film
stress.
According to this method, the sample is
scanned in a wide-angle x-ray goniometer and
crystalline polyethylene, showing sharp ‘powder’ rings
(This figure has been taken from Bower (2002), Fig. 3.9,
p. 81)
the scattering intensity is plotted as a function of
the 2y angle.
References
Bower DI (2002) An introduction to polymer physics.
Cambridge University Press, Cambridge/New York/
Melbourne/Madrid/Cape Town/Singapore/São Paulo
Guinier A (1963) X-ray diffraction in crystals, imperfect
crystals and amorphous bodies. W. H. Freeman and
Company, San Francisco
Nozue Y, Shinohara Y, Amemiya Y (2007) Application of
microbeam small- and wide-angle x-ray scattering to
polymeric material characterization. Polym
J 39:1221–1237
Stribeck N (2007) X-ray scattering of soft matter. Springer
laboratory manuals in polymer science. Springer, Ber-
lin/Heidelberg
X

X-Ray Diffraction (XRD) nl ¼ 2dsiny

where n is the “order” of the plane, l is the

Alberto Cassetta
wavelength of the X-ray, d is the distance
Istituto di Cristallografia - CNR UOS di,
between the planes of the family, and y is the
Trieste, Italy
angle between the wave and the plane. Further-
more, a complex but well-defined mathematical
relation links the diffracted waves directions and
X-ray diffraction occurs when an electromag-
intensities with the electron density inside the
netic wave of wavelength of the order of magni-
diffracting object (Warren 1990).
tude of 1 Å interacts with an ordered array of
Therefore, due to their relationship with the
atoms like a molecular or ionic crystal. When
spatial arrangements of the atoms inside a peri-
the electromagnetic wave interacts with the elec-
odic structure, the acquisition of the diffracted
trons of an atom, a secondary wave (of the same
rays from a material having an internal atomic
wavelength) is scattered in all directions by the
periodicity (from 1D to 3D) may give important
atom itself. The secondary waves produced by
insights into the atomic structure of the material
the three-dimensional regular array of atoms
itself.
give rise to interference phenomena which can
Experimentally, an X-ray diffraction experi-
be destructive or constructive depending on the
ment depends on the physical state of the matter:
relative disposition of the atoms. Constructive
crystalline (single crystal or polycrystalline), an
interference results in diffracted rays scattered
ordered surface (2D periodicity only), or even
only along well-defined directions. The direc-
with an order in one dimension only like in fibers.
tions and the intensities of the diffracted rays
In any case the experiments require three
depend on the crystal symmetry and on the
essential parts: an X-ray source which is in
atomic number and spatial distribution of the
general monochromatic (conventional sources
atoms inside the crystal and the set of diffracted
or synchrotron), a goniometer which is used to
rays, thus containing information about the three-
orient the sample according to the Bragg’s law,
dimensional atomic structure of the crystal.
and a detector which may be mono- or
Following Bragg’s description of X-ray
bidimensional and is used to collect the diffracted
diffraction, we can assume a crystal as made of
rays from the sample (Roe 2000).
infinite planes containing atoms and whose
X-ray diffraction is a well-established tech-
orientations are dependent from the crystal unit
nique in membranes science (Bower 2002),
cell parameters. Each family of planes will then
mostly used for structural characterization but
diffract according to Bragg’s law (Warren 1990):
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1102-2
2 X-Ray Diffraction (XRD)

X-Ray Diffraction (XRD), a 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Fig. 1 (a) 2D powder
2000 2000
diffraction pattern of a
copolymer based on
alternate benzothiadiazole 1800 1800
and dioctylfluorene
moieties and (b) its 1600 1600
integrated pattern
(Courtesy of Drs W. Porzio 1400 1400
and L. Barba)
1200 1200
Rows

1000 1000

800 800

600 600

400 400

200 200

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Columns
b 50000

40000
Intensity (arb. units)

30000

20000

10000

0
0 3 6 9 12 15 18 21
2q (∞)

also for the analysis of physical processes occur-
ring at membrane interfaces.
X-ray diffraction has been the main technique
for the determination of crystalline polymers
structure. From the diffraction pattern of well-
aligned polymer crystallites, it is possible to
obtain the unit cell parameters, by inspecting the
diffraction pattern geometry and intensities.
A more quantitative study, normally carried out
on polycrystalline samples (powder diffraction,
Fig. 1), may lead to the structural determination
of the unit cell content, thus giving a molecular
model of the crystalline polymer. Besides, poly-
mer crystal diffraction patterns generally do not
X-Ray Diffraction (XRD) 3

contain the full information needed for a com- analysis of the membrane diffraction pattern
plete crystal structure determination, and a may give important insights into the material
modeling procedure is employed by exploiting modification upon membrane preparation.
crystal packing hypothesis based on polymer
physics knowledge. The final accepted model is
the one which best reproduces the experimental
References
diffraction pattern.
X-ray diffraction is also used in polymer Bower DI (2002) An introduction to polymer physics.
chemistry to estimate the crystallinity index, by Cambridge University Press, Cambridge, UK
evaluating the different contributions to the total Roe RJ (2000) Methods of x-ray and neutron scattering in
diffracted intensity of the amorphous and crystal- polymer science. Oxford University Press, Oxford
Warren BE (1990) X-ray diffraction. Dover, New York
line components of the sample.
Finally, if one or more of the components of
the membrane are in the crystalline state, the
X
X-Ray Synchrotron
Alberto Cassetta
Istituto di Cristallografia - CNR UOS di Trieste,
Trieste, Italy
Synchrotron radiation (SR) is produced when
charged particles moving at relativistic speed
are forced to change their trajectory by a mag-
netic field. Those particles, typically electrons,
loose energy under the form of electromagnetic
radiation, and due to the their relativistic speed,
the emitted radiation is confined in a narrow cone
along the direction of the electron’s motion
(Fig. 1), with a continuous energy spectrum rang-
ing from far infrared to X-ray regions.
In a synchrotron, bunches of electrons circu-
late in a closed orbit and the electrons are forced
to change their directions by magnets, producing
intense SR beams tangentially to the magnets
themselves. The radiation thus produced is
extremely intense and collimated in a narrow
vertical angle and can deliver to the sample
huge amounts of X-ray photons, several order of
magnitude more than conventional laboratory
sources (Duke 2008).
Nowadays, dedicated synchrotrons are built in
order to produce extremely brilliant (intense and
collimated) X-ray beams, whose properties
depend on the synchrotron construction parame-
ters. Apart from intensity and collimation, SR
possesses other interesting properties: a
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1103-1
continuous spectrum, a high degree of polariza-
tion, and a well-defined time structure. All of
these properties can be properly tuned for specific
X-ray experiments. Apart from bending magnets,
which keep the electrons in a closed path, other
magnetic devices called insertion devices
(wigglers and undulators) are inserted in the
straight sections of modern storage rings and
can produce even more intense and collimated
X-ray beams (Fig. 2).
SR is conveyed into a pipe, the beamline,
where it is optically modified in terms of wave-
length selection, focusing properties and final
beam size. It is finally delivered to the sample,
according to the kind of experiment
(Margaritondo 2002).
Synchrotrons are generally built for specific
SR wavelengths with specific machine character-
istics. Lower-energy X-ray beams normally indi-
cated as “soft X-rays” have energies roughly in
the range 100–1,000 eV (10–1 nm), whereas
“hard X-rays” are in the range of 10–100 keV
(0.1–0.01 nm).
The X-rays produced by synchrotrons have
very attractive characteristics for the materials
science researcher, which can exploit not only
the high photon flux of the SR but also the high
collimation of the beam.
Highly brilliant X-ray beam with a size of few
mm to few hundreds of nm has been produced and
used for microdiffraction experiments. With such
a small beam section, the scanning of a single
polymeric fiber was possible pinpointing to
2 X-Ray Synchrotron

electrons
electrons

relativistic speed
radiation
non-relativistic speed

radiation

X-Ray Synchrotron, Fig. 1 Simplified representation of the angular distribution of emitted radiation from electrons
moving at relativistic and nonrelativistic speed and traveling in a circular path

X-Ray Synchrotron, Fig. 2 Sketch of a modern (wigglers, undulators); (D) quadrupole magnets; (E)
SR-dedicated storage ring. (A) Emitted synchrotron radi- radio-frequency cavity; (F) injection magnet. Electron
ation; (B) bending magnets; (C) insertion devices path is represented in magenta

domain inhomogeneities in both size and orien- microbeam approach was also applied to SAXS
tations (Riekel and Davies 2004). The same and WAXS techniques.
X-Ray Synchrotron
Highly intense and extremely collimated SR
beams have also been largely used in SAXS
experiments, to provide structural information
on the nm size of polymeric and biological mem-
branes (like lipid bilayers). Soft matter, like bio-
logical membranes, is well known as low X-ray
scattering material, and the intense SR beam is a
unique tool for SAXS studies. Moreover, the
strong collimation of the beam allows a resolu-
tion impossible to be reached with conventional
sources. Wavelength tunability is another charac-
teristic of SR largely exploited in SAXS, where
time structure of SR has been used in time-
resolved experiments (Chu and Hsou 2001).
X-ray-based imaging techniques applied to
hard and soft matter gained a great benefit from
the use of intense and small X-ray beam as for
tomographic methods. X-ray photoelectron spec-
troscopy methods also received a great impulse
3
from the use of X-ray synchrotron radiation.
Chemical analysis with photoelectron spectros-
copy requires tunable and brilliant SR beams in
order to chemically and electronically character-
ize surfaces like metal-based membranes.
References
Chu B, Hsou B (2001) Small-angle x-ray scattering of
polymers. Chem Rev 101:1727–1761
Duke P (2008) Synchrotron radiation. Oxford University
Press, New York
Margaritondo G (2002) Elements of synchrotron light.
Oxford University Press, New York
Riekel C, Davies RJ (2004) Applications of synchrotron
radiation micro-focus techniques to the study of poly-
mer and biopolymer fibers. Curr Opin Colloid Inter-
face Sci 9:396–403
X
X-Ray Synchrotron
Microtomography
Alberto Cassetta
Istituto di Cristallografia - CNR UOS di Trieste,
Trieste, Italy
Tomography has its roots in radiology: an X-ray
beam hits a sample and the transmitted beam is
recorded by a detector. The ratio of the transmit-
ted to incident intensities will depend on the line
integral of the absorption coefficient m of the
materials (which increase with the atomic num-
ber Z) along the beam path in the sample. The
resulting image will thus be a 2D projection of the
volumetric absorption coefficient of the sample
itself. In tomography many 2D images
(radiography) are acquired at different sample
orientations, for a total angle of 180 . The images
are then combined together through a mathemat-
ical algorithm in order to give a 3D reconstruc-
tion, in the form of sliced 2D maps, of the
different absorption coefficient inside the sample,
clearly related to its chemical composition.
Synchrotron X-ray sources are unique in their
properties for tomographic analysis. The intense
synchrotron X-ray beam allows the resolution of
subtle variations in absorptivity due to an
extremely good signal-to-noise ratio. Moreover,
a synchrotron X-ray beam can be considered
essentially parallel which simplifies the mathe-
matical treatment of image reconstruction, which
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1104-2
actually assumes a parallel beam. Synchrotron
radiation can be tuned for the optimization of
the contrast between the chemically different
constituents of the sample and for avoiding aber-
rations originating from the use of polychromatic
beams. Finally, exploiting the partial coherence
of a synchrotron X-ray beam, “phase contrast”
microtomographic techniques, based on the dif-
ferent refractive index of different materials, can
be used in order to gain further resolution in
image reconstruction. On the whole, synchrotron
radiation-computed microtomography (SR-mCT)
allows a spatial resolution on mm and even
sub-mm order which results in a digital recon-
struction of the scanned volume apt for qualita-
tive and quantitative analysis (Bonse and Busch
1996).
The setup of a typical SR-mCT experiment
requires an X-ray source in the range of the hard
X-ray region (from 8 keV upward) having a linear
size of few tens of mm or less. The X-ray beam is
monochromatized and reduced to the appropriate
size by a slits system. The sample, generally of
few mm in linear dimensions, is mounted on a
holder and fitted onto a goniometer for proper
orientations. Images are typically collected from
a 2D detector which is often a scintillator opti-
cally coupled with a high-resolution CCD camera
with a small pixel size. Depending on the
beamline setup, focusing elements may also be
present before and after the sample in order to
gain further resolution. Given the high brightness
of the synchrotron beam, hundreds to thousands
2 X-Ray Synchrotron Microtomography

Monochromator
X-ray beam Detector
Sample
Synchrotron
Slits
Goniometer
3D reconstruction
sliced maps

Image
Processing

X-Ray Synchrotron Microtomography, Fig. 1 Schematic representation of a synchrotron radiation

microtomography experiment

of images can be collected in a relatively small
amount of time. Image processing is computed
offline by using appropriate algorithms such as
the “filtered back projection” or “direct Fourier
inversion” methods which are found in dedicated
image reconstruction software packages (Fig. 1).
SR-mCT is a valuable tool in membrane struc-
ture analysis as provided by a nondestructive
method for the investigation, at the micrometric
size, of both the bulk and the interface structure
of the membrane. Tomographic methods do not
require specific sample preparation, finally giv-
ing a high-resolution 3D representation of the
“native” sample under study.
SR-mCT has been widely used in order to gain
insights into the water distribution in polymer
electrolyte membrane fuel cells (PEMFC) in
response to various operation conditions. By
using SR-mCT the correlation between the wet-
ness of the polymer electrolyte membrane, its
structure, and its proton conductivity has been
established (Manke et al. 2011).
A typical application of SR-mCT to membrane
science is the structural investigation of the
membrane porosity. Exploiting the different
absorption coefficient between the polymer and
water is possible to investigate the porosity of the
membrane in a quantitative way. Different poros-
ity across the membrane is easily spotted from 3D
sample reconstruction, and an estimation of the
shape and dimensions of the pores is also possible
due the high resolution attainable with SR-mCT
(Remigny et al. 2007).
References
Bonse U, Busch F (1996) X-ray computed
microtomography (mCT) using synchrotron radiation
(SR). Prog Biophys Mol Biol 65:133–169
Manke I, Markötter H, Tötzke C, Kardjilov N,
Grothausmann R, Dawson M, Hartnig C, Haas S,
Thomas D, Hoell A, Genzel C, Banhart J (2011) Inves-
tigation of energy-relevant materials with synchrotron
x-rays and neutrons. Adv Eng Mat 13:712–729
Remigny JC, Meireles M, Thibault X (2007) Morpholog-
ical characterization of a polymeric microfiltration
membrane by synchrotron radiation computed
microtomography. J Membr Sci 305:27–35
G
Galacto-oligosaccharide Production
by Membrane Operations
Chiranjib Bhattacharjee1 and Dwaipayan Sen2
1
Department of Chemical Engineering, Jadavpur
University, Kolkata, West Bengal, India
2
Department of Chemical Engineering, Heritage
Institute of Technology, Kolkata, West Bengal,
India
▶ Membrane separation process is one of the
mostly coveted applications in different segments
of industries, especially, in food engineering and
effluent treatment sectors. One of the substantial
advantages that attributes to the membrane sepa-
ration process is the separation of the macromol-
ecules (with respect to the membrane) without
much operational complexity. This ensures the
reusability and high yield of the separated com-
ponents as retentate. However, membrane sepa-
ration process has some primal intricacies that
sometimes constraint the application of the pro-
cess, especially, in food processing industries as
prominent technology. One of such complexities
attribute to primarily membrane fouling (Fig. 1)
that reduces the performance as well as the reus-
ability of the membrane. Polysaccharides’ foul-
ing of the membrane is such a significant
contributor to the foulant genre that might reduce
the performance of the separation process
(Metzger et al. 2007). Separation of galacto-
oligosaccharides (GOS) from the reaction
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1105-1
medium comprising of sugars and other saccha-
rides using membrane separation technique could
be one of the tempting issues in recent pasts that
has been explored by food scientists. During
membrane separation process, the primary objec-
tive that has to be decided by the user is the proper
selection of membrane molecular weight cutoff
(MWCO) and the membrane material itself that
has low vulnerability toward the carbohydrate
adsorption on the membrane. The molecular
weight of GOS varies from di to penta units of
monosaccharides (340–828 Da). However, for-
mation of more than tri could be sometimes triv-
ial because of the steric hindrance that resists
attaching the mono-sugar unit with the galactosyl
moiety (Chen et al. 2002). Hence, the
nanofiltration with 300 Da membrane could be a
better cutoff in separating GOS from other sugars
present in the reaction mixture (Sen et al. 2011).
Moreover, the membrane material is one of the
key issues that control the yield of GOS. Sen
et al. (2011) studied that polyethersulfone (PES)
and cellulose triacetate (CTA) membrane could
interact with the monosaccharides produced dur-
ing enzymatic reaction and results an inhibition
of the enzyme restricting the production of GOS.
Aforesaid fouling of the membrane because of
sugars and polysaccharides leads to an imple-
mentation of diafiltration, where the reaction
mixture is continuously diluted with a volume
of water (either in batch (Fikar et al. 2010) or
continuous process) depending on the volume
concentration factor (VCF) (given by the ratio
2 Galacto-oligosaccharide Production by Membrane Operations
Galacto-oligosaccharide Production by Membrane
Operations, Fig. 1 Fouling of membrane
of the feed volume and retentate volume after
batch) maintained during the diafiltration.
Grandison et al. (2002) studied the purification
of produced GOS with two different
nanofiltration membrane modules, dead-end and
cross-flow, in diafiltration mode and concluded
cross-flow nanofiltration yields more purified
GOS. In addition, they had compared their results
with different sets of membrane, where they con-
cluded thin-film composite membrane performs
better than cellulose triacetate membrane in the
purification of GOS. One of the reasons that attri-
butes to an enhanced purification in cross-flow
system is the sweeping action across the mem-
brane, which removes the fouling layer of the
deposited sugars on the membrane. In 2007,
Mellal et al. had used multi-shaft rotating disk
system in order to purify oligosaccharides to
depict the applicability of high-sheared mem-
brane modules. Das et al. (2011) had shown that
nanofiltration with rotating disk membrane mod-
ule, another high-sheared membrane module,
will create enough turbulence over the membrane
enough to disrupt the concentration polarization
and yield purified GOS. Therefore, purification of
GOS is one of the prime concerns that can be
done with a convenient membrane separation
scheme attributing to some mechanically modi-
fied low fouling devices.
References
Chen C-S, Hsu C-K, Chiang B-H (2002) Optimization of
the enzymic process for manufacturing low-lactose
milk containing oligosaccharides. Process Biochem
38:801–808
Das R, Sen D, Sarkar A, Bhattacharyya S, Bhattacharjee C
(2011) A comparative study on the production of
galacto-oligosaccharide from whey permeate in recy-
cle membrane reactor and in enzymatic batch reactor.
Ind Eng Chem Res 50:806–816
Fikar M, Kovács Z, Czermak P (2010) Dynamic optimi-
zation of batch diafiltration processes. J Membr Sci
355:168–174
Grandison AS, Goulas AK, Rastall RA (2002) The use of
dead-end and cross-flow nanofiltration to purify prebi-
otic oligosaccharides from reaction mixtures,
Songklanakarin. J Sci Technol 24:915–928
Mellal M, Ding LH, Jaffrin MY, Delattre C, Michaud P,
Courtois J (2007) Separation and fractionation of
oligouronides by shear-enhanced filtration. Sep Sci
Technol 42:349–361
Metzger U, Le-Clech P, Stuetz RM, Frimmel FH, Chen V
(2007) Characterisation of polymeric fouling in mem-
brane bioreactors and the effect of different filtration
modes. J Membr Sci 301:180–189
Sen D, Sarkar A, Gosling A, Gras SL, Stevens GW,
Kentish SE, Bhattacharya PK, Barber AR,
Bhattacharjee C (2011) Feasibility study of enzyme
immobilization on polymeric membrane: a case study
with enzymatically galacto-oligosaccharides produc-
tion from lactose. J Membr Sci 378:471–478
P
Plasma-Enhanced Chemical Vapor
Deposition
Antonella Milella and Fabio Palumbo
Department of Chemistry, University of Bari
“Aldo Moro”, Institute of Nanotechnology
(CNR-NANOTEC), Bari, Italy
Plasma-enhanced chemical vapor deposition
(PECVD) is a process of film formation onto a
substrate when a plasma is applied to a proper
vapor or gas precursor. PECVD coatings can be
both organic and inorganic, depending on the
precursor choice and the experimental conditions
used for the deposition. When the deposited film
is organic, the PECVD process is commonly
referred to as “plasma polymerization,” and the
precursor is termed monomer. However, plasma-
deposited films pretty much differ from conven-
tional polymers since their structure has no
repeating unit. The layers deposited by PECVD
are typically: (i) well adherent, (ii) pine-hole-
free, (iii) amorphous and cross-linked, and
(iv) conformal and 3D object compatible,
(v) with tunable chemical composition and struc-
ture. This process allows for the deposition of
films with thickness in the range 10–10,000 nm,
with deposition rates normally of the order of tens
of nm/s and in some cases hundreds of nm/s.
The growth mechanism of PECVD coatings,
known as activated growth mechanism (AGM),
has been deeply investigated (d’Agostino 1990;
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1106-1
Milella et al. 2005; d’Agostino and Palumbo
2012) and is summarized in Fig. 1.
The monomer (Mon, step 1) is fragmented in
the gas phase by electron impact (see ▶ Cold
Plasma in this encyclopedia), with the formation
of different radicals (R). Ion bombardment of the
substrate and of the growing film influences the
deposition rate since impinging ions transfer
energy to the surface, eventually creating surface
defect sites (active sites) with reduced activation
energies for dissociative chemisorptions
(Substrate*, step 2). Radical species can then
adsorb and react with the active sites, thus con-
tributing to film growth (step 3). Bombardment of
material surface by low-energy ions can lead to
breakage of chemical bonds, surface diffusion,
and heating, which contribute to film densifica-
tion and to enhanced film-substrate adhesion.
Moreover, the energy transfer by impinging ions
can favor the molecular dissociative chemisorp-
tion. High-energy ion bombardment can deter-
mine dramatic rearrangement of the structure of
the growing film, such as sputtering of surface
atoms, structural damage, and high internal
stress. In this extremely reactive scenario, the
film grows with a complex and cross-linked
structure and with a not conventional chemical
composition.
Instead of sticking directly to the surface of the
growing polymer, radicals can also polymerize in
the gas phase forming oligomers (Rn, step 4) or
even powders (step 5) which can be afterwards
included in the growing film (step 6). However,
2 Plasma-Enhanced Chemical Vapor Deposition
Mon (gas) + e
1
R (gas) + e
2 mer. The challenge in this kind of process is to
Substrate + I+ Substrate*
3 ity, which can be easily cleaved in plasma. This is
R (gas) + Substrate* a- (film)
5 plasma by properly adjusting process parameters.
4
n R (gas) R n(gas)
6 6
a- (film)
Plasma-Enhanced Chemical Vapor Deposition,
Fig. 1 Sketch of the activated growth model
this second route generally leads to polymers less
compact and with poor adhesion to the substrate.
Based on this mechanism it appears quite
straightforward that the chemical composition
and structure of PECVD films can be finely
tuned by properly adjusting process parameters
such as input power, pressure, feed composition,
substrate temperature, and self-bias (see ▶ Cold
Plasma in this encyclopedia).
In the field of membrane processing, PECVD
can be used both to modify the surface of com-
mercially available membranes and to prepare
freestanding ones. These membranes mainly
find applications in the field of gas and liquid
separation, fuel cells, sensors, and biomaterials
(Roualdes et al. 2010; Memoli et al. 2007; De
Bartolo et al. 2005).
The gas and liquid permeability of membranes
can be tuned with the aid of suitable PECVD
coatings, through the control of the surface wet-
tability or inducing specific chemical interactions
between the permeant molecules and the film.
Silicon oxide-like coatings have been widely
exploited as barrier to control gas and vapors
permeation (Coclite et al. 2010; Creatore
et al. 2001; Julbe et al. 2008). Acid and base
functionalized coatings can be deposited on con-
ventional membranes to enhance their liquid or
vapor separation performances (Weibel
et al. 2007).
PECVD ion exchange membranes can mainly
find application for the production of planar pro-
ton exchange membrane fuel cells. Commonly,
the membranes are prepared feeding the plasma
with an acid precursor and a fluorocarbon mono-
retain in the deposited films the acid functional-
usually obtained by lowering the energy of the
Powders Proton conductivities in the range of
10 3–2 mS/cm have been reported; however,
values as high as 180 mS/cm have been recently
achieved (Brault et al. 2006; Thery et al. 2010).
Polyethersulfone (PES) membranes have been
coated with plasma-polymerized acrylic acid for
the subsequent immobilization of galactonic acid
through a hydrophilic spacer arm molecule. This
strategy allowed the setup of a bioreactor for
biomimicking the cellular microenvironment
accomplishing long-term maintenance and dif-
ferentiation of human hepatocytes (Memoli
et al. 2007; De Bartolo et al. 2005).
References
Brault P, Roualdes S, Caillard A, Thomann A-L,
Mathias J, Durand J, Coutanceau C, Leger J-M,
Charles C, Boswell R (2006) Solid polymer fuel cell
synthesis by low pressure plasmas: a short review. Eur
Phys J Appl Phys 34:151–156
Coclite AM, Milella A, d’Agostino R, Palumbo F (2010)
On the relationship between the structure and the bar-
rier performance of plasma deposited silicon dioxide-
like film. Surf Coat Technol 204:4012–4017
Creatore M, Palumbo F, d’Agostino R, Fayet P (2001) RF
plasma deposition of SiO2-like films: plasma phase
diagnostics and gas barrier film properties optimiza-
tion. Surf Coat Technol 163:142–144
d’Agostino R (1990) Plasma deposition, treatments and
etching of polymers. Academic, San Diego
d’Agostino R, Palumbo F (2012) Comment on “Ion-
assisted processes of polymerization in low-pressure
plasmas”. Plasma Process Polym 9:844–849
De Bartolo L, Morelli S, Lopez LC, Giorno L,
Campana C, Salerno S, Rende M, Detomaso L,
Gristina R, d’Agostino R, Drioli E (2005) Biotransfor-
mation and liver-specific functions of human hepato-
cytes in culture on RGD-immobilized plasma-
processed membranes. Biomaterials 26:4432–4441
Julbe A, Rouessac V, Durand J, Ayral A (2008) New
approaches in the design of ceramic and hybrid mem-
branes. J Membr Sci 316:176–185
Memoli B, De Bartolo L, Favia P, Morelli S, Lopez LC,
Procino A, Barbieri G, Curcio E, Giorno L, Esposito P,
Cozzolino M, Brancaccio D, Andreucci V,
Plasma-Enhanced Chemical Vapor Deposition
d’Agostino R, Drioli E (2007) Fetuin-A gene expres-
sion, synthesis and release in primary human hepato-
cytes cultured in a galactosylated membrane
bioreactor. Biomaterials 28:4836–4844
Milella A, Palumbo F, Favia P, Cicala G, d’Agostino
R (2005) Deposition mechanism of nanostructured
thin films from tetrafluoroethylene glow discharges.
Pure Appl Chem 77:399–414
Roualdes S, Rouessac V, Durand J (2010) Plasma Mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
3
membrane science and engineering. Elsevier,
Kidlington, pp 159–197
Thery J, Martin S, Faucheux V, Le Van Jodin L, Truffier-
Boutry D, Martinent A, Laurent J-Y (2010) Fluorinated
carboxylic membranes deposited by plasma enhanced
chemical vapour deposition for fuel cell applications.
J Power Sources 195:5573–5580
Weibel DE, Vilani C, Habert AC, Achete CA (2007) Sur-
face modification of polyurethane membranes using
acrylic acid vapour plasma and its effects on the
pervaporation precesses. J Membr Sci 293:124–132
C
Cold Plasma
Antonella Milella and Fabio Palumbo
Department of Chemistry, University of Bari
“Aldo Moro”, Institute of Nanotechnology
(CNR-NANOTEC), Bari, Italy
Plasma can be defined as a partially ionized gas
which contains approximately equal numbers of
positive and negative particles (Chapman 1980;
Chen 1974; Grill 1994; Thornthon and Greene
1994; d’Agostino 1990; Milella 2008).
Plasmas can be roughly classified into hot
plasmas (also defined as near-equilibrium
plasmas) and cold plasmas (or nonequilibrium
plasmas). Hot plasmas are characterized by very
high temperatures of electrons and heavy parti-
cles (atoms, molecules, or ions) and they are
almost fully ionized. In cold plasmas, instead,
the electron temperature is relatively high
(1–10 eV), while the translational energy of
heavy particles remains very low, with tempera-
ture close to the room one and the ionization
degree is typically low (around 10 4 –10 6).
When an electric field is applied to a gas, energy
is transferred more efficiently to the free elec-
trons naturally present in the gas than to the
ions. The accelerated electrons, then, transfer
the energy to heavier particles through elastic
and inelastic collisions. At low pressure the col-
lision frequency is very low; moreover, because
of the large mass difference between electrons
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1107-1
and heavy particles, the transfer of kinetic energy
is inefficient. Hence, in this nonequilibrium state,
the gas temperature cannot increase, while elec-
trons gain enough kinetic energy to promote exci-
tation, ionization, fragmentation, and formation
of reactive species by inelastic collisions with
heavy particles. In this scenario, energetic elec-
trons can produce high temperature chemistry in
a gas at low temperature, and this allows the
treatment of thermally sensitive materials like
polymers.
Since electrons are much faster than other
particles, every surface immersed in the plasma
immediately develops a negative charge which
accelerates ions. As a matter of fact, the plasma
potential is always the most positive one.
A low-pressure cold plasma apparatus typi-
cally consists of a vacuum chamber, a pumping
unit, a gas feeding system and gas controllers,
pressure gauge, a power supply, and a power
transfer device. Electrodes can be driven both
by AC and by DC power supply. AC discharges,
commonly run in the radiofrequency (RF) and
microwave (MW) range, are more stable and
suitable for insulators (e.g., ceramic and poly-
mers) processing. In case of RF glow discharges,
the operating frequency is generally 13.56 MHz
in order to avoid interferences with communica-
tions. At this frequency, only electrons can follow
the instantaneous variations of the applied elec-
tric field, while ions are driven by an average
potential.
2 Cold Plasma
At the steady state, the total ion and electron
charge flow to a given electrode during an RF
cycle must balance to zero and a self-bias that is
negative with respect to the plasma potential
develops. If the surface is electrically isolated,
the potential at the steady state is named floating
potential and it is also negative with respect to the
plasma potential. As a consequence, each surface
immersed in a plasma will be bombarded by ions.
It should be also highlighted that cold plasmas
can be also ignited at atmospheric pressure, and
since the late 1980s, an increasing interest has
grown in the application of such plasmas (e.g.,
dielectric barrier discharge, corona, and atmo-
spheric jet) to material processing (Kogelschatz
2003).
Cold plasmas can modify the surface of mate-
rial by depositing thin films (plasma-enhanced
chemical vapor deposition), by grafting specific
chemical functionalities (plasma treatment), or
by ablating materials (plasma etching).
Membranes can be processed by means of
cold plasmas to activate the surface by introduc-
ing specific chemical groups such as hydroxyl,
carboxyl, and amino moieties. This can be
accomplished by feeding the plasma
non-polymerizable gases/vapor such as O2,
H2O, NH3, and N2/H2. Alternatively,
functionalized coatings can be deposited for the
same purposes (e.g., acrylic acid or allylamine
based). These treatments allow to tune surface
properties of membranes, notably wettability
and molecular adsorption, or to serve as anchor
for specific biomolecules or catalysts (Favia
et al. 2008; Fontananova et al. 2006; Roualdes
et al. 2010).
References
Chapman B (1980) Glow discharge processes. Sputtering
and plasma etching. Wiley, New York
Chen FF (1974) Introduction to plasma physics. Plenum
Press, New York
d’Agostino R (1990) Plasma deposition, treatments and
etching of polymers. Academic, San Diego
Favia P, Sardella E, Lopez LC, Laera S, Milella A,
Pistillo B, Intranuovo F, Nardulli M, Gristina R,
d’Agostino R (2008) Plasma assisted surface modifi-
cation processes for biomedical materials and devices.
In: G€uçeri S, Fridman A (eds) Plasma assisted decon-
tamination of biological and chemical agents.
Springer, Dordrecht, pp 203–226
Fontananova E, Donato L, Drioli E, Lopez LC, Favia P,
d’Agostino R (2006) Heterogenization of
polyoxometalates on the surface of plasma-modified
polymeric membranes. Chem Mater 18:1561–1568
Grill A (1994) Cold plasma in materials fabrication-from
fundamentals to applications. IEEE Press, New York
Kogelschatz U (2003) Dielectric-barrier discharges: their
history, discharge physics, and industrial applications.
Plasma Chem Plasma Proc 3:1–46
Milella A (2008) Plasma processing of polymers. In:
Encyclopedia of polymer science and technology.
Wiley
Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
membrane science and engineering. Elsevier,
Kidlington, pp 159–197
Thornthon JA, Greene JE (1994) Plasmas in deposition
processes. In: Bunshah RF (ed) Handbook of deposi-
tion technologies for films and coatings. Science tech-
nology and applications. Noeys Publications, New
Jersey, pp 55–107
C
Crystal Nucleation
Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
Crystal nucleation is the first stage of a crystal-
lization process and leads to the formation of
distinct crystal nuclei. It is a local phenomenon
of aggregation, and it is said to be homogeneous
when it occurs in the bulk of the solution and
heterogeneous on very small solid particles,
such as amorphous clusters or crystalline parti-
cles. In both cases, the formation of crystal nuclei
requires well-oriented collisions between mole-
cules to occur. The activation energy necessary to
induce nucleation is represented by the free
energy of germination D(Gg) shown in Eq. 1
(Mullin 1972), consisting of a positive term
called interfacial free energy (in red color in
Fig. 1) and a negative term called free energy of
aggregation (in green color in Fig. 1):



DGg ¼ 4prr 2  4pr 3 SkT =3V (1)
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1126-2
In the Eq. 1, V is the volume of the molecule to
crystallize, r is the interfacial free energy, T is the
temperature, k is the Boltzmann factor, and r is
the average radius of the crystal nuclei. DGg
reaches a maximum value for a given nucleus
radius (Fig. 1); therefore, only crystal nuclei
that grow up to this dimension are stable, while
smaller nuclei dissolve before to pass the next
crystal growth. In order to reduce the energy of
activation, high S value, that is an estimation of
the supersaturation level of the solution, is
required. Supersaturation is an essential condi-
tion required during each stage of the crystalliza-
tion process; however, the nucleation, being the
most energy expensive stage of the entire crys-
tallization process, requires higher supersatura-
tion level to take place. The mechanism and the
rate of nucleation strongly influence quality and
quantity of the produced crystals; therefore,
many efforts are devoted to control the nucleation
in order to obtain crystals having high quality.
One of the main problems in industrial or labora-
tory crystallization processes is the excess of
nucleation that usually leads to a rain of tiny
poor-quality crystals. The use of filtered solutions
is the solution commonly adopted to overcome
this problem; however, in the cases where
2 Crystal Nucleation
Crystal Nucleation,
Fig. 1 Effect of the
nucleus radius (r) on the
free energy of germination
DGg (in black color).
Interfacial free energy and
free energy of aggregation
are reported in red and
green color, respectively
nucleation is welcome, the presence of dust or
small foreign particles, such as mica or silica able
to promote heterogeneous nucleation, can repre-
sent an advantage (Falini et al. 2002; Saridakis
and Chayen 2009). These particles, also called
crystallization seeds, act as nucleant and usually
increase the chances of crystallization by facili-
tating the proper molecular orientation during the
formation of the crystal nuclei (Bolanos-Garcia
and Chayen 2009). The result is the reduction of
the activation energy and, consequently, the
decrease of the supersaturation level required to
induce the formation of crystal nuclei with
respect to that required in the homogeneous
nucleation. In these conditions, nucleation could
even occur in the metastable zone where crystals
grow larger and better ordered than those grown
at higher supersaturation level. The direct contact
between crystallizing solution and an irregular
surface can induce heterogeneous nucleation, as
occurs in membrane crystallizers (Di Profio
et al. 2003, 2005). The local entrapping of the
solute molecules in the pores of the membrane
causes an increase of the local level of supersat-
uration (Curcio et al. 2006), inducing the forma-
tion of crystal nuclei also in the presence of lower
amount of initial substance. For this reason,
membrane crystallizers are particularly attractive
for crystallization processes where the solute is
expensive, such as in the case of proteins. In
addition, a fine regulation of the nucleation rate
can be achieved by managing the transmembrane
flux of the solvent from the crystallizing solution
toward the stripping solution located on the other
side of the membrane. Nucleation mechanism on
the membrane (Fig. 2) consists of a first phase
where solute molecules are adsorbed on the sur-
face by means of attractive interactions able to
properly orient the molecule and that usually
drive the growth of the crystal toward a specific
crystal structure (Di Profio et al. 2009). The effec-
tive control of the nucleation process by means of
an appropriate choice of the porosity and hydro-
phobicity of the membrane and by managing the
transmembrane flux makes membrane
Crystal Nucleation 3

crystallizers particularly suitable for industrial

applications.

References

Bolanos-Garcia VM, Chayen NE (2009) New directions

in conventional methods of protein crystallization.
Prog Biophys Mol Biol 101:26–37
Curcio E, Fontananova E, Di Profio G, Drioli E (2006)
Influence of the structural properties of poly(vinyli-
dene fluoride) membranes on the heterogeneous nucle-
ation rate of protein crystals. J Phys Chem
B 110:12438–12445
Di Profio G, Curcio E, Cassetta A, Lamba D, Drioli
E (2003) Membrane crystallization of lysozyme:
kinetic aspects. J Cryst Growth 257:359–369
Di Profio G, Perrone G, Curcio E, Cassetta A, Lamba D,
Drioli E (2005) Preparation of enzyme crystals with
tunable morphology in membrane crystallizers. Ind
Eng Chem Res 44:10005–10012
Di Profio G, Curcio E, Ferraro S, Stabile C, Drioli
E (2009) Effect of supersaturation control and hetero-
geneous nucleation on porous membrane surfaces in
the crystallization of L-glutamic acid polymorphs.
Cryst Growth Des 9:2179–2186
Falini G, Fermani S, Conforti G, Ripamonti A (2002)
Protein crystallisation on chemically modified mica
surfaces. Acta Crystallogr D 58:1649–1652
Mullin JW (1972) Crystallization. Butterworths, London
Saridakis E, Chayen NE (2009) Towards a ‘universal’
nucleant for protein crystallization. Trends Biotechnol
27:99–106

Crystal Nucleation, Fig. 2 Mechanism of crystal nucle-

ation on membrane. Solute molecules (red spheres) are
adsorbed on the surface and are trapped inside the pores of
the membrane, resulting in an increase of local
concentration
C
Crystal Polymorphism
Polymorphism
Benny Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
The term polymorphism comes from the Greek
word polus = many and morph = shape, and it
is the propriety of the chemical substances to
exist in more crystal forms, each having a specific
arrangement of atoms or ions in the crystal lattice.
Crystal polymorphism includes the allotropy
phenomenon, which refers to pure elements.
Crystal forms that differ for packing or for molec-
ular conformation are said packing or conforma-
tional polymorphs, respectively. From a
thermodynamic viewpoint, polymorphism can
be of two kinds: enantiotropic (Fig. 1a), in the
case of crystal forms stable in a precise range of
temperature and pressure (e.g., the system rhom-
bic sulfur-monoclinic sulfur in Fig. 1b), and
monotropic (Fig. 1c), in the case of crystalliza-
tion process that spontaneously evolves toward a
crystal form characterized by lower internal
energy with respect to the other forms
(metastable forms). Generally, monotropes and
enantiotropes can be recognized by their heats
of fusion, since monotropes come from exother-
mic processes and enantiotropes from endother-
mic processes. Whatever is the kind of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1127-2
polymorphism, under static crystallization condi-
tions, the probability of carrying out crystalliza-
tion precisely at the boundary that separates the
polymorphic forms is small; therefore only one
crystal form appears at the end of the crystal
growth. The mechanism that explains the poly-
morphism involves the stage of crystal nuclei
formation. During the nucleation stage, some
molecules can leave the preformed aggregates,
leading to their complete dissolution. The surviv-
ing aggregates provide the new differently
arranged templates for the subsequent growth
stage, and the molecular arrangement in largest
amount will form the nuclei that will grow in a
particular crystal form. The critical dimension
that the aggregates must reach to survive depends
of the supersaturation level; therefore, the entire
process is under kinetic control rather than ther-
modynamic (Volmer 1939; Ostwald 1987).
Today, the interest for the phenomenon of poly-
morphism is increasing, particularly for pharma-
ceutical industry where its study is became
integral part of the drug optimization process
(Brittain 1999). Paracetamol (Beyer et al. 2001),
famotidine (Lu et al. 2007), and piroxicam
(Giordano et al. 1998) are the classical examples
of drugs crystallized in several forms, each hav-
ing different chemical and pharmaceutical pro-
prieties. Usually, pharmaceutical industry prefers
the most stable form with respect to that metasta-
ble, although, at the same concentration, the latter
is more available in the organism due to its higher
solubility. Also protein molecules can crystallize
2 Crystal Polymorphism

a b

Pressure
Free energy
Monoclinic form 153°C
1420 atm
95°C Liquid
1 atm
A form
Rhombic 445°C
form
115°C
10-5 atm Gas
115°C
B form 10-5 atm

Tx TmB TmA temperature temperature

c
Free energy

A form

B form

TmB TmA temperature

Crystal Polymorphism, Fig. 1 Enantiotropic and
monotropic systems. (a) Variation of free energy with
temperature for enantiotropic substances. The tempera-
ture Tx, which marks the boundary between stability
zones for A and B forms, is below the melting tempera-
tures of the two substances (TmA and TmB). (b) Phase
diagram for the enantiotropic system rhombic sulfur-
monoclinic sulfur. (c) Variation of free energy with tem-
perature for enantiotropic substances. No crossing of free
energy curves belonging to the A and B forms can be
observed below of their melting temperatures (TmA and
TmB)

in several crystal forms, as a consequence of the
different conformations assumed by peptide
chain in a given condition. A classic example of
polymorphism for crystal of proteins is the lyso-
zyme that crystallizes in six different crystalline
forms. Another important example is the
ubiquitin, whose crystal form depends on the
nature and the amount of the metal ion used
during the crystallization (Arnesano et al. 2011;
Falini et al. 2009). The technology of membrane
crystallizers gives the opportunity to drive the
crystallization toward a specific polymorph.
This is possible by regulating the degree and the
rate to which of supersaturation is reached
through the managing of the transmembrane
flux and an accurate choose of the membrane
properties (Di Profio et al. 2007, 2009, 2013).
So crystallization assisted by membrane can
occur both under thermodynamic and kinetic
control: low evaporation rates through the mem-
brane allow the growth of the more stable nuclei
at the expense of the less stable forms
(thermodynamic control), while the induction of
a more rapid nucleation increases in the presence
of higher evaporation rates and increases the con-
version rate from the stable to the metastable
form (kinetic control). The relative amount of
the two forms depends on the ratio between the
conversion and crystallization rate. Similarly, the
production of a specific polymorph can be
obtained by using antisolvent membrane crystal-
lization processes (Di Profio et al. 2010).
Crystal Polymorphism
References
Arnesano F, Belviso BD, Caliandro R, Falini G,
Fermani S, Natile G, Siliqi D (2011) Crystallographic
analysis of metal-ion binding to human ubiquitin.
Chemistry 17:1569–1578
Beyer T, Day GM, Price SL (2001) The prediction, mor-
phology, and mechanical properties of the polymorphs
of paracetamol. J Am Chem Soc 123(21):5086–94
Brittain HG (1999) Polymorphism in pharmaceutical
solids. Marcel Dekker, New York
Di Profio G, Tucci S, Curcio E, Drioli E (2007) Selective
glycine polymorph crystallization by using micropo-
rous membranes. Cryst Growth Des 7:526–530
Di Profio G, Curcio E, Ferraro S, Stabile C, Drioli
E (2009) Effect of supersaturation control and hetero-
geneous nucleation on porous membrane surfaces in
the crystallization of l-glutamic acid polymorphs.
Cryst Growth Des 9:2179–2186
Di Profio G, Caridi A, Caliandro R, Guagliardi A,
Curcio E, Drioli E (2010) Fine dosage of antisolvent
3
in the crystallization of l-histidine: effect on polymor-
phism. Cryst Growth Des 10:449–455
Di Profio G, Reijonen MT, Caliandro R, Guagliardi A,
Curcio E, Drioli E (2013) Insights into the polymor-
phism of glycine: membrane crystallization in an elec-
tric field. Phys Chem Chem Phys 15:9271–9280
Falini G, Fermani S, Tosi G, Arnesano F, Natile G (2009)
Structural probing of Zn(II), Cd(II) and Hg(II) binding
to human ubiquitin. Chem Commun (Camb)
45:5960–5962
Giordano F, Gazzaniga A, Moyano JR, Ventura P, Zanol
M, Peveri T, Carima L (1998) Crystal forms of
piroxicam pivalate: preparation and characterization
of two polymorphs. J Pharm Sci 87(3):333–337
Lu J, Wang XJ, Yang X, Ching CB (2007) Cryst Growth &
Des 2007(7):1590–1598
Ostwald WZ (1987) Studien uber die Bildung und
Umwandlung fester Korper. Z Phys Chem 22:289–330
Volmer M (1939) Kinetik der Phasenbildung. Steinkopf,
Leipzig
C
Crystal Purity
Benny Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
Crystal purity is the parameter used to indicate
the contamination level of a crystal and repre-
sents one of the most important properties of the
crystalline materials. Crystal purity is also an
index of the heterogeneity of the substance to
crystallize, in particular in the presence of pro-
teins or nucleic acids, whose uncontrolled modi-
fications may increase the number of species in
the crystallizing solution. Contaminants may dis-
tort the crystal lattice, affect the crystal features,
such as diffraction quality, and change the crystal
morphology in particular when the impurities are
incorporated in the crystal at different rates into
adjacent steps on the crystal surface. However,
the main feature of a low-purity crystal is its
higher internal energy with respect to that in
absence of impurities (van Enckevort and van
der Berg 1998; Davis et al. 2004), which causes
an increase of the crystal solubility and a decrease
of the effective supersaturation level of the solu-
tion containing the substance to crystallize: the
higher the contamination, the more difficult the
crystallization because the dissolution probabil-
ity of the crystals increases. Given this, many
efforts should be devoted to adequately purify
the substance to crystallize, by paying attention
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1128-2
to the purity grade of the chemicals employed in
each step. Particular attention should be paid for
precipitant agents, since they are used in very
high concentrations: accordingly, salts and poly-
meric precipitants, such as polyethylene glycol or
alcohols, should be recrystallized or purified,
respectively. Once the crystal is formed, washing
procedures may be carried out to increase crystal
purity by removing many of the surface impuri-
ties or those specifically attached inside the crys-
tal. However, the technique is quite risky, since
the washing solvent should be able to remove the
impurities without dissolving the crystal.
Although contamination is usually the first
cause of unsuccessful crystallization, the alone
presence of impurities is not sufficient to frustrate
the crystallization attempts. Crystal features,
such as crystal lattices having weak interactions
between atoms or containing large empty spaces
where foreign molecules have possibility to fit,
should be avoided to reduce the probability of
crystal contamination. Impurities are included in
a crystal as a result of the processes that occur
concomitantly to the crystallization (in particular
during the nucleation) or after that crystal growth
has finished. Particularly, the degree of crystal
purity depends on the ratio between the rates of
these inclusion processes with that of the crystal-
lization process that, being a purification process,
pushes toward the recovery of the desired product
without contaminations (Burton et al. 1953): usu-
ally, slow crystallizations allow the substance to
crystallize to properly fit in the lattice, differently
2 Crystal Purity
from more rapid precipitations, where the inser-
tion of the impurities results facilitate. In addi-
tion, high supersaturation often leads to
contaminant inclusions that reduce the crystal
purity. At the present, membrane technology rep-
resents one of more promising tools to produce
high-purity crystal. By controlling the transmem-
brane flux, membrane crystallizer can limit the
maximum level of supersaturation and reduce the
growth rate to reach the critical threshold, beyond
which inclusion of impurities occurs (Weckesser
and Konig 2008; Mullin 1993). Today, the
advances made in the development of
membrane-assisted crystallization allow produc-
ing crystalline materials having the purities
required for their commercialization as purified
product. One of the most important examples is
represented by the production of sodium carbon-
ate crystals having purity grade that reaches
ca. 99.5 % also starting from crystallizing solu-
tions containing concentrations ranging from 0.2
to 0.6 M of impurities, such as sodium nitrate,
sodium sulfate, and sodium chloride
(Ye et al. 2013). In addition, membrane devices
are also used to produce high-purity cocrystal, a
challenge particularly interesting for pharmaceu-
tical industry.
References
Burton JA, Prim RC, Slichter WP (1953) The distribution
of solute in crystals grown from the melt. Part
I. Theoretical. J Chem Phys 21:1987–1991
Davis KJ, Dove PM, Wasylenki LE, Deyoreo JJ
(2004) Morphological consequences of differential
Mg2+ incorporation at structurally distinct steps on
calcite. Am Mineral 89:714–720
Mullin JW (1993) Crystallization, 3rd edn. Butterworth-
Heinemann, Oxford
van Enckevort WJP, van der Berg (1998) Impurity
blocking of crystal growth: a Monte Carlo study.
J Cryst Growth 183:441–455
Weckesser D, Konig A (2008) Particle shape and purity in
membrane based crystallization. Chem Eng Technol
31:157–162
Ye W, Lin L, Shen J, Luis P, Van der Bruggen B (2013)
Cryst Growth Des 13:2362–2372
C
Crystal Seeding
Benny Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
Synonyms
Seeding
Crystal seeding is a technique widely employed
to provide preformed templates (seeds) on which
new molecules can converge to form crystals.
Crystal seeding is said homogeneous if the
seeds are made of the same molecule to crystal-
lize, as occurs in macroseeding, microseeding,
and streak seeding, and heterogeneous if it fore-
sees the use of foreign material, such as porous
silicon and mica (Saridakis and Chayen 2009), as
in the case of cross seeding and epitaxial growth.
Whatever the kind of used seeds, their presence
generally makes less energetically expensive the
entire crystallization process, because it allows
the passing directly to the crystal growth stage
without dealing with the intrinsic uncertainties of
the nucleation. However, the usage of seeds
might have the disadvantage to affect the crystal
growth and the forming crystal lattice (Hermes
et al. 2011; Liu et al. 2007). The first step for
much of seeding techniques is the production of
seeds: during this phase, preformed crystals are
washed to remove defects and impurities that
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1129-3
could block the crystal growth, stabilized in an
appropriate solution, and crushed by using a glass
homogenizer or by using spherical beads. Once
the seed stock has been obtained, pre-equilibrium
conditions (e.g., temperature, precipitant agents,
additives, etc.) of the solution to seed are care-
fully determined together with the appropriate
level of supersaturation, in order to avoid the
trigger of a self-nucleation that would frustrate
all following efforts. In the absence of such infor-
mation, the seeding process could result in a
dissolving of the seeds or in a rain of tiny and
poor-quality crystals. In order to assess seeding
conditions, protein crystallographers usually
exploit streak seeding technique, where a syn-
thetic or natural fiber (Bergfors 2003) is used to
crush existing crystals and to introduce the
resulting small crystalline particles into different
pre-equilibrated solutions: mode and timing of
seed growth allow to determine both the appro-
priate range of pre-equilibration conditions and
the dilution of the seed stock. Although the tech-
niques of seeding were initially developed with
the aim to optimize and make more reproducible
the crystallization processes performed in labo-
ratory, today they are widely employed also in
high-throughput processes that range from the
industrial crystallizations to the preparation of
devices employed in membrane reactors or in
separation processes, such as membranes of zeo-
lite (Li et al. 2005) or silicate crystals (Hasegawa
et al. 2006). Preparation of these membrane
devices is very challenging because it requires a
2 Crystal Seeding
Crystal Seeding, Table 1 Seeding procedures for zeo-
lite membrane preparation
Seeding procedure References
Secondary growth Lovallo and Tsapatsis (1996)
Dip coating (Lovallo et al. 1998; Bernal
et al. 2001)
Spin coating Mintova and Bein (2001)
Rubbing (Kusakabe et al. 1998;
Hasegawa et al. 2002)
Cationic polymer use (Hedlund et al. 1999; Weh
et al. 2002)
Cross-flow filtration Pera-Titus et al. (2005)
Dead-end filtration Huang et al. (2004)
(vacuum seeding)
strong control of the seeding in order to obtain
high-quality membranes having determined fea-
tures, such as a specific crystalline orientation
(Caro et al. 2000). Several seeding techniques
have been developed to produce a membrane of
zeolite crystal (Table 1), and the secondary
growth together with dip coating is considered
among those most promising: secondary growth
exploits a hydrothermal treatment of the mem-
brane support that has been previously covered
with layers of seeds (Lovallo and Tsapatsis
1996), while dip coating takes advantage from
the capillary force to aid the deposition of crystal
seeds (Lovallo et al. 1998; Bernal et al. 2001). In
addition, filtration procedures, such as cross-flow
filtration and dead-end filtration (Pera-Titus
et al. 2005; Huang et al. 2004), based on the
seed deposition on the membrane support under
the action of a difference of pressure applied,
have been also developed.
References
Bergfors T (2003) Seeds to crystals. J Struct Biol
142:66–76
Bernal MP, Xomeritakis G, Tsapatsis M (2001) Tubular
MFI zeolite membranes made by secondary (seeded)
growth. Catal Today 67:101–107
Caro J, Noack M, Kolsch P, Schafer R (2000) Zeolite
membranes-state of their development and perspec-
tive. Micropor Mesopor Mater 38:3–24
Hasegawa Y, Sotowa KI, Kusakabe K, Morooka S (2002)
The influence of feed composition on CO oxidation
using zeolite membranes loaded with metal catalysts.
Micropor Mesopor Mater 53:37–43
Hasegawa Y, Ikeda T, Nagase T, Kiyozumi Y, Hanaoka T,
Mizukami F (2006) Preparation and characterization
of silicalite-1 membranes prepared by secondary
growth of seeds with different crystal sizes. J Membr
Sci 280:397–405
Hedlund J, Noack M, Kolsch P, Creaser D, Caro J, Sterte
J (1999) ZSM-5 membranes synthesized without
organic templates using a seeding technique.
J Membr Sci 159:263–273
Hermes M, Vermolen ECM, Leunissen ME, Vossen DLJ,
van Oostrum PDJ, Dijkstra M, van Blaaderen A (2011)
Nucleation of colloidal crystals on configurable seed
structures. Soft Matter 7:4623–4628
Huang A, Lin YS, Yang W (2004) Synthesis and proper-
ties of A-type zeolite membranes by secondary growth
method with vacuum seeding. J Membr Sci 245:41–51
Kusakabe K, Kuroda T, Morooka S (1998) Separation of
carbon dioxide from nitrogen using ion-exchanged
faujasite-type zeolite membranes formed on porous
support tubes. J Membr Sci 148:13–23
Li G, Lin RS, Kikuchi E, Matsukata M (2005) Growth
mechanism of a preferentially oriented mordenite
membrane. J Zhejiang Univ Sci B 6:369–372
Liu YX, Wang XJ, Lu J, Ching CB (2007) Influence of the
roughness, topography, and physicochemical proper-
ties of chemically modified surfaces on the heteroge-
neous nucleation of protein crystals. J Phys Chem
B 111:13971–13978
Lovallo MC, Tsapatsis M (1996) Preferentially oriented
submicron silicalite membranes. AIChE
J 42:3020–3029
Lovallo MC, Gouzinis A, Tsapatsis M (1998) Synthesis
and characterization of oriented MFI membranes pre-
pared by secondary growth. AIChE J 44:1903–1913
Mintova S, Bein T (2001) Microporous films prepared by
spin-coating stable colloidal suspensions of zeolites.
Adv Mater 13:1880–1883
Pera-Titus M, Llorens J, Cunill F, Mallada R, Santamarıa
J (2005) Preparation of zeolite NaA membranes on the
inner side of tubular supports by means of a controlled
seeding technique. Catal Today 104:281–287
Saridakis E, Chayen NE (2009) Towards a ‘universal’
nucleant for protein crystallization. Trends Biotechnol
27:99–106
Weh K, Noack M, Sieber I, Caro J (2002) Permeation of
single gases and gas mixtures through faujasite-type
molecular sieve membranes. Micropor Mesopor Mater
54:27–36
C
Crystallizing Solution
Benny Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
Crystallizing solution (also called crystallizing
cocktail) is the ensemble of chemicals able to
promote the crystallization of a substance in a
given physical condition (e.g., temperature,
vibrations, surface of crystallization, etc.). Crys-
tallization requires that the solution containing
the substance to crystallize is supersaturated
with respect to the latter, namely, that the solute
concentration is higher than its solubility limit
but lower than the precipitation threshold: an
appropriately formulated crystallizing solution
reduces the solubility of the substance (both in
the case of small inorganic/organic molecules
and biological macromolecules, such as pro-
teins), enabling a more easily reaching of the
crystallization range, where spontaneous forma-
tion of the first crystalline nuclei and their next
growth can occur. Usually, crystallizing solution
consists of a precipitating agent, a substance
whose concentration is inversely correlated to
the solubility of the molecule to crystallize, and
a buffer salt able to stabilize the pH during the
crystallization process. In order to optimize the
crystallization, additives, whose concentration is
lower than that of the main components, can be
added. In the case of crystallization of proteins,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1131-1
ligands and cofactors can be exploited to stabilize
the protein or to increase its conformational
purity. Notwithstanding it is common to classify
the components of a crystallizing solution
according to these three categories, a sharp dis-
tinction is not possible because a substance might
act as precipitating agent in a given cocktail and
be used as an additive in a different case. Besides
to affect the solubility, the components forming
the crystallizing solution have to weakly interact
with the molecule of the substance to crystallize
(Wilson 2003). Differently, stronger interactions
make more soluble the substance to crystallize,
while the absence of interactions drastically
reduces the solubility, resulting in an amorphous
precipitation. As the space of the conditions
(nature and concentration of each component)
promoting weak interactions is usually very
small, it is necessary to explore several formula-
tions before obtaining the best one. One of the
most used methods to deal with the crystallizing
solution formulation problem is the multivariate
analysis that allows testing several successful
events of crystallization against a high-
dimensional space represented by the crystalliza-
tion conditions (Segelke 2001). Depending on the
crystallization method, the concentration of each
component of the crystallizing solution can vary
or keep unchanged during the crystallization pro-
cess: no change occurs in the case of the batch
method where the level of supersaturation is
directly adjusted on the crystallizing solution.
Conversely, the component concentrations
2 Crystallizing Solution
Crystallizing Solution, Fig. 1 Vapor phase transfer in
membrane crystallizers. (a) On the crystallizing solution
side, the solute concentration increases due to the solvent
removal triggered by the gradient of vapor pressure
between the two sides of the membrane. (b) In the case
change when the supersaturation level is reached
in the time by using vapor or liquid diffusion
techniques. Techniques that exploit membranes
to put in contact a crystallizing solution
containing the molecule to crystallize and a strip-
ping hypertonic solution or an antisolvent on the
other side of the membrane (distillate side)
belong to the latter category. Due to its hydro-
phobicity, membrane is not wet by the two liquids
on the two sides and the flux of solvent molecules
through the membrane can occur by vapor diffu-
sion (Fig. 1a). Accordingly, it is possible to
achieve a fine regulation to the rate to which
solute increases its concentration in the crystal-
lizing solution by managing the transmembrane
flux. Similarly, in the case of antisolvent mem-
brane devices, vapor diffusion triggers the
increase of the antisolvent concentration inside
the crystallizing solution (Fig. 1b), resulting in a
decrease of the solute solubility (Di Profio
et al. 2009). By using hydrophilic membranes, it
is possible to exploit liquid-phase transfer: in this
case, crystallizing solution is directly pressed
through a porous membrane in an antisolvent
(or vice versa). This technique has been used to
of antisolvent membrane crystallizers, the solubility of the
solute decreases due to the increase of the antisolvent
concentration inside the crystallizing solution usually gen-
erated by a temperature difference between the two sides
of the membranes
produce crystal of L-asparagine with narrow size
distribution (Zarkadas and Sirkar 2006).
Cross-References
▶ Antisolvent
▶ Antisolvent Membrane Devices
▶ Crystallization
▶ Hydrophobicity
▶ Multivariate Analyses
▶ Solubility
References
Di Profio G, Stabile C, Caridi A, Curcio E, Drioli E (2009)
Antisolvent membrane crystallization of pharmaceuti-
cal compounds. J Pharm Sci 98:4902–4913
Segelke BW (2001) Efficiency analysis of sampling pro-
tocols used in protein crystallization screening. J Cryst
Growth 232:553–562
Wilson WW (2003) Light scattering as a diagnostic for
protein crystal growth-a practical approach. J Struct
Biol 142:56–65
Zarkadas DM, Sirkar KK (2006) Antisolvent crystalliza-
tion in porous hollow fiber devices. Chem Eng Sci
61:5030–5048
C
Crystallization
Benny Danilo Belviso
Istituto di Cristallografia, Consiglio Nazionale
delle Ricerche (C.N.R), Bari, Italy
Crystallization is a phase transition that takes
place from the liquid toward the solid state
resulting in the formation of crystals; less fre-
quently, the deposition of crystals can also
occur starting from the gas state. In any case,
crystallization process represents a particular
kind of solidification in which the molecules or
ions of a given substance arrange themselves in
an orderly fashion according to a substance-
specific three-dimensional lattice. Differently, in
the absence of orderly arrangement, solidification
process leads to amorphous precipitates or to
solids consisting of a mix of crystalline and amor-
phous areas (as it happens for some polymers).
Crystallization takes place when the solution
containing the substance to crystallize reaches
the supersaturation state, namely, when the con-
centration of this substance overcomes the solu-
bility limit while remaining below the threshold
of precipitation. The kinetics and the thermody-
namics of the crystallization depend on the super-
saturation level that, hence, represents the driving
force of the entire process. Crystallization con-
sists of two major events: nucleation and crystal
growth. Nucleation occurs in the metastable zone
(Fig. 1, in yellow) as a consequence of the rapid
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1132-1
local molecular collisions characterizing the
homogeneous phase (solution or gas) in condition
of supersaturation. Crystalline nuclei, the
smallest molecular aggregates having a structure
ordered according to periodic rules, can be
formed only when well-oriented collisions
between particles take place. The smallest nuclei
dissolve, while crystal nuclei having critical
dimensions pass to the next step, where other
molecules of solute can converge on the
preformed aggregates. This stage is called crystal
growth and takes place in the labile zone (Fig. 1,
in pink). During the crystal accretion, also the
concentration of contaminants on crystal surface
increases causing a slowdown of the growth up to
its complete stop. The adding of small particles,
such as small crystals or amorphous solids
(Saridakis and Chayen 2009), can promote the
crystallization process by acting as nucleation
centers. Although the rates of nucleation and
crystal growth increase with the supersaturation
level, fast crystallization processes at low super-
saturation are possible in the presence of crystal
defects. Today, advanced crystallization tech-
niques allow getting crystals with few defects
even starting from lower levels of supersatura-
tion. This is possible by means of an effective
control of the nucleation and crystal growth steps,
as occurs in the case of the membrane-assisted
crystallization (Drioli et al. 2012), where the
entire crystallization process takes place on a
support consisting of a polymeric membrane
that acts also as active surface for heterogeneous
2 Crystallization

Crystallization,
Fig. 1 Crystallization
phase diagram. Crystal
nucleation takes place in
metastable zone (in yellow)
and crystals growth in
labile zone (in pink), both
belonging to the
supersaturation zone. The
condition of
supersaturation is reached
when solute concentration
is slightly higher than the
solubility (gray line);
differently, a much higher
solute concentration leads
to amorphous precipitation
(light cyan area)

nucleation (Di Profio et al. 2010a). On the other References

side of the membrane (distillate side), a stripping
solution allows the removal of the solvent from
the crystallizing solution. The high hydrophobic-
ity of the membrane prevents its wetting,
allowing that the mass transfer between crystal-
lizing solution and stripping solution takes place
only by vapor diffusion mechanism. Since the
solute species, such as macromolecules and elec-
trolytes, have lower volatility than the solvent,
only the latter passes from the crystallizing solu-
tion to the stripping solution through the mem-
brane, by resulting in an increase of solute
concentration. Therefore, the driving force of
the membrane-assisted crystallization is
represented by the vapor pressure gradient at
both sides of the membrane. Kinetics and ther-
modynamics of the nucleation process can be
modulated according to the transmembrane flux
and the features of the membrane, offering the
opportunity of a more rationale design of the
crystallization process. Crystallization on mem-
brane has been extensively tested both on small
molecules (Di Profio et al. 2010b, 2013) and on
large macromolecules, such as proteins (Di Profio
et al. 2005; Curcio et al. 2005).
Curcio E, Simone S, Di Profio G, Drioli E, Cassetta A,
Lamba D (2005) Membrane crystallization of lyso-
zyme under forced solution flow. J Membr Sci
257:134–143
Di Profio G, Curcio E, Drioli E (2005) Trypsin crystalli-
zation by membrane-based techniques. J Struct Biol
150:41–49
Di Profio G, Curcio E, Drioli E (2010a) Supersaturation
control and heterogeneous nucleation in membrane
crystallizers: facts and perspectives. Ind Eng Chem
Res 49:11878–11889
Di Profio G, Caridi A, Caliandro R, Guagliardi A,
Curcio E, Drioli E (2010b) Fine dosage of antisolvent
in the crystallization of L-histidine: effect on polymor-
phism. Cryst Growth Des 10:449–455
Di Profio G, Reijonen MT, Caliandro R, Guagliardi A,
Curcio E, Drioli E (2013) Insights into the polymor-
phism of glycine: membrane crystallization in an elec-
tric field. Phys Chem Chem Phys 15:9271–9280
Drioli E, Di Profio G, Curcio E (2012) Progress in mem-
brane crystallization. Curr Opin Chem Eng 1:178–182
Saridakis E, Chayen NE (2009) Towards a ‘universal’
nucleant for protein crystallization. Trends Biotechnol
27:99–106
N
Nanofiltration for Reuse of Sharpless solvent, using an aqueous system that includes a
Catalytic Systems surfactant, such as sodium dodecyl sulfate and
Frederico Castelo Ferreira
Department of Bioengineering, Instituto Superior
Técnico, Institute for Bioengineering and
Biosciences, Universidade de Lisboa, Lisbon,
Portugal
Nanofiltration for reuse of Sharpless catalytic
systems combines reaction and separation in a
single vessel, allowing successive reaction and
filtration steps, to recycle the catalytic system in
successive batches with isolation of the chiral
product on the permeated solution. The Sharpless
catalysis is a robust strategy for production of
chiral 1,2-diols from olefins at high yields and
enantiomer excesses, using a catalytic system
based on OsO4 or K2OsO2(OH)4 salt and a chiral
dimeric ligand (Bolm et al. 2000; Kolb
et al. 1994). Chiral ligands used are based on a
cinchona alkaloid (dihydroquinidine or
dihydroquinine) with phathalazina, pyrimidine,
or indoline groups. The reaction requires a
co-oxidant, which can be organic or inorganic,
such as N-methylmorpholine-N-oxide (NMO) or
K3Fe(CN)6, respectively. The reaction media is
conventionally an aqueous/organic (50 v/v% sol-
vent) mixture with tert-butanol, methyl tert-butyl
ether, or acetone. The feasibility of Sharpless
reaction was also attained for a range of seven
different olefins on the absence of organic
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1149-1
sodium cholate, or an ionic liquid such as
hexadecyltrimethylammonium bromide (Branco
and Afonso 2002; Branco et al. 2008). Moreover,
the use of aqueous/surfactant or ionic liquid sys-
tems avoids the continuous gradual slow addi-
tion, required to obtain high enantiomer
excesses in the aqueous/organic system. Wide-
spread industrial application of the Sharpless sys-
tem has been restricted by the high cost of the
catalyst and toxicity of the osmium species.
Aqueous and ▶ organic solvent nanofiltration
had been assayed to isolate chiral product and
recycle the osmium salt and chiral ligand
hydroquinidine 1,4-phthalazinediyl diether
(molecular weights, MW, of 368 Da and
779 Da, respectively) (Branco et al. 2008;
Ferreira et al. 2007) into successive reactions.
NMO with a molecular weight of 135 Da was
used as co-oxidant for both aqueous/organic and
aqueous/surfactant systems. Starmem120, a
polyimide membrane with nominal ▶ molecular
weight cutoff (MWCO) of 200 Da, was used for
the aqueous/organic system, composed of a
water/acetone (25 v% acetone) mixture, with a
lower water content than in the conventional
Sharpless system, to improve solvent mixture
flux through the membrane (Ferreira
et al. 2007). On the other hand, a ▶ polyamide
membrane, Desal DK, with a MWCO of about
250 Da, was used in the aqueous/surfactant sys-
tem to retain both catalytic system and sodium
2 Nanofiltration for Reuse of Sharpless Catalytic Systems

K2Os2(OH)4 1st cycle addition only:

Chiral dimeric ligand OH K2Os2(OH)4
R’ Chiral dimeric ligand
R’ (Surfactant or Ionic liquid)
R Co−oxidant R
Reaction media
OH Every cycle
addition: Chiral
Nanofiltration for Reuse of Sharpless Catalytic Sys- Olefin Diol
tems, Fig. 1 Reaction scheme for asymmetric Co−oxidant
dihydroxylation of olefins Solvent/Water
(only water)
cholate (Mw 460.6 g.mol 1), the surfactant used Nanofiltration for Reuse of Sharpless Catalytic Sys-
(Branco et al. 2008). In both systems, each tems, Fig. 2 Scheme of nanofiltration-reaction succes-
reaction-membrane filtration cycle included a sive cycles
first reaction step at atmospheric pressure, with-
out permeation, and a second ▶ nanofiltration over numbers (TON), (i.e., total product obtained
step in which a pressure of 10–20 bar was applied by catalyst used) with beneficial impact on Sharp-
as driving force to promote solution permeation less reaction economics and osmium contamina-
through the membrane. The next cycle started by tion of the product (Figs 1 and 2).
making up the feed volume with addition of sol-
vent/water or only water in the water/surfactant
system. Different steady states, concerning prod- References
uct concentration in the vessel, can be reached
according with ▶ concentration factors (i.e., the Bolm C, Hildebrand JP, Muniz K (2000) 6E Recent
Advances in Asymmetric Dihydroxylation and
ratio of initial per final volume) used. Product Aminohydroxylation. In: Ojima I (ed) Catalytic asym-
concentration can be important in the final pro- metric synthesis, 2nd edn. VCH, Weinheim, p 399
cess yield due to reaction inhibition by the prod- Branco LC, Afonso CAM (2002) Catalytic asymmetric
uct. ▶ Diafiltration strategies with feeding of dihydroxylation of olefins using a recoverable and
reusable OsO42 in ionic liquid [bmim][PF6]. Chem
additional solvent/water (or water alone) can Commun 3036–3037
also be employed in the ▶ nanofiltration step to Branco LC, Ferreira FC, Santos JL, Crespo JG, Afonso
reach lower product concentrations in the vessel CAM (2008) Sharpless asymmetric dihydroxylation of
and recovery higher product amounts in the per- olefins in water-surfactant media with recycling of the
catalytic system by membrane nanofiltration. Adv
meate. However, for higher diavolumes, when Synth Catal 350:2086–2098
catalyst and surfactant have rejections lower Ferreira FC, Branco LC, Verma KK, Crespo JG, Afonso
than 100 %, losses of the catalytic system into CAM (2007) Application of nanofiltration for re-use of
the permeate can become significant. Moreover Sharpless catalytic system in asymmetric
di-hydroxylation. Tetrahedron-Asymmetry
isolation of the more diluted product from per- 18:1637–1641
meate is more challenging. Overall, the applica- Kolb C, VanNieuwenhze MS, Sharpless KB (1994) Cata-
tion of nanofiltration for reuse of the osmium lytic asymmetric dihydroxylation. Chem Rev
catalytic system as the potential to improve turn 94(8):2483
P
Positron Annihilation Lifetime
Spectroscopy (PALS)
Geoffrey Geise
Department of Chemical Engineering, University
of Virginia, Charlottesville, VA, USA
Positron annihilation lifetime spectroscopy is
used to determine the average lifetimes and inten-
sities of positron species in molecular media
(Schrader and Jean 1988; Jean et al. 2003).
These lifetime and intensity data can provide
information about the molecular-scale nature of
the material (Jean et al. 2003; Pethrick 1997).
Typically, PALS is performed by surrounding a
positron source (e.g., 22NaCl) with the sample of
interest and placing it between two detectors
(Jean et al. 2003). One detector is sensitive to
the photon that is produced when the positron
forms, and the other detector is sensitive to the
photon that is emitted when the positron annihi-
lates (Jean et al. 2003). The signals from these
detectors can be processed and sorted to deter-
mine the length of time between each formation
and annihilation event (Schrader and Jean 1988;
Jean et al. 2003; Pethrick 1997). This information
can be further processed and analyzed to deter-
mine the average lifetime of each positron spe-
cies that forms and annihilates in the sample
(Schrader and Jean 1988; Jean et al. 2003;
Pethrick 1997). Additionally, the intensity or the
concentration of each positron species that forms
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1150-2
and annihilates in the sample can be determined,
and these data can provide additional information
about the nature of the sample.
The lifetime of a positron depends on the
positron’s electronic state and its environment
(Schrader and Jean 1988; Jean et al. 2003;
Pethrick 1997). When a positron combines with
an electron to form positronium, para-
positronium (p-Ps) is formed if the spin states of
the electron and positron are parallel, and ortho-
positronium (o-Ps) is formed when the spin states
of the electron and positron are antiparallel
(Pethrick 1997). The lifetime of p-Ps is
0.125 ns, and in molecular media the average
o-Ps lifetime typically falls in the range of
0.5–5 ns (Pethrick 1997). The lifetime of free
positrons in molecular media is typically around
0.4 ns (Pethrick 1997).
Because the average lifetimes of free positrons
and o-Ps in molecular media are sensitive to their
environment, these lifetimes can be related to the
size of molecular-scale void space or free volume
in the media (Pethrick 1997; Mallon 2003; Ju
et al. 2010; Xie et al. 2011; Hill et al. 1996,
2005; Rowe et al. 2009; Tao 1972; Eldrup
et al. 1981; Zhang et al. 2012; Freeman and
Yampolskii 2010; Liao et al. 2011; Chen
et al. 2012). The small size of positrons and
positronium allows PALS to probe angstrom-
scale void spaces in molecular media (Pethrick
1997; Hill et al. 2005). Additionally, in some
materials, the intensity of o-Ps can be related to
the concentration of void spaces in the material,
2 Positron Annihilation Lifetime Spectroscopy (PALS)
but this relationship can be disrupted by the
chemical nature of the sample (Pethrick 1997;
Xie et al. 2011; Kobayashi et al. 2009). This
feature is useful for studying nonporous mem-
branes for both gas and liquid separations
because free volume in these materials is related
to the diffusion of small molecules through the
material (Ju et al. 2010; Xie et al. 2011; Hill
et al. 1996, 2005; Rowe et al. 2009; Zhang
et al. 2012; Freeman and Yampolskii 2010;
Chen et al. 2012; Yampol’skii et al. 2006;
Cohen and Turnbull 1959; Matteucci et al. 2006).
Cross-References
▶ Polymeric Membrane Characterization Using
PALS
▶ Positron Annihilation Spectroscopy
References
Chen GQ, Scholes CA, Doherty CM, Hill AJ, Qiao GG,
Kentish SE (2012) Modeling of the sorption and trans-
port properties of water vapor in polyimide mem-
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Cohen MH, Turnbull D (1959) Molecular transport in
liquids and glasses. J Chem Phys 31:1164–1169
Eldrup M, Lightbody D, Sherwood JN (1981) The tem-
perature dependence of positron lifetimes in solid
pivalic acid. Chem Phys 63:51–58
Freeman B, Yampolskii Y (2010) Membrane gas separa-
tion. Wiley, West Sussex
Hill AJ, Weinhold S, Stack GM, Tant MR (1996) Effect of
copolymer composition on free volume and gas per-
meability in poly(ethylene terephthalate)-poly(1,4
cyclohexylenedimethylene terephthalate)
copolyesters. Eur Polym J 32:843–849
Hill AJ, Freeman BD, Jaffe M, Merkel TC, Pinnau
I (2005) Tailoring nanospace. J Mol Struct
739:173–178
Jean YC, Mallon PE, Schrader DM (2003) Principles and
applications of positron and positronium chemistry.
World Scientific, London
Ju H, Sagle AC, Freeman BD, Mardel JI, Hill AJ
(2010) Characterization of sodium chloride and water
transport in poly(ethylene oxide) hydrogels. J Membr
Sci 358:131–141
Kobayashi Y, Mohamed HFM, Ohira A (2009) Positro-
nium formation in aromatic polymer electrolytes for
fuel cells. J Phys Chem B 113:5698–5701
Liao K-S, Chen H, Awad S, Yuan J-P, Hung W-S, Lee
K-R, Lai J-Y, Hu C-C, Jean YC (2011) Determination
of free-volume properties in polymers without
orthopositronium components in positron annihilation
lifetime spectroscopy. Macromolecules 44:6818–6826
Mallon PE (2003) Application to polymers. In: Jean YC,
Mallon PE, Schrader DM (eds) Principles and appli-
cations of positron and positronium chemistry. World
Scientific, Singapore, pp 253–280
Matteucci S, Yampolskii Y, Freeman BD, Pinnau I (2006)
Transport of gases and vapors in glassy and rubbery
polymers. In: Yampolskii Y, Pinnau I, Freeman BD
(eds) Materials science of membranes for gas and
vapor separation. Wiley, London, pp 1–47
Pethrick RA (1997) Positron annihilation – a probe for
nanoscale voids and free volume? Prog Polym Sci
22:1–47
Rowe BW, Pas SJ, Hill AJ, Suzuki R, Freeman BD, Paul
DR (2009) A variable energy positron annihilation
lifetime spectroscopy study of physical aging in thin
glassy polymer films. Polymer 50:6149–6156
Schrader DM, Jean YC (1988) Studies in physical and
theoretical chemistry 57: positron and positronium
chemistry. Elsevier, New York
Tao SJ (1972) Positronium annihilation in molecular sub-
stances. J Chem Phys 56:5499–5510
Xie W, Ju H, Geise GM, Freeman BD, Mardel JI, Hill AJ,
McGrath JE (2011) Effect of free volume on water and
salt transport properties in directly copolymerized
disulfonated poly(arylene ether sulfone) random
copolymers. Macromolecules 44:4428–4438
Yampol’skii Y, Pinnau I, Freeman BD (2006) Materials
science of membranes for gas and vapor separation.
Wiley, London
Zhang S, Zhang R, Jean YC, Paul DR, Chung T-S
(2012) Cellulose esters for forward osmosis: charac-
terization of water and salt transport properties and
free volume. Polymer 53:2664–2672
P
Positron Annihilation Spectroscopy
Geoffrey Geise
Department of Chemical Engineering,
University of Virginia, Charlottesville,
VA, USA
Synonyms
Positron annihilation technique
Positron annihilation spectroscopy (PAS) is a
tool for studying positron and positronium chem-
istry (Schrader and Jean 1988; Jean et al. 2003;
Pethrick 1997). Positrons, which are positively
charged electrons, interact with molecular
media to form a variety of different electronic
states, and these species subsequently annihilate
(Schrader and Jean 1988; Jean et al. 2003). Pos-
itronium, which is a neutral atom composed of a
positron and an electron, can also interact with
molecular media and subsequently annihilate
(Jean et al. 2003). In addition to forming positro-
nium, positrons can also interact with molecules
in molecular media (Schrader and Jean 1988;
Jean et al. 2003). Positron-electron annihilation
produces photons, and PAS measures the ener-
gies and momenta of these photons (Pethrick
1997). Furthermore, these photons can be
detected as single events, and this information
can be used to determine the photon’s emission
time and the lifetime of the positron or
# Springer-Verlag Berlin Heidelberg 2016
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1151-3
positronium atom (a separate characteristic pho-
ton resulting from formation of the positron can
also be detected) (Jean et al. 2003; Pethrick
1997). Because the electronic state of the positron
and its environment in molecular media affect the
annihilation process, PAS can provide informa-
tion about the electron density and electron
momentum of the annihilation site (Schrader
and Jean 1988; Jean et al. 2003; Pethrick 1997;
Hill et al. 2005; Tao 1972; Eldrup et al. 1981).
PAS is performed by irradiating a sample with
positrons. Typically, the positron source for PAS
is 22Na (often prepared as a salt, such as 22NaCl)
(Jean et al. 2003; Pethrick 1997). Other positron-
emitting isotopes or beam-line sources, however,
can be used to perform PAS (Jean et al. 2003;
Rowe et al. 2009). One benefit of a beam-line
source as opposed to an isotope source, such as
22
Na, is the ability to control the energy of the
incident positron, which in turn, determines the
positron’s depth of penetration into the sample
(Jean et al. 2003; Rowe et al. 2009). Therefore,
PAS can be used to probe material properties as a
function of depth from the surface (typically
ranging from a few nanometers to several micro-
meters) when an appropriate beam-line source is
available (Jean et al. 2003; Rowe et al. 2009).
Three techniques, positron annihilation life-
time spectroscopy (PALS), Doppler broadening
spectroscopy (DBS), and angular correlation of
annihilation radiation (ACAR), are commonly
used to perform PAS although other specialized
techniques exist (Jean et al. 2003; Pethrick 1997).
2 Positron Annihilation Spectroscopy
While DBS and ACAR provide information
about positron annihilation mechanisms, PALS
can provide information about the molecular-
scale structure of molecular media (Pethrick
1997). As a result, PALS is often used to charac-
terize molecular-scale voids (i.e., free volume) in
membranes (Pethrick 1997; Hill et al. 2005;
Rowe et al. 2009; Yampol’skii et al. 2006; Park
et al. 2007; Ju et al. 2010; Xie et al. 2011; Tung
et al. 2009; Zhang et al. 2012).
Cross-References
▶ Polymeric Membrane Characterization Using
PALS
▶ Positron Annihilation Lifetime Spectroscopy
(PALS)
References
Eldrup M, Lightbody D, Sherwood JN (1981) The tem-
perature dependence of positron lifetimes in solid
pivalic acid. Chem Phys 63:51–58
Hill AJ, Freeman BD, Jaffe M, Merkel TC, Pinnau
I (2005) Tailoring nanospace. J Mol Struct
739:173–178
Jean YC, Mallon PE, Schrader DM (2003) Principles and
applications of positron & positronium chemistry.
World Scientific, London
Ju H, Sagle AC, Freeman BD, Mardel JI, Hill AJ
(2010) Characterization of sodium chloride and water
transport in poly(ethylene oxide) hydrogels. J Membr
Sci 358:131–141
Park HB, Jung CH, Lee YM, Hill AJ, Pas SJ, Mudie ST,
Van Wagner E, Freeman BD, Cookson DJ (2007) Poly-
mers with cavities tuned for fast selective transport of
small molecules and ions. Science 318:254–258
Pethrick RA (1997) Positron annihilation – a probe for
nanoscale voids and free volume? Prog Polym Sci
22:1–47
Rowe BW, Pas SJ, Hill AJ, Suzuki R, Freeman BD, Paul
DR (2009) A variable energy positron annihilation
lifetime spectroscopy study of physical aging in thin
glassy polymer films. Polymer 50:6149–6156
Schrader DM, Jean YC (1988) Studies in physical and
theoretical chemistry 57: positron and positronium
chemistry. Elsevier, New York
Tao SJ (1972) Positronium annihilation in molecular sub-
stances. J Chem Phys 56:5499–5510
Tung K-L, Jean Y-C, Nanda D, Lee K-R, Hung W-S, Lo
C-H, Lai J-Y (2009) Characterization of multilayer
nanofiltration membranes using positron annihilation
spectroscopy. J Membr Sci 343:147–156
Xie W, Ju H, Geise GM, Freeman BD, Mardel JI, Hill AJ,
McGrath JE (2011) Effect of free volume on water and
salt transport properties in directly copolymerized
disulfonated poly(arylene ether sulfone) random
copolymers. Macromolecules 44:4428–4438
Yampol’skii Y, Pinnau I, Freeman BD (2006) Materials
science of membranes for gas and vapor separation.
Wiley, London
Zhang S, Zhang R, Jean YC, Paul DR, Chung T-S
(2012) Cellulose esters for forward osmosis: charac-
terization of water and salt transport properties and
free volume. Polymer 53:2664–2672
P
Polymeric Membrane
Characterization by PALS
Geoffrey Geise
Department of Chemical Engineering,
The University of Texas at Austin, Austin
TX, USA
The size of free volume elements in polymeric
membrane materials can be related to the average
lifetime of either free positrons or ortho-
positronium (o-Ps) in the polymer measured
using positron annihilation lifetime spectroscopy
(PALS) (Mallon 2003; Hill et al. 1996, 2005;
Pethrick 1997; Liao et al. 2011). Additionally,
for some polymers, the average o-Ps intensity
can be combined with the average o-Ps lifetime
to determine the polymer’s fractional free vol-
ume (FFV) (Mallon 2003; Hill et al. 2005;
Pethrick 1997; Matteucci et al. 2006). In some
polymers, however, positron-polymer interac-
tions can disrupt the relationship between o-Ps
intensity and the concentration of void space
(or free volume elements) in the polymer (Liao
et al. 2011; Jean et al. 2003; Xie et al. 2011;
Hirata et al. 1997; Kobayashi et al. 2009).
Free volume information is useful for charac-
terizing nonporous polymer membrane materials
because the diffusion coefficients of penetrants in
the polymer matrix are related to the polymer’s
free volume (Cohen and Turnbull 1959). Many
studies have correlated transport properties (e.g.,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1153-2
permeability and diffusivity) with free volume
determined using PALS (Hill et al. 1996, 2005;
Matteucci et al. 2006; Xie et al. 2011; Freeman
and Yampolskii 2010; Ju et al. 2010; Rowe
et al. 2009; Zhang et al. 2012; Chen et al. 2012;
Tung et al. 2009; Merkel et al. 2002; Nagel
et al. 2002; Alentiev et al. 1997; Yampolskii
et al. 1994; Kim et al. 2005). These studies
include polymers for gas separation membranes
and liquid (e.g., desalination) membranes. These
correlations further suggest that PALS is a valu-
able tool for characterizing polymer free volume.
In addition to correlating with transport proper-
ties, PALS data have been shown to correlate
with various thermal and mechanical properties
of polymers (Mallon 2003; Pethrick 1997).
The average o-Ps lifetime in a polymer can be
related to the average size of the polymer’s free
volume elements using the Tao-Eldrup model
when the average free volume element radius is
around or smaller than 10 Å (Mallon 2003;
Pethrick 1997; Tao 1972; Eldrup et al. 1981). In
general, as free volume elements become larger,
o-Ps lifetime increases (Hill et al. 2005; Pethrick
1997). Additionally, the average free positron
lifetime may be related to the size of the poly-
mer’s free volume elements (Liao et al. 2011).
The Tao-Eldrup model assumes that the poly-
mer’s average free volume element size can be
represented by a sphere (Mallon 2003; Pethrick
1997; Tao 1972; Eldrup et al. 1981). With this
assumption, the volume of a free volume element
in the polymer can be calculated geometrically
2 Polymeric Membrane Characterization by PALS
using the radius obtained from the Tao-Eldrup
model (Mallon 2003).
Cross-References
▶ Positron Annihilation Lifetime Spectroscopy
(PALS)
▶ Positron Annihilation Spectroscopy
References
Alentiev AY, Yampolskii YP, Shantarovich VP, Nemser
SM, Plate NA (1997) High transport parameters and
free volume of perfluorodioxole copolymers. J Membr
Sci 126:123–132
Chen GQ, Scholes CA, Doherty CM, Hill AJ, Qiao GG,
Kentish SE (2012) Modeling of the sorption and trans-
port properties of water vapor in polyimide mem-
branes. J Membr Sci 409–410:96–104
Cohen MH, Turnbull D (1959) Molecular transport in
liquids and glasses. J Chem Phys 31:1164–1169
Eldrup M, Lightbody D, Sherwood JN (1981) The tem-
perature dependence of positron lifetimes in solid
pivalic acid. Chem Phys 63:51–58
Freeman B, Yampolskii Y (2010) Membrane gas separa-
tion. Wiley, West Sussex
Hill AJ, Weinhold S, Stack GM, Tant MR (1996) Effect of
copolymer composition on free volume and gas per-
meability in poly(ethylene terephthalate)-poly(1,4
cyclohexylenedimethylene terephthalate)
copolyesters. Eur Polym J 32:843–849
Hill AJ, Freeman BD, Jaffe M, Merkel TC, Pinnau
I (2005) Tailoring nanospace. J Mol Struct
739:173–178
Hirata K, Kobayashi Y, Ujihira Y (1997) Effect of halo-
genated compounds on positronium formation in poly-
carbonate and polysulfone matrices. J Chem Soc
Faraday Trans 93:139–142
Jean YC, Mallon PE, Schrader DM (2003) Principles and
applications of positron and positronium chemistry.
World Scientific, London
Ju H, Sagle AC, Freeman BD, Mardel JI, Hill AJ
(2010) Characterization of sodium chloride and water
transport in poly(ethylene oxide) hydrogels. J Membr
Sci 358:131–141
Kim SH, Kwak SY, Suzuki T (2005) Positron annihilation
spectroscopic evidence to demonstrate the flux-
enhancement mechanism in morphology-controlled
thin-film-composite (TFC) membrane. Environ Sci
Technol 39:1764–1770
Kobayashi Y, Mohamed HFM, Ohira A (2009) Positro-
nium formation in aromatic polymer electrolytes for
fuel cells. J Phys Chem B 113:5698–5701
Liao K-S, Chen H, Awad S, Yuan J-P, Hung W-S, Lee
K-R, Lai J-Y, Hu C-C, Jean YC (2011) Determination
of free-volume properties in polymers without
orthopositronium components in positron annihilation
lifetime spectroscopy. Macromolecules 44:6818–6826
Mallon PE (2003) Application to polymers. In: Jean YC,
Mallon PE, Schrader DM (eds) Principles and appli-
cations of positron and positronium chemistry. World
Scientific, Singapore, pp 253–280
Matteucci S, Yampolskii Y, Freeman BD, Pinnau I (2006)
Transport of gases and vapors in glassy and rubbery
polymers. In: Yampolskii Y, Pinnau I, Freeman BD
(eds) Materials science of membranes for gas and
vapor separation. Wiley, London, pp 1–47
Merkel TC, Freeman BD, Spontak RJ, He Z, Pinnau I,
Meakin P, Hill AJ (2002) Ultrapermeable, reverse-
selective nanocomposite membranes. Science
296:519–522
Nagel C, Gunther-Schade K, Fritsch D, Strunskus T,
Faupel F (2002) Free volume and transport properties
in highly selective polymer membranes. Macromole-
cules 35:2071–2077
Pethrick RA (1997) Positron annihilation – a probe for
nanoscale voids and free volume? Prog Polym Sci
22:1–47
Rowe BW, Pas SJ, Hill AJ, Suzuki R, Freeman BD, Paul
DR (2009) A variable energy positron annihilation
lifetime spectroscopy study of physical aging in thin
glassy polymer films. Polymer 50:6149–6156
Tao SJ (1972) Positronium annihilation in molecular sub-
stances. J Chem Phys 56:5499–5510
Tung K-L, Jean Y-C, Nanda D, Lee K-R, Hung W-S,
Lo C-H, Lai J-Y (2009) Characterization of multilayer
nanofiltration membranes using positron annihilation
spectroscopy. J Membr Sci 343:147–156
Xie W, Ju H, Geise GM, Freeman BD, Mardel JI, Hill AJ,
McGrath JE (2011) Effect of free volume on water and
salt transport properties in directly copolymerized
disulfonated poly(arylene ether sulfone) random
copolymers. Macromolecules 44:4428–4438
Yampolskii YP, Bespalova NB, Finkelshtein ES, Bondar
VI, Popov AV (1994) Synthesis, gas-permeability, and
gas sorption properties of fluorine-containing
norbornene polymers. Macromolecules 27:2872–2878
Zhang S, Zhang R, Jean YC, Paul DR, Chung T-S
(2012) Cellulose esters for forward osmosis: charac-
terization of water and salt transport properties and
free volume. Polymer 53:2664–2672
T
Ternary Pd-Alloy Membranes
Thijs Peters
SINTEF Materials and Chemistry, Oslo, Norway
Palladium (Pd) has high solubility and diffusivity
of hydrogen and shows therefore great promise as
a membrane material for medium to high temper-
ature hydrogen separation (250–550  C). In pure
Pd, however, an a-to-b-hydride phase transition
may occur in hydrogen below about 290  C, and
only a few cycles through this transition make the
material brittle and must be avoided. By alloying
Pd with different elements, the phase transition
can be suppressed, and the majority of the work
related to Pd-alloy membranes applies particu-
larly alloys with 20–30 wt.% Ag and 40 wt.%
Cu. The drawback is, however, that these alloys
are to various degrees prone to poisoning by CO-
and sulfur-containing gases leading to reduced
H2 flux or even to a complete membrane failure.
Research therefore currently focuses on develop-
ing more advanced ternary or quaternary alloys
that may be needed to improve the mechanical,
thermal, and chemical stability of Pd-based
membranes.
The main problems with membrane reliability
are related to their corrosion resistance and struc-
tural changes that occur during operation. Palla-
dium and Pd-alloys have therefore been alloyed
with additional other metals, including Ru,
Mo, W, Y, Ta, V, Rh, Nb, Cr, Ni, and Fe, to
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1163-1
obtain greater mechanical strength and to inhibit
undesired grain growth resulting in an increased
temperature stability. Doping Pd with higher
melting point metals (such as Ru or Pt) seems to
enhance the thermal stability of the membrane. In
terms of corrosion resistance, various approaches
involving ternary Pd-alloys are being followed.
Fcc Pd-Cu membranes are known for their sulfur
tolerance but are less permeable than Pd. Several
studies have therefore focused on improving the
hydrogen flux through Pd-Cu membranes by
adding a third element. In this respect, Ag is
most particularly interesting since Pd-Ag has a
higher hydrogen permeability compared to pure
Pd. Another approach is to alloy the high-flux
Pd-Ag alloy membrane with ternary elements to
enhance the sulfur tolerance without significantly
reducing the high permeability of this alloy. The
Pd-Ag-Au alloy developed along this route
displayed higher initial H2 permeability than
pure Pd and, consistent with resistance to bulk
sulfide formation, lower permeability loss in H2S
than pure Pd. This indicates that the addition of
small amounts of Au to the high-flux Pd-Ag alloy
membrane improves the sulfur tolerance of this
alloy and that this could be an interesting
approach in the development of high-flux
Pd-based alloy membranes with improved sulfur
tolerance. Still, however, flux targets remain a
challenge for new alloys in large-scale applica-
tions in the presence of sulfur impurities.
P
Pd-Based Membrane: Exposure
to Coal Gas
Thijs Peters
SINTEF Materials and Chemistry, Oslo, Norway
Pd-based membranes have frequently been stud-
ied in membrane reactors for steam reforming
(SR-MR) and water-gas shift (WGS-MR) reac-
tions to simultaneously achieve a high methane
conversion and production of pure H2. A key
feature of this process intensification is that such
a membrane reactor would produce both a high-
pressure CO2 stream and high-purity H2. Synthe-
sis gas may also be produced by gasification of
coal or biomass, enabling production of hydrogen
from these important sources. Downstream
processing of gasification effluents, i.e., separa-
tion or further reaction, is however more chal-
lenging than in the case of natural gas because of
the wide range of possible impurities and
by-products associated with the coal or biomass.
Coal-derived synthesis gas can contain up to
15,000 ppm H2S as well as COS (<0.1 %),
NH3 + HCN (<0.3 %), C2 hydrocarbons,
polyaromatic hydrocarbons (PAHs), halides
(such as CH3F, CH3Cl at around 2 ppmv),
heavy metals (such as Hg, Cd, Pb), tellurides
(arsenides, selenium, antimony), alkali metals
(Na, K, Ca), phosphorous, tars, and other
unknown compounds, in concentrations varying
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1165-1
with the source of the feedstock and the gasifica-
tion technology applied. Even though some field
tests applying Pd-based membranes in actual
coal-derived syngas have been performed, the
reactivity of the majority of these compounds
with Pd and its alloys is not known.
With current understanding, production of
hydrogen from coal and other sulfur-containing
sources is challenging for Pd-based membranes
particularly due to their limited stability toward
sulfur. Even a few ppm of sulfur in the gas
reduces the flux drastically due to strong surface
adsorption leading to reduced permeability,
while higher concentrations (typically above
100 ppm depending on operating temperature)
even lead to a complete deterioration of the mem-
brane caused by formation of bulk Pd4S. This has
led to the development of a number of new alloys
with higher sulfur tolerance (see entry “▶ Ter-
nary Pd-Alloy Membranes”). Still, however, flux
targets remain a challenge for these alloys in
large-scale applications in the presence of sulfur
impurities. For application of Pd-alloy mem-
branes in coal-derived synthesis gas, sulfur
needs thus to be removed by processes such as
ZnO beds and hydrodesulfurization. This
desulfurized synthesis gas may still contain
trace levels of H2S, and it is therefore important
to assess the stability of Pd-alloy membranes
under long-term exposure to trace levels of H2S
and to determine the upper acceptable H2S level.
P
Pd-Based Membrane: Scale-Up
Thijs Peters
SINTEF Materials and Chemistry, Oslo, Norway
Pd-based membrane technology is currently the
standard for small-scale H2 production
(~0.25–150 Nm3/h) in the electronics industry
as they can provide hydrogen to nine-nines
purity, meeting the most stringent requirements
for semiconductor fabrication processes. The
technological standard for the production of
ultrahigh purity hydrogen is based on self-
supported rolled foils or drawn tubes with thick-
ness range of 50–100 mm. To increase cost-
effectiveness compared to alternative technolo-
gies and processes, driven by the prospected use
of hydrogen as an energy carrier, composite
membranes with a reduced thickness of the Pd
layer on a mechanically strong support are being
developed. Here, the most frequently applied
membrane-manufacturing technique, electroless
plating, has low cost and is applicable for large-
scale production; see Pd alloy membrane prepa-
ration techniques. Along this route, tubular com-
posite membranes on porous metal supports have
been developed by several companies, like Shell/
CRI-Criterion, Pall Corporation, and Plansee/
Linde for application in membrane-intensified
steam reformer concepts. CRI Criterion currently
produces membranes of ODs up to 2 in. and
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1166-1
lengths up to 24 in. In addition, tubular mem-
branes on ceramic support for application in
WGS membrane reactors are offered on a
pre-commercial basis by ECN/Hysep ®. These
modules, currently with membrane area up to
0.5 m2, are only suitable for hydrogen separation.
The nominal capacity of the largest membrane
module equals 3.5–6 Nm3
h 1, based on the
obtained hydrogen flux applying reformate with
33 % H2, an inlet pressure of 25 bar and H2 outlet
pressure of 4 bar.
For successful commercialization of Pd-based
membranes, the membrane must have sufficient
permeability, selectivity, robustness, and durabil-
ity in relevant environments. Therefore, many
companies and research institutes are as well
working on pilot projects to demonstrate the tech-
nical feasibility of the Pd membrane technology.
Although this effort is still mainly limited to
laboratory-scale membranes or modules, some
new (pre)commercial membrane modules have
been successfully applied in pilot plant and indus-
trial facilities. Tokyo Gas uses plate-type mem-
branes incorporating Pd-based foils supported on
stainless steel carriers in their 40 Nm3/h-class
membrane reformer, and a membrane reforming
pilot plant with 20 Nm3/h of hydrogen capacity
has been constructed by Kinetics Technology in
Italy to investigate different types of Pd-based
membranes.
H
Hollow Fiber Spinning
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
Hollow fibers are fabricated by extruding or
pumping a dope solution through a spinneret fol-
lowing different methods such as melt spinning,
dry spinning, wet spinning, or dry/wet spinning.
The spinneret has a tube-in-orifice structure with
typical dimensions 0.5–1 mm inner diameter and
0.9–2 mm outer diameter. A simple experimental
device for the hollow fiber spinning by dry/wet
spinning is shown in Fig. 1. In some spinning
systems, a circulation pump is employed instead
of the gas cylinder (i.e., nitrogen) to drive the
dope solution through the spinneret. The dope
solution under gas pressure is forced to pass
through the spinneret the annular space of the
spinneret. The internal coagulant (bore liquid) is
driven through the central tube either by the grav-
ity force or by means of a circulation pump. The
dope solution, after being extruded from the spin-
neret, enters into a coagulation bath before trav-
eling a certain distance of air gap (i.e., the
distance between the spinneret and the coagula-
tion bath), which may vary from 0 (wet spinning)
to more than 1 m. In wet spinning, the dope
solution is extruded directly into the precipitating
liquid (external coagulant). In this technique the
spinneret is submerged in the coagulation bath
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1174-2
causing immediate fiber precipitation and solidi-
fication. In the dry/wet spinning, coagulation of
the internal surface of the nascent fiber starts
immediately after its extrusion from the spin-
neret, whereas the external surface experiences
coalescence and orientation of polymer aggre-
gates through the air gap before gelation in the
external coagulation bath takes place. After spin-
ning, the nascent fibers are oriented by means of
guiding wheels and finally pulled into a
collecting reservoir by a wind-up drum. Only a
fiber with sufficient mechanical integrity can pass
over the guiding wheels to the collecting bath.
During spinning, the take-up velocity is generally
kept at the same speed as the free-falling velocity
of the nascent fiber to prevent stretching of the
fiber (Khayet and Matsuura 2011).
Prior to the drying step, the spun hollow fibers
usually go through the solvent exchange and
other posttreatment procedures in order to
remove residual solvents, prevent hollow fiber
shrinkage, eliminate possible defects, and reduce
pore collapse. Conventional solvent exchange
step before drying consists of immersion of the
obtained hollow fibers in one non-solvent or suc-
cessive immersion in several non-solvent mix-
tures containing components with lower surface
tensions than water. Mixtures of water with
increased concentrations of lower surface tension
components such as methanol and ethanol can be
employed. Hexane can also be employed for fur-
ther solvent exchange since its surface tension is
even lower than alcohols and it is volatile.
2 Hollow Fiber Spinning

Hollow Fiber Spinning,

Fig. 1 Schematic diagram
of a typical hollow fiber
spinning system: 1 spinning
dope tank; 2 regulating
pressure valve; 3 pressure
gauge; 4 dope vessel;
5 dope valve; 6 bore liquid
vessel; 7 bore liquid pump;
8 spinneret; 9 air gap; 10
coagulation bath; 11 wind-
up drum; 12 fiber collecting
reservoir; 13 wash water
(Reprinted from Khayet
et al. (2009). Copyright
2009, with kind permission
from Elsevier)

The hollow fibers can be spun at room temper-
ature (20–22  C) or at a temperature higher than
the ambient temperature. During spinning the
take-up speed is normally maintained nearly the
same as the dope extrusion speed so that no
external elongational stresses, except gravity,
can be applied to the nascent hollow fiber.
A very large air gap distance may lead to flow
instability of the fiber resulting in nonuniform
fiber dimensions. Examples of typical applied
spinning parameters of different poly(vinylidene
fluoride), PVDF, dope solutions are bore liquid
flow rate (0.5–3 ml/min), air gap distance
(0–3 cm), take-up speed (free fall, 5 m/min),
dope solution flow rate (2–4 ml/min), applied
pressure over the dope solution (138–207 kPa),
and temperature of the coagulants (15.5–25  C)
(Wu et al. 2005, 2006, 2007; Wang et al. 2008).
In dry spinning, air or an inert gas is used
instead of the bore liquid so that solidification is
achieved through evaporation of the solvent. As
the dope solution exit the spinneret, air or an inert
gas is used to evaporate the solvent(s) so that the
fiber solidifies and collected on a take-up wheel.
Spinning is followed by stretching of the as-spun
fibers to orient the polymer chains along the gas
gap (i.e., fiber axis). The as-spun fibers do not
come into contact with a precipitating liquid. In
dry spinning and melt spinning, the dimensions
of the spinneret are not so crucial because the
fiber dimensions are mainly determined by the
ratio of the extrusion rate and “tearing rate”
(Mulder 1992). The gas flow used for solvent
evaporation and solidification of the fibers influ-
ences to a significant extent the quality of the
produced fibers.
In melt spinning, the polymer is first com-
pressed, heated, and melted by an extrusion
screw, then forced through the annular space of
the spinneret. The polymer solidifies by cooling
after being extruded from the spinneret and then
collected by means of take-up wheels. The spin-
ning rate in melt spinning (thousands of meter per
minute) is much higher than that used in the
Hollow Fiber Spinning
dry/wet spinning technique (meters per minute)
(Mulder 1992).
The spinneret geometry, the dope solution,
and the spinning conditions (bore fluid type and
its flow rate, dope solution extrusion rate, take-up
speed, air gap distance, external coagulant, spin
draw ratio, spinning temperature, cold stretching,
etc.) affect the hollow fiber geometrical parame-
ters (inner and outer diameters, thickness), its
internal structure, as well as the structural mor-
phology of the inner and outer surfaces.
References
Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
Khayet M, Garcı́a-Payo MC, Qusay FA, Zubaidy MA
(2009) Structural and performance studies of poly
3
(vinyl chloride) hollow fiber membranes prepared at
different air gap lengths. J Membr Sci 330:30–39
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
Wang KY, Chung TS, Gryta M (2008) Hydrophobic
PVDF hollow fiber membranes with narrow pore size
distribution and ultra-skin for the fresh water produc-
tion through membrane distillation. Chem Eng Sci
63:2587–2594
Wu B, Tan X, Teo WK, Li K (2005) Removal of benzene/
toluene from water by vacuum membrane distillation
in a PVDF hollow fiber membrane module. Sep Sci
Technol 40:2679–2695
Wu B, Tan X, Li K, Teo WK (2006) Removal of 1,1,1-
trichloroethane from water using a poly(vinylidene
fluoride) hollow fiber membrane module: vacuum
membrane distillation operation. Sep Purif Technol
52:301–309
Wu B, Li K, Teo WK (2007) Preparation and characteri-
zation of poly(vinylidene fluoride) hollow fiber mem-
branes for vacuum membrane distillation. J Appl
Polym Sci 106:1482–1495
H
Hollow Fiber
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
In general a hollow fiber is a cylindrical geometry
of any material having a hollow space with
an external diameter approximately less
than 0.5 mm (Fig. 1). It may have different
cross-sectional shapes such as round, trilobal,
pentagonal, octagonal, etc. Both smooth and
corrugated-shaped hollow fibers were fabricated
from different micro-engineered or smart
spinnerets (Fig. 2). Various types of spinnerets
(i.e., single or dual spinnerets, straight annular or
conical spinnerets, microstructured orifice in
spinneret) with different configurations and
dimensions are used in spinning hollow fibers
(Khayet and Matsuura 2011). The difference
between capillary, tubular, and hollow fiber is
simply a matter of dimensions. The approximate
diameter of a capillary membrane is between 0.5
and 5 mm, while that of a tubular membrane is
higher than 5 mm (Mulder 1992). Since hollow
fibers are mechanically self-supporting, the fiber
dimensions are very important. A hollow fiber
has an inner diameter (di) and outer diameter
(do), while the thickness (d) of the hollow
fiber wall is the difference between the outer
radius and the inner radius. The primary process
variables establishing hollow fiber diameters and
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1175-2
thickness are spinneret geometry. Other spinning
parameters such as the bore liquid (fluid) flow
rate, the dope extrusion rate, the take-up velocity
and the air gap distance can modify the geomet-
rical parameters of the spun hollow fibers.
For example, Wu et al. (2007) found that the
thickness of the poly(vinylidene fluoride),
PVDF, hollow fibers prepared by wet spinning
technique decreased with the increase of the
internal coagulant (bore liquid) flow rate. For
example, when the bore liquid flow rate was
increased from 1.1 to 1.5 ml/min and further to
1.8 ml/min, the corresponding thickness of the
PVDF hollow fibers decreased from 188 to
176 mm and further to 155 mm. An enhancement
of the inner diameter and a reduction of the outer
diameter of the hollow fibers with the increase of
the bore liquid flow rate were detected.
The process of fabricating synthetic hollow
fiber membranes is more difficult than that of
flat sheet membranes. In general, the process is
carried out by extruding or pumping a dope solu-
tion through a spinneret (Fig. 1) following differ-
ent methods such as melt spinning, dry spinning,
wet spinning, or dry/wet spinning. In melt spin-
ning and dry spinning, the dimensions of the
spinneret are not so crucial because the fiber
dimensions are mainly determined by the ratio
of the extrusion rate and “tearing rate” (Khayet
and Matsuura 2011). In wet spinning and wet/dry
spinning, the spinneret has a tube-in-orifice struc-
ture with typical dimensions 0.5–1 mm inner
diameter and 0.9–2 mm outer diameter.
2 Hollow Fiber

Hollow Fiber, a Outer diameter

Fig. 1 Hollow fiber (a) (do): 500 μm
and cross-section of c Polymer
common spinnerets (b, c)
used for fabrication of
b solution
Polymer
hollow fibers by (a) wet Thickness (δ) solution
spinning and dry/wet d =(do-di)/2
spinning and (b) melt
spinning and dry spinning
Bore
liquid
Inner diameter (di)

Hollow Fiber, Fig. 2 Scanning electron microscopy (a) and inner (b) microstructure (Reprinted from
(SEM) images of polyethersulfone/polyimide (PES/PI) (Nijdam et al. 2005). Copyright 2005, with kind permis-
blend hollow fiber membranes with a corrugated outer sion from Elsevier)

The first hollow fiber membranes were pat-
ented by Mahon in late the 1960s (Mahon
1966a, b). Various types of hollow fiber mem-
branes, hydrophobic or hydrophilic, dense or
porous, single or double layered, have been pro-
posed for different membrane separation pro-
cesses leading to a fast growth of synthetic
membrane technology. Since then significant
efforts have been made to develop new hollow
fibers with desirable structures and morphol-
ogies. However, until now, various scientists
admit that understanding the mechanisms of hol-
low fiber formation is rather qualitative than
quantitative. It is not easy to control the charac-
teristics of hollow fibers because various impor-
tant spinning parameters are involved
simultaneously. For example, the preparation of
the hollow fiber membrane by the dry/wet
spinning or wet spinning techniques requires
both internal (bore liquid) and external coagu-
lants and involves more controlling parameters
than the flat sheet membrane. Shape and dimen-
sion of the spinneret, viscosity of the spinning
dope (whether hollow fibers can be spun from
the dope), temperature of the spinning dope,
properties of the internal and external coagulants,
flow rate of the bore liquid, dope extrusion rate,
length and humidity of the air gap, wind-up
speed, and fiber take-up speed are some of those
examples. As a consequence, the major parts of
hollow fibers that appeared in the literature with
different structures and morphologies are based
mostly on trial-and-error experiments.
Hollow fibers are mechanically self-
supporting, have good flexibility, and are easy
to assemble in module and to handle for different
Hollow Fiber
Hollow Fiber, Fig. 3 Cross-sectional structure of PVDF
hollow fiber membranes prepared with wet spinning tech-
nique and dry/wet spinning technique using 20 wt.%
PVDF in the solvent N-methylpyrrolidone (NMP) and
applications. The feed is supplied to either the
inside or outside of the fiber, and the permeate
passes through the fiber wall to the other side of
the fiber. The fiber wall may have an asymmetric
structure being the active skin layer placed to the
feed side. A bundle of hollow fibers are often
mounted in a shell and tube module, which is
featured by a very large packing density (i.e.,
high surface area per unit module volume), and
therefore the size of the hollow fiber module is
smaller than other modules for a given perfor-
mance capacity. The packing capacity of a hol-
low fiber module may reach 500–9,000 m2/m3
resulting in a high productivity per unit volume.
Spinning corrugated hollow fibers is similar to
spinning smooth cylindrical fibers; the only dif-
ference is the use of a modified spinneret (Cao
et al. 2004; Çulfaz et al. 2010; Nijdam et al. 2005;
Wang et al. 2004). For example, to prepare a
hollow fiber with a corrugated inner microstruc-
ture instead of a cylindrical needle, the spinneret
is fabricated with a structured needle. To spin a
hollow fiber with a corrugated outer surface, a
microstructured orifice is incorporated to the
spinneret. Figure 2 shows SEM images of corru-
gated hollow fiber membranes.
3
40 wt.% NMP aqueous solution as internal coagulant
(Reprinted from (Bonyadi et al. 2007). Copyright 2007,
with kind permission from Elsevier)
The use of corrugated membrane surfaces is to
enhance the heat and mass transfer by increasing
the membrane surface area and the turbulence
near the membrane surface. Corrugations act as
turbulence promoters but also may lead to an
increase of pressure drop in the flow channel. It
was observed that the size of the corrugations on
the fiber was very sensitive to the air gap length
and even disappeared from the external surface
for high air gap lengths. When used in gas sepa-
ration, the selectivity (oxygen/nitrogen) and
permeance of polyethersulfone/polyimide
(PES/PI) blend corrugated hollow fiber mem-
brane were found to be similar to those of smooth
cylindrical fibers (i.e., circular-shaped fibers) pre-
pared under the same operating conditions. How-
ever, the gas permeate flow was increased by
19 %, which is the increase of membrane surface
area due to corrugations (Nijdam et al. 2005). It is
worth quoting that an increase of membrane sur-
face area of 89 % can be obtained with a corru-
gated hollow fiber membrane (Çulfaz et al. 2010).
Furthermore, PES/PVP blend hollow fiber mem-
branes were used in UF, and it was found that the
water permeability, molecular weight cutoff, and
pore size distribution of both the corrugated and
4 Hollow Fiber
circular-shaped fibers were similar (Çulfaz
et al. 2010). This indicates a higher permeate
flow of the corrugated hollow fiber compared to
the circular-shaped fiber and a similar UF sepa-
ration factor.
Instabilities and irregularities may occur dur-
ing hollow fiber spinning inducing corrugations
at their external or internal contours. These cor-
rugations can be eliminated increasing the air gap
distance (Fig. 3). The number of corrugations in
the internal surface of the hollow fiber mem-
branes is reduced approaching a final circular
shape. The hydrodynamic instability, which
leads to nonuniform cross-section and wavy
geometry, might be due to the pressure induced
in the nascent fiber (as a result of diffusion/con-
vection, precipitation, densification, and shrink-
age), which will buckle the rigid elastic shell
formed at the interface between the bore fluid
and the spinning dope solution (Bonyadi
et al. 2007).
References
Bonyadi S, Chung TS, Krantz WB (2007) Investigation of
corrugation phenomenon in the inner contour of
hollow fibers during the non-solvent induced phase-
separation process. J Membr Sci 299:200–210
Cao C, Chung TS, Chen SB, Dong ZJ (2004) The study of
elongation and shear rates in spinning process and its
effect on gas separation performance of poly(ether
sulfone) (PES) hollow fiber membranes. Chem Eng
Sci 59:1053–1062
Çulfaz PZ, Rolevink E, van Rijn C, Lammertink RGH,
Wessling M (2010) Microstructured hollow fibers for
ultrafiltration. J Membr Sci 347:32–41
Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
Mahon HI (1966a) Permeability separatory apparatus and
membrane element, method of making the same and
process utilizing the same. US Patent 3,228,876
Mahon HI (1966b) Permeability separatory apparatus and
process using hollow fibers. US Patent 3,228,877
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
Nijdam W, de Jong J, van Rijn CJM, Visser T, Versteeg L,
Kapantaidakis G, Koops GH, Wessling M (2005) High
performance micro-engineered hollow fiber mem-
branes by smart spinneret design. J Membr Sci
256:209–215
Wang KY, Matsuura T, Chung TS, Guo WF (2004) The
effects of flow angle and shear rate within the spinneret
on the separation performance of poly(ethersulfone)
(PES) ultrafiltration hollow fiber membranes. J Membr
Sci 240:67–79
Wu B, Li K, Teo WK (2007) Preparation and characteri-
zation of poly(vinylidene fluoride) hollow fiber mem-
branes for vacuum membrane distillation. J Appl
Polym Sci 106:1482–1495
M
Melt Spinning
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
Melt spinning is a fiber fabrication technique
from polymers or polymer/diluent systems that
can be melted. Both fibers (filaments) and hollow
fibers can be prepared by melt spinning tech-
nique. The polymer is first compressed, heated,
and melted by an extrusion screw, then forced to
pass through a spinneret of different geometries.
The polymer solidifies by cooling (thermal pre-
cipitation) after being extruded from the spin-
neret and then collected by means of take-up
wheels. The spinning rate in melt spinning
(thousands of meter per minute) is much higher
than that used in the dry/wet spin technique
(meters per minute) (Mulder 1992).
It is possible to prepare both porous and
nonporous hollow fibers by thermal precipitation
also known as thermally induced phase separa-
tion (TIPS). Figure 1 shows a typical example of
the systems used (Khayet and Matsuura 2011;
Matsuyama et al. 2003). A given amount of a
dope solution (polymer/diluent system) is mixed
under a nitrogen atmosphere in the vessel heated
at a temperature above the melting temperature of
the blend. The homogeneous polymer/diluent
melt blend is then fed to a spinneret by a gear
pump under nitrogen pressure of about 0.2 MPa.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1176-2
The spinneret shows an outer and an inner tube.
A diluent can also be introduced into the inner
tube of the spinneret to make a lumen of the
hollow fiber. The fiber extruded from the spin-
neret enters in the water bath under a controlled
temperature to induce phase separation and solid-
ification by means of polymer crystallization.
Simultaneously, the nascent fiber is wound by
using a take-up winder at several speeds. The
diluent present in the fiber is then following dif-
ferent methods that depend on the type of the
diluent. Other than the dope solution, the vari-
ables involved in hollow fiber membrane prepa-
ration via the TIPS technique are the air gap
distance, which is the distance from the spinneret
to water bath or to take-up wheels, the spinning
temperature, the water bath temperature, the
take-up speed, the spin draw ratio, the extrusion
rate of the blend, the flow rate of the diluent in the
inner tube of the spinneret, the cold stretching
through the air gap, the temperature of the poly-
mer/diluent blend and its composition, etc.
The TIPS technique is caused by a tempera-
ture change and typically consists of the follow-
ing basic steps (Khayet and Matsuura 2011;
Lloyd 1990):
i. A homogeneous solution is first formed by
melt blending a polymer and a liquid or solid
having a low molecular weight and a high
boiling point, referred to as the diluent (i.e.,
does not cause dissolution or swelling of the
polymer at room temperature). The initial
2 Melt Spinning

1.58 mm

0.83 mm
N2

polymer
solution

bore liquid

0.6 mm

mixing motor mixing vessel

spinneret
air gap

cool water bath

take-up winder

Melt Spinning, Fig. 1 Schematic diagram of a hollow fiber preparation system via thermally induced phase separation
(TIPS) technique (Reprinted from (Matsuyama et al. 2003). Copyright 2003, with kind permission from Elsevier)

temperature must be less than the boiling
point of the diluent and is typically
25–100  C greater than the melting tempera-
ture or glass transition temperature of the
polymer. The polymer must be stable at this
initial temperature. To avoid confusion, the
term diluent will be used instead of solvent,
hereafter. The diluent acts as a solvent only
when it can dissolve all polymers. When the
solvent power decreases sufficiently so that
liquid-liquid demixing takes place, the term
solvent is not appropriate anymore.
ii. The hot solution is extruded or spun in the
desired shape including a hollow fiber.
iii. The solution is cooled at controlled rate or
quenched to induce phase separation and
solidification.
iv. The diluent(s) that is trapped in the polymer
matrix during phase separation and solidifi-
cation is removed by solvent extraction
procedure.
v. The extractant is removed by evaporation to
yield microporous structures if required.
vi. Posttreatment processing might be applied to
improve the desired separation characteris-
tics of the TIPS membrane. Stretching might
be included in this step.
TIPS can be applied to a wide range of poly-
mers, including those that cannot be otherwise
formed into membranes because of poor solubil-
ity in solvent.
The type of phase separation (liquid-liquid
phase separation, solid-liquid phase separation,
combined liquid-liquid and solid-liquid phase
Melt Spinning
separation) that is likely to occur for a given
system (composition and temperature) is indi-
cated by the phase diagram (Khayet and
Matsuura 2011; Laxminarayan et al. 1994). This
is a useful tool explaining the morphology and
bulk structure of TIPS membranes. Polymers
such as polyethylene (PE), polypropylene (PP),
and poly(2,6-dimethyl-1,4-phenylene ether)
(PPE) were used in melt spinning (Khayet and
Matsuura 2011).
References
Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
3
Laxminarayan A, McGuire KS, Kim SS, Lloyd DR
(1994) Effect of initial composition, phase separation
temperature and polymer crystallization on the forma-
tion of microcellular structures via thermally induced
phase separation. Polymer 35:3060–3068
Lloyd DR (1990) Microporous membrane formation via
thermally-induced phase separation. I Solid-liquid
phase separation. J Membr Sci 52:239–261
Matsuyama H, Okafuji H, Maki T, Teramoto M, Kubota
N (2003) Preparation of polyethylene hollow fiber
membrane via thermally induced phase separation.
J Membr Sci 223:119–126
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
D
Dope Solution
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
Dope solution is a homogeneous thermodynami-
cally stable polymer solution formed by a poly-
mer or a copolymer, solvent or a solvent mixture,
and/or additive(s) (i.e., the additive can be a sec-
ond polymer, a non-solvent, organic or inorganic
particles of different sizes, etc.). It is also possible
to add a non-solvent to the polymer solution to
such an extent that all the components are still
miscible. In this case, care must be taken because
demixing may occur by the addition of the
non-solvent to the polymer solution so that it
becomes thermodynamically unstable. Some-
times nanoparticles or nanotubes are dispersed
in the polymer solution.
To prepare a dope solution, the polymer must
be soluble in a solvent or a solvent mixture. The
solvent has a close solubility parameter with the
polymer. The solvent and the non-solvent must
be miscible and the viscosity of the dope solution
must be high (i.e., more than 100 P).
After preparing the polymer solution, this
should be filtered to remove impurities and insol-
uble contaminants. Subsequently, the resulted
dope solution should be degassed before loading
into the dope vessel for fabrication of either flat
sheet or ▶ hollow fiber membranes. The spinning
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1177-2
dope suitable for ▶ hollow fiber fabrication by
dry/wet spinning or wet spinning techniques gen-
erally has a much greater viscosity and elasticity
than that used for the fabrication of flat sheet
membranes by the phase inversion technique.
The used polymer limits the solvent(s) and the
non-solvent(s) that can be used to prepare the
dope solution for the phase inversion process.
Water is frequently used as a non-solvent. For
example, among others, the solvents dimethyl
formamide (DMF) and dimethyl acetamide
(DMAC) were used to prepare dope solutions
from polysulfone, poly(ether sulfone), poly
(vinylidene fluoride), polyacrylonitrile, cellulose
acetate, polyimide, or poly(ether imide).
To prepare membranes by thermal precipita-
tion, for example, thermally induced phase inver-
sion (TIPS) membranes, the dope solution is a
polymer/diluent system adequate to form a
homogeneous melt blend, which will be cooled
or quenched to induce phase separation (i.e.,
liquid–liquid phase separation, solid–liquid
phase separation, or combined liquid–liquid and
solid–liquid phase separation). For TIPS mecha-
nism the diluent should be miscible with the
considered polymer at high temperatures, should
have a relatively low molecular weight together
with a low volatility at high temperatures, and
should be thermally stable at high temperatures.
For example, the used diluent for poly(vinylidene
fluoride), PVDF, is dimethyl phthalate, dioctyl
phthalate, dioctyl sebacate, dibutyl phthalate,
2 Dope Solution
P permeability of the fabricated phase inversion
Miscible
region
Dope
solution a b c d Membrane
Tie Immiscible
line region
S NS
Dope Solution, Fig. 1 Schematic phase diagram of an
isothermal ternary system (polymer, P; solvent, S and
non-solvent, NS)
g-butyrolactone, propylene carbonate, or dibutyl
sebacate.
The parameters affecting the physical and
chemical characteristics of the dope solution are
the polymer, the solvent(s), the non-solvent addi-
tive(s), and their concentrations as well as the
temperature. These characteristics affect the
structural morphology of the formed flat sheet
membranes and hollow fibers. The polymer con-
centration in the dope solution is one of the rele-
vant factors affecting membrane structure. For
example, the increase of the polymer concentra-
tion in the dope solution results in a high-volume
fraction of polymer and consequently a low
porosity and small pore size. A significant reduc-
tion of the porosity was observed with increasing
PVDF concentration in the spinning dope from
15 to 20 wt% (Wu et al. 2007). However, over
this PVDF concentration range, no apparent
effect on the mean pore size of the prepared
hollow fibers was observed. Fabrication of mem-
branes by the phase inversion technique from
dope solutions with a very low polymer concen-
tration is practically impossible. For instance,
when the polymer content is less than a threshold
value, for example, 10 wt% for PVDF, the
resulting membranes become inconsistent and
holes start to appear within the membrane (Ortiz
de Zárate et al. 1995). In the phase inversion
process, non-solvent additive in the dope solution
acts as a pore-forming agent improving the
membrane. In general, when the concentration
of the non-solvent additive is increased in the
dope solution, the pore size and porosity of the
prepared membrane increase (Khayet and
Matsuura 2001).
The maximum amount of non-solvent that can
be added to a dope solution can be determined
from the ternary phase diagram presenting the
composition of the polymer, solvent, and the
non-solvent. In this case, the dope solution must
be in one phase region where all the components
are completely miscible with each other. Figure 1
shows an isothermal ternary system (polymer, P;
solvent, S, non-solvent, NS). The pure compo-
nents (P, S, NS) are localized at the corners of
the triangle, and any point within the triangle
represents a mixture of all three components.
Within a certain compositionally defined range
of thermodynamic states, all three components
are completely miscible, whereas in a different
range, the system decomposes into two distinct
phases. The solid black line is the liquid–liquid
boundary, called the binodal which separates the
miscible region at the left from the immiscible
region at the right. The thermodynamic parame-
ter describing the miscibility of two or more
components (e.g., polymer and diluent) is the
Gibbs free energy of mixing, for which an expres-
sion was given by the Flory-Huggins lattice the-
ory (Flory 1965).
During membrane preparation, the dope solu-
tion at the left side of the binodal in the P-S axis is
immersed in a non-solvent so that the final com-
position will be displaced to the right side in the
phase diagram toward the P-NS axis. Different
composition paths can occur (Khayet and
Matsuura 2011). For example, the path (a, b, c,
d) starts from a dope solution with a low initial
polymer volume fraction on the P-S axis and the
ratio of the rate of solvent outflux to that of the
non-solvent influx is relatively high. When the
dope solution crosses the binodal, two separate
phases will begin to form. Those are a polymer-
rich phase represented by the upper end of the tie
line and a polymer-poor phase represented by the
lower end of the tie line. If the amount of the
polymer-rich phase is large relative to the amount
Dope Solution
of the polymer-poor phase, droplets of the latter
phase are dispersed in the continuous polymer-
rich phase and form pores in the continuous poly-
mer matrix. The obtained final membrane at the
P-NS axis is asymmetric (i.e., a dense surface
layer at the film/gelation media interface
followed by a porous sub-layer). The film com-
position starts from the point “a,” passes through
points “b” and “c” (polymer densification point),
and finally reaches the point “d” along the com-
position path. “b” is the point where the phase
separation starts and “c” is the point where the
polymer solidification starts to occur. Exchange
of solvent and non-solvent will lead to the final
formation of the membrane, the porosity of which
is determined by the point on the P-NS line (e.g.,
point “d”) (Khayet and Matsuura 2011).
3
References
Flory PJ (1965) Principles of polymer chemistry. Cornell
University Press, Ithaca
Khayet M, Matsuura T (2001) Preparation and character-
ization of polyvinylidene fluoride membranes for
membrane distillation. Ind Eng Chem Res
40:5710–5718
Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
Ortiz de Zárate JM, Peña L, Mengual JI (1995) Character-
ization of membrane distillation membranes prepared
by phase inversion. Desalination 100:139–148
Wu B, Li K, Teo WK (2007) Preparation and characteri-
zation of poly(vinylidene fluoride) hollow fiber mem-
branes for vacuum membrane distillation. J Appl
Polym Sci 106:1482–1495
D
Dry Spinning
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
Dry spinning is an extrusion technique used for
fabrication of fibers (filaments) or hollow fibers
using a viscous dope solution containing polymer
(s) dissolved in a volatile solvent or in a solvent
mixture with a high volatility. The dope solution
is pumped (extruded) through a filter and then
through a spinneret or tiny orifices (i.e., jets) in
a heated drying chamber. As the dope solution
exit the spinneret, air or an inert gas is used to
evaporate the solvent(s) so that the fiber solidifies
and collected on a take-up wheel. Spinning is
followed by stretching of the as-spun fibers to
orient the polymer chains along the gas gap
(fiber axis). In dry spinning the as-spun fibers do
not come in contact with any precipitating liquid
(bore liquid, external coagulant). Dry spinning
differs from dry/wet spinning and wet spinning
in that the solidification is achieved through
evaporation of the solvent carried out by a stream
of air or an inert gas. In dry spinning and melt
spinning, the dimensions of the spinneret are not
so crucial because the fiber dimensions are
mainly determined by the ratio of the extrusion
rate and “tearing rate” (Mulder 1992). The gas
flow used for solvent evaporation and solidifica-
tion of the fibers influences to a significant extent
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1178-2
the quality of the produced fibers. In dry/wet
spinning and wet spinning, precipitating liquids
are involved (bore liquid, external coagulant). In
dry spinning, the fiber does not need to be dried
like in wet spinning and dry/wet spinning. Exam-
ples of polymer used for production of fibers by
dry spinning are cellulose acetate,
polyacylonitrile, polyurethane, and fibers based
on poly-m-phenylene isophthalamide, polybenzi-
midazoles, polyamidoimides, and polyimides. In
general, dry spinning is used for polymers that
cannot be used in melt spinning. The concentra-
tion of the spinning dope solution and the spin-
ning speeds is higher than those used in dry/wet
spinning and wet spinning. Spinning speeds
range between 300 and 1000 m/min. The spin-
ning rate in melt spinning (thousands of meters
per minute) is much higher than that used in the
dry/wet spin technique (meters per minute)
(Mulder 1992).
When a polymer solution is extruded through
a tube in orifice spinneret, shear stress is induced
within the spinneret (Fig. 1) (Khayet and
Matsuura 2011). There are at least three forces
(stresses) applied upon the dope solution:
(i) shear and elongation stresses within the spin-
neret, (ii) gravity induced by the weight of the
spun hollow fiber, and (iii) stress induced by the
take-up system (i.e., wind-up drum or take-up
wheel). It is known that the stress affects dramat-
ically the polymer molecular orientation and
relaxation at the outer surface of the nascent
fiber. The effects of elongation and relaxation
2 Dry Spinning

Dry Spinning, b Bore fluid

Fig. 1 Schematic
presentation of die swell
(gas)
occurring in the nascent a Dope solution
fiber (a) and hollow fiber Dope Dope
(b) when extruded from a solution solution
spinneret

Spinneret Spinneret

Gas gap Gas gap

Formed fiber Hollow fiber

after exiting from the spinneret will play impor-
tant roles on final hollow fiber structure. Further-
more, the induced elongation stresses outside the
spinneret from gravity through the air gap com-
plicate the kinetics and dynamics of the phase
inversion process. In addition, non-Newtonian
polymer solutions may exhibit die swell and
relaxation after exiting from spinneret.
Molecular chains tend to align themselves
much better, and this enhanced orientation causes
the polymer molecules to pack closer to each
other leading to a tighter skin fiber structure.
The molecular orientation induced by shear stress
within the spinneret might relax in the air gap
region, before reaching the take-up wheel, if the
elongation stress along the spin line is small as
spinning dope solution is a viscoelastic fluid or
might be enhanced if the spin line stress is high.
In other words, the elongation stress caused by
gravity along the spinning line becomes more
pronounced with increasing the distance between
the spinneret or jets and the take-up wheel.
References
Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
E
External Coagulant in Fiber
Preparation
Khayet Mohamed
Department of Applied Physics I, Universidad
Complutense de Madrid, Madrid, Spain
External coagulant is a non-solvent liquid or a
mixture of solvent/non-solvent in a collecting
bath (coagulation bath) used for fabrication of
fibers by the dry-/wet-spinning technique or the
wet-spinning technique. Coagulation of the
external surface of the nascent fiber can start
immediately after its extrusion from the spinneret
(wet spinning) or after the as-spun fiber crosses
an air gap (i.e., distance between the spinneret
and the coagulation bath) through which the
external surface experiences coalescence and ori-
entation of polymer aggregates (wet/dry spin-
ning). In general, the nascent fiber is partially
coagulated by the internal coagulant (bore liquid)
and/or through the air gap by solvent evaporation,
and finally the coagulation is completed in the
coagulation bath by an external coagulant.
The type of the external coagulant affects con-
siderably the structural morphology of the
resulted fiber. Usually, water is the preferred
external coagulant because of its low cost and
environmental friendliness. The proper choice
of the coagulant is very important because
the rate of demixing (i.e., phase separation) and
the resultant inner and outer surface structures of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1179-2
the hollow fiber strongly depend on the chemistry
and the composition of the coagulant. The molec-
ular sizes and solubility parameters of the used
solvent and the internal and the external coagu-
lant play important roles on hollow fiber mor-
phology. Solvent of a large size may have
difficulties to leach out during the coagulation
step. The difference in solubility parameters
between the spinning dope solution and the bore
liquid (internal coagulant) or the external coagu-
lant affects the coagulation rate and subsequently
the porosity of the spun hollow fiber membrane.
The interactions between solvent and external
coagulant and between solvent and polymer play
important roles affecting the rate of polymer pre-
cipitation. The temperature of the external coag-
ulant affects also the polymer precipitation rate.
The maximum amount of solvent that can be
added to the non-solvent in the coagulation bath
can be roughly determined by the position of the
binodal (liquid-liquid boundary separating the
miscible region from the immiscible one) in the
ternary phase diagram presenting the composi-
tion of the polymer, solvent, and non-solvent.
When the binodal shifts toward the polymer/sol-
vent axis, more solvent can be added in the exter-
nal coagulant. It is also possible to change from
porous to nonporous external fiber surface by
adding solvent to the coagulation bath (Mulder
1992). For example, when a strong coagulant
such as water for poly(vinylidene fluoride),
PVDF, polymer is used for hollow fiber fabrica-
tion, a dense and smooth surface with no obvious
2 External Coagulant in Fiber Preparation
External Coagulant in Fiber Preparation,
Fig. 1 Cross-sectional scanning electron microscopy
(SEM) structure of PVDF hollow fiber membranes pre-
pared with different coagulants: (a) water coagulant; (b)
pores is formed. However, when a weaker coag-
ulant is employed such as methanol, which may
be mixed with water, the roughness of the formed
hollow fiber surface may increase considerably
due partially to the formation of pores. These are
the reasons for using the coagulants: 80 wt.%
N-methylpyrrolidone (NMP) aqueous solution
by Wang et al. (2008) for preparation of PVDF
hollow fiber membranes and 80 wt.% methanol
aqueous solution by Bonyadi and Chung (2007)
for fabrication of dual hydrophilic/hydrophobic
hollow fiber membranes for direct contact mem-
brane distillation (DCMD) process. Figure 1
shows the effects of the external coagulant on
the cross-sectional structure of porous hydropho-
bic hollow fiber membranes (Khayet et al. 2002).
Water and 50 % (by volume) ethanol in water
were used as internal and external coagulants. In
Fig. 1a prepared with water as internal and exter-
nal coagulants, long finger-like voids are formed
near the inner surface, while smaller cavities are
formed near the outer surface. Between the inner
and outer layers, sponge-like structure appears. In
Fig. 1b the outer layer is eliminated when ethanol
is added to the external coagulant. The addition of
ethanol delays the external coagulation process
and the finger-like structure changes to a sponge-
like structure. The slow coagulation of the hollow
fiber membranes can be explained on the basis of
internal coagulant water and external coagulant 50 %
ethanol in water (Reprinted from (Khayet et al. 2002).
Copyright 2002, with kind permission from Elsevier)
the mutual diffusivity of solvent/non-solvent
exchange and solubility parameters of the mate-
rials involved in hollow fiber spinning. The addi-
tion of ethanol in water reduces the diffusion of
non-solvent into the nascent hollow fiber mem-
brane and consequently decreases the rate of pre-
cipitation. Khayet et al. (2002) observed an
increase of the external surface roughness of
PVDF hollow fibers when ethanol was added to
the external coagulant and attributed the result to
the increase of the pore size at the outer surface as
ethanol was added in the coagulation bath.
References
Bonyadi S, Chung TS (2007) Flux enhancement in mem-
brane distillation by fabrication of dual layer
hydrophilic-hydrophobic hollow fiber membranes.
J Membr Sci 306:134–146
Khayet M, Feng CY, Khulbe KC, Matsuura T (2002)
Preparation and characterization of polyvinylidene
fluoride hollow fiber membranes for ultrafiltration.
Polymer 43:3879–3890
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer Academic Publishers, Dordrecht
Wang KY, Chung TS, Gryta M (2008) Hydrophobic
PVDF hollow fiber membranes with narrow pore size
distribution and ultra-skin for the fresh water produc-
tion through membrane distillation. Chem Eng Sci
63:2587–2594
B
Bore Liquid: Solvent and
Non-solvent
Khayet Mohamed
Department of Applied Physics, Universidad
Complutense de Madrid, Madrid, Spain
Bore injection liquid is an internal coagulant
pumped through the inner tube of the spinneret
used for fabrication of hollow fibers by the
dry/wet spinning technique or the wet spinning
technique. Figure 1 shows schematic illustrations
of the cross-sections of the spinneret used in these
techniques. The spinneret has a tube-in-orifice
structure with typical dimensions 0.5–1 mm
inner diameter and 0.9–2 mm outer diameter.
The bore liquid is one of the controlling
parameters of the wet spinning and dry/wet spin-
ning techniques used to fabricate hollow fibers. It
must be a non-solvent or a non-solvent mixture
exhibiting a low affinity with the polymer solu-
tion (dope solution). The solubility parameter of
the bore liquid must be different from that of the
polymer to be coagulated. The interactions
between solvent and coagulant and between sol-
vent and polymer play important roles affecting
the rate of polymer precipitation (coagulation,
solidification). For poly(vinylidene fluoride)
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1180-4
(PVDF) polymer solution as an example, water
is a strong coagulant commonly used for fabrica-
tion of hollow fibers. In the dry/wet spinning or
wet spinning, the polymer solution under gas
pressure is extruded from the annular space of
the spinneret, whereas the internal coagulant
(bore liquid) is driven through the central tube
of the spinneret either by gravity force or by
means of a circulation pump. Coagulation of the
internal surface of the nascent fiber starts imme-
diately after its extrusion from the spinneret,
whereas the external surface experiences coales-
cence, and orientation of polymer aggregates
through the air gap before gelation in the external
coagulation (i.e., non-solvent or non-solvent mix-
ture) bath. The air gap is the vertical distance
between the spinneret and the liquid coagulation
bath and it may vary from 0 (wet spinning) to
more than 1 m (dry/wet spinning). The bore liq-
uid and the solvent exchange by diffusion and
then the polymer solution become thermodynam-
ically unstable. Demixing may take place from
the bore side or lumen side and from the shell or
outside of the as-spun fiber. Two types of
demixing are possible: liquid–liquid demixing
and gelation or crystallization. Gelation is not a
phase separation process whereas crystallization
involves a solid–liquid demixing. In order to
determine the composition or temperature at
2 Bore Liquid: Solvent and Non-solvent
a hollow fiber may increase considerably due par-
Polymer
solution
Bore
liquid
Bore
b liquid
Polymer Polymer
solution solution
Bore Liquid: Solvent and Non-solvent,
Fig. 1 Transversal (a) and lateral (b) cross-sections of a
common spinneret used in dry/wet spinning and wet spin-
ning techniques
which the solution is no longer thermodynami-
cally stable, turbidity or cloud points must be
determined. Cloud points are defined as the
moment when the solution changes from clear
to turbid. To localize the cloud point of a ternary
system, a possible method is titration of polymer
solution containing polymer and solvent with
non-solvent or with a mixture of solvent and
non-solvent at a given temperature until perma-
nent turbidity is detected. The turbidity point can
be detected by turbidity measurements or light
scattering methods.
When a strong bore liquid coagulant such as
water for PVDF polymer is used for the fabrication
of a hollow fiber membrane, a dense and smooth
surface with no obvious pores is formed. How-
ever, when a weaker coagulant is employed such
as methanol, which may be mixed with water, the
roughness of the internal surface of the formed
tially to the formation of pores. Figure 2 shows the
effects of the bore liquid coagulant on the cross-
sectional structure of porous hydrophobic hollow
fibers prepared by the dry/wet spinning technique
(Khayet et al. 2002). Water and 50 % (by volume)
ethanol in water were used as internal and external
coagulants. Different cross-sectional structures
can be observed. In Fig. 2a prepared with water
as internal and external coagulants, long finger-
like voids are formed near the inner surface, while
smaller cavities are formed near the outer surface.
Between the inner and outer layers, sponge-like
structure appears. The inner layer is reduced when
ethanol is added to the internal coagulant as can be
seen in Fig. 2b. A uniform sponge-like structure
extends over the entire hollow fiber cross-section,
in Fig. 2c, when ethanol is added to both the
internal and external coagulants. The addition of
ethanol delays the coagulation process, and a long
finger-like structure changes to a short finger-like
structure and further to a sponge-like structure.
The slow coagulation of the hollow fibers can be
explained on the basis of the mutual diffusivity of
solvent/non-solvent exchange and solubility
parameters of the materials involved in hollow
fiber spinning. The addition of ethanol in water
reduces the diffusion of non-solvent into the
nascent hollow fiber and consequently decreases
the rate of precipitation (coagulation, precipita-
tion). The surface roughness increased when eth-
anol was added to the bore liquid coagulant, which
is due to the increase of the pore size. The pores at
the inner surfaces of the hollow fibers are larger
than those at the outer surfaces, and the pore size
increases both at the inner and at the outer surfaces
as ethanol was added to the coagulants (Khayet
et al. 2002). A decrease of the porosity of PVDF
hollow fibers was also observed with the addition
of ethanol in the bore liquid.
Bore Liquid: Solvent and Non-solvent 3

Bore Liquid: Solvent and Non-solvent, Fig. 2 Cross- coagulant, (b) internal coagulant 50 % ethanol in water
sectional scanning electron microscopy (SEM) structure and external coagulant water, (c) 50 % ethanol in water
of PVDF hollow fiber membranes prepared by wet/dry coagulant (Reprinted from Khayet et al. (2002), Copyright
spinning technique with different coagulants: (a) water 2002, with kind permission from Elsevier)

Reference fluoride hollow fiber membranes for ultrafiltration.

Polymer 43:3879–3890
Khayet M, Feng CY, Khulbe KC, Matsuura T (2002)
Preparation and characterization of polyvinylidene
M
Membrane (Definition, Function,
Structure)
Lidietta Giorno and Enrico Drioli
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, National
Research Council of Italy, Rende(CS), Calabria,
Italy
Synonyms
Membrane classification; Membrane definition;
Membrane function
A precise and complete definition of a membrane
that covers all its aspects is rather difficult, even
when the discussion is limited to synthetic struc-
tures. Various definitions have been reported in
the literature, most of them focusing on the selec-
tive properties of the membrane. For example,
Lonsdale defined a synthetic membrane as an
interphase that separates two phases and restricts
the transport of various components in a specific
manner (Lonsdale et al. 1982). In new membrane
processes, such as membrane contactors, the
membrane is a nonselective barrier that separates
and contacts two adjacent phases. Therefore, in
the most general sense, we can define a mem-
brane as a discontinuous phase between two adja-
cent phases that permits the exchange of matter,
energy, and information between the phases with
selective or nonselective properties.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1187-2
Separation of a mixture in a membrane pro-
cess is the result of different transport rates of
different components through the membrane.
The transport rate of a component through a
membrane is determined by driving forces such
as concentration, pressure, temperature, and elec-
trical potential gradients, as well as by the con-
centration and mobility of the component in the
membrane matrix.
A membrane can be homogeneous or hetero-
geneous, symmetric or asymmetric in structure
(Strathmann et al. 2006). It may be solid or liquid
and may consist of organic, inorganic, or biolog-
ical materials as well as a mixture of them. Mem-
branes made of inorganic components dispersed
in the organic matrix are called mixed matrix
membranes. Membranes made of biological
components contained in organic or inorganic
materials are called biohybrid membranes.
When membranes are engineered with materials
that transfer principles from biology, they are
termed biomimetic membranes. Bioinspired
membranes are a broader term compared to
biomimetic. They are synthetic membranes that
mimic the structure and function of their natural
counterpart. A biomimetic membrane is also
bioinspired, but not necessarily the other way
round.
A membrane may be neutral or it may carry
positive or negative charges, or functional groups
with specific binding or complexing abilities. Its
thickness can be less than 100 nm to more than a
millimeter. The electrical resistance may vary
2 Membrane (Definition, Function, Structure)
a membrane with
specific selectivity
R1 R2
R3
R1 R2 R1
R3
driving force
ΔC, Δp, ΔT
Membrane (Definition, Function, Structure),
Fig. 1 Schematic drawing illustrating (a) a membrane
which is selective for the transport of different compo-
nents such as two enantiomers and (b) a membrane which
from more than 1,000,000 Ω cm2 to less than 1 Ω
cm2.
The term “membrane,” therefore, includes a
great variety of materials and structures, and a
membrane can often be better described by its
function rather than by its structure. Some mate-
rials, such as protective coatings or packaging
materials, show typical membrane properties
and are in fact membranes. Most materials func-
tioning as membranes have the characteristic
property in common of restricting the passage of
different components in a very specific manner.
In some cases, they may restrict the passage of the
same component, depending on the state: a
hydrophobic polymeric membrane may allow
the passage of water as vapor phase but not as
liquid phase, as, for example, in membrane dis-
tillation. In other cases, e.g., membrane
contactors, the porous structure of the membrane
material functions as a barrier that keeps in con-
tact two adjacent phases between which a mass
transfer occurs and separates them at the same
time. In this case the membrane has no direct
effect on the transport of various components
and is nonselective toward the passing species.
The concept of a selective and nonselective mem-
brane is illustrated in Fig. 1 which shows (a) a
b membrane with no specific
component selectivity
liquid vapour
phase phase
R2
R3
driving force
ΔC, Δp, ΔT
separates a liquid and a vapor phase and allows passage of
vapor molecules but is not selective for the transport of
different components
membrane which is highly selective and capable
of separating, e.g., two enantiomers, and (b) a
membrane that acts as a barrier between two
phases and avoids the mixing of the phases but
has no selective properties related to the transport
of different components from one phase to the
other.
A porous structure represents a very simple
form of a membrane, which closely resembles
the conventional filter as far as the mode of sep-
aration is concerned. These membranes consist of
a solid matrix with defined holes or pores which
have diameters ranging from less than 1 nm to
more than 10 mm. The macromolecular size of the
species to be separated plays an important role in
determining the pore size of the membrane to be
utilized and the related membrane process.
Porous membranes with average pore diameters
larger than 50 nm are classified as macroporous,
and those with average pore diameters in the
intermediate range between 2 and 50 nm are
classified as mesoporous. Membranes with
average pore diameters between 0.1 and 2 nm
are classified as microporous. Dense membranes
have no individual permanent pores, but the
separation occurs through fluctuating free
volumes, by solution-diffusion mechanism
Membrane (Definition, Function, Structure) 3

Membrane (Definition, Function, Structure), Fig. 2 Schematic classification of membranes, related processes, and
separated components

Membrane (Definition, Function, Structure), Fig. 3 Porous symmetric (a) and asymmetric membrane (b)

(Strathmann et al. 2010). The schematic repre-
sentation of such classification is illustrated in
Fig. 2.
In pressure-driven membrane processes, the
separation of the various components is achieved
by a sieving mechanism with the pore diameters
and the particle sizes being the determining
parameters. In thermally driven membrane pro-
cesses, the separation is based on the principle of
phase equilibrium, and the non-wettability of
membrane pores is the determining parameter.
Membrane structure may be symmetric
(Fig. 3a), i.e., the pore diameters do not vary
over the membrane cross section, or they can be
asymmetric (Fig. 3b), i.e., the pore diameters
increase from one side of the membrane to the
other typically by a factor of 10–1,000.
The mechanism by which certain components
are transported through a membrane can also be
very different. In some membranes, for example,
the transport is based on viscous flow of a mixture
through individual pores of the membrane caused
by a hydrostatic pressure difference between the
two phases separated by the membrane. This type
of transport is referred to as viscous flow. The
components that permeate through the membrane
4 Membrane (Definition, Function, Structure)

a b

Membrane (Definition, Function, Structure), Fig. 4 Schematic diagram illustrating (a) the sieving mechanism of a
porous membrane and (b) the solution-diffusion mechanism in a nonporous membrane

Material Configuration
polymer flat-sheet
ceramic Membrane spiral wound
glass classification tubular
metal capillary
liquid hollow fiber

composite structures:
homogeneous skin layer
Structure
symmetric symmetric asymmetric
asymmetric
integral asymmetric

homogeneous films cylindrical pores sponge-type structures porous skin layer homogeneous skin layer

Membrane (Definition, Function, Structure), Fig. 5 General classification of membranes

are transported by convective flow through
macropores under a pressure gradient as driving
force and the separation occurs because of size
exclusion as indicated in (Fig. 4a). Darcy’s Law
describes this type of transport. It is the dominant
form of mass transport in micro- and ultrafiltra-
tion but also occurs in other membrane processes.
If the transport through a membrane is based
on the solution and diffusion of individual mole-
cules in the nonporous membrane matrix due to a
concentration or chemical potential gradient, the
transport is referred to as diffusion. The separa-
tion occurs because of different solubility and
diffusivity of components into the membrane
material as indicated in (Fig. 4b).
Fick’s law describes this type of transport. The
diffusion of molecules through homogeneous
dense membranes occurs through the free volume
elements, or empty spaces between polymer
chains caused by thermal motion of the polymer
molecules, which fluctuate in position and vol-
ume on the same time scale as the molecule
permeates. The transition between fluctuating
free volumes and individual permanent pores is
controversial. In general it is considered in the
range of 5–10 Å in diameter.
Membrane (Definition, Function, Structure) 5

This form of mass transport is dominant in References

reverse osmosis, gas separation, and
pervaporation but it may occur in other Lonsdale HK (1982) The growth of membrane technol-
ogy. J Membr Sci 10:81
processes, too.
Strathmann H, Giorno L, Drioli E (2006) An introduction
If an electrical potential gradient across the to membrane science and technology. CNR Publisher,
membrane is applied to achieve the desired trans- Roma. ISBN 88-8080-063-9
port of certain components through the mem- Strathmann H, Giorno L, Drioli E (2010) Basic aspects in
polymeric membrane preparation, in Comprehensive
brane, the transport is referred to as migration.
membrane science and engineering, E. Drioli, L.
Migration occurs in electrodialysis and related Giorno Eds, Elsevier BV, pp. 91-111, ISBN: 978-0-
processes and is limited to the transport of com- 444-53204-6
ponents carrying electrical charges such as ions.
The general classification of membranes, on
the basis of material, structure, and configuration,
is illustrated in Fig. 5.
M
Membrane Bioreactors for Cell
Growth
Loredana De Bartolo
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende(CS),
Italy
Membrane bioreactors composed of semiperme-
able membranes and bioreactors are very attrac-
tive for the culture of animal, plant, and microbial
cells. For mammalian cell cultures, membrane
bioreactors are mainly used to produce biochem-
icals such as vaccines, interferons, hormones,
growth factors, viruses, and monoclonal anti-
bodies and to act as artificial organs. More
recently, membrane bioreactors found applica-
tions in the area of regenerative medicine for
developing functional tissues from cells in com-
bination with a suitable matrix to support and
accelerate regenerative healing. In these devices,
usually cells are immobilized in a compartment
separate from the feed medium containing nutri-
ents that diffuse through the membrane to the cell
compartment. Membrane with suitable MWCO
allows the retention of cells and the separation of
cell products from the feeding stream. Multiple
functions are performed by membrane in the bio-
reactor: (i) compartmentalization of cells, (ii) the
selective transport of nutrients and metabolites to
the cells and the removal of catabolites and cell
products, (iii) wide surface for adhesion of
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1190-1
anchorage-dependent cells, and (iv) protection
of cells from shear stress. The efficiency of the
overall system depends on the cells (viability,
functions, density), membranes (configuration,
structure, size, morphology, pore size distribu-
tion, physicochemical and mechanical proper-
ties), and hydrodynamic parameters (flow rate,
transmembrane pressure, residence time, shear
stress, etc.). A critical point in the design of an
efficient membrane bioreactor for cell growth is
the overall transmembrane mass flux of metabo-
lites, catabolites, cell regulatory, and related sol-
uble factors that need to be considered.
Molecules contained in the culture medium,
which are fed and produced by cells, are com-
prised on a wide range of molecular sizes (from
small electrolytes to large proteins) and physico-
chemical properties (hydrophilic, hydrophobic
molecules). The transport of low MW nutrients
and metabolites is assumed to occur by diffusion,
whereas convection phenomena are supposed to
regulate the mass transfer of macromolecular
species and proteins (Giorno et al. 2011). Surface
properties of membranes need to be also consid-
ered in the design of a membrane bioreactor for
the culture and expansion of adherent cells that
are in tight contact with the membrane surface.
Membranes should have surface characteristics
in terms of morphology and physicochemical
and mechanical properties that favor the adhesion
process and the integration of cells. Membrane
bioreactors have been investigated for the culture
of lymphocytes, liver cells, embryonic stem cells,
2 Membrane Bioreactors for Cell Growth
progenitor cells, and stem cells. These devices
have been used in replacement therapy for acute
and chronic organ failure and in the management
of immunological disease as well as in tissue
engineering for the realization of tissue-
engineered constructs and defined models
supporting investigations on cell function, tissue
development, and drug testing. Different config-
urations of membrane bioreactor have been
explored for the culture and growth of mamma-
lian cells. Primary cells, immortalized cells, and
stem cells can be cultured (a) on flat-sheet mem-
branes, (b) in the lumen or shell of hollow fiber
membranes in suspension or attached to the mem-
brane surface, (c) in a network of hollow fiber
membranes, (d) in a spirally wound membrane
device, (e) in multibore fibers, and (f) in
gas-permeable membrane bioreactor. Flat mem-
brane bioreactor is a simple device that has been
developed for the small-scale culture of cells
(e.g., neurons, hepatocytes) as tool for drug
screening and toxicological studies (De Bartolo
et al. 2006a). In this device a microporous flat-
sheet membrane separates the medium compart-
ment from the cells that are adhered on the mem-
brane. Advanced bioreactors use additionally
gas-permeable membranes (e.g., fluorocarbon
membranes), which are permeable to oxygen,
carbon dioxide, and water vapor, in order to
improve the oxygenation of cells. In this device
cells receive oxygen directly from the bottom
membrane sheet where they are seeded and indi-
rectly from the microporous membrane in contact
with the medium overlaying the cells (De Bartolo
et al. 2006b). Hollow fiber membrane bioreactors
are the most used bioreactors for high cell density
culture. In these devices cells usually are cultured
in the shell of a bundle of hollow fiber mem-
branes parallel-assembled, and the medium
flows in the lumen (De Bartolo et al. 2007b).
Alternatively cells can be cultured inside the
lumen of hollow fiber and the medium flows in
the shell (Demetriou et al. 1986). In both cases
the medium and cell compartments communicate
through the pores of the fiber wall. Advanced
designs of bioreactors using a network of hollow
fiber membranes with different properties have
been developed for the culture of cells in order to
improve the mass transfer (Gerlach et al. 1994).
Spirally wound bioreactor has been proposed for
the culture of hepatocytes and other mammalian
cells. This bioreactor consists of spiral-wound
membranes, and some devices include also a
layer of polypropylene hollow fiber membranes
for cell oxygenation (Flendrig et al. 1997). Bio-
reactors using multibore capillaries have been
developed in the last years for the culture of
human hepatocytes (De Bartolo et al. 2007a).
This device is composed of multibore membranes
of modified poly(ethersulfone) constituted of
seven compartments represented by seven capil-
laries arranged in one single fiber. The seven
compartments communicate through a porous
foamy support structure that is located in between
the capillaries. In this bioreactor human hepato-
cytes have been cultured inside the lumen of the
multibore fibers and lumen in the shell compart-
ment. In the last years membrane bioreactors
have been developed for the expansion and
transdifferentiation of stem cells to be used in
cell therapy and tissue engineering applications
(Salerno et al. 2013).
References
De Bartolo L, Salerno S, Giorno L, Morelli S, Barbieri G,
Curcio E, Rende M, Drioli E (2006a) Membrane bio-
reactor using pig hepatocytes for in vitro evaluation of
anti-inflammatory drugs. Catal Today 118:172–180
De Bartolo L, Salerno S, Morelli S, Giorno L, Rende M,
Memoli B, Procino A, Andreucci VE, Bader A, Drioli
E (2006b) Long-term maintenance of human hepato-
cyte in oxygen permeable membrane bioreactor. Bio-
materials 27(27):4794–4803
De Bartolo L, Morelli S, Rende M, Campana C, Salerno S,
Quintiero N, Drioli E (2007a) Human hepatocyte mor-
phology and functions in a multibore fiber bioreactor.
Macromol Biosci 7:671–680
De Bartolo L, Piscioneri A, Cotroneo G, Salerno S,
Tasselli F, Campana C, Morelli S, Rende M, Caroleo
MC, Bossio M, Drioli E (2007b) Human lymphocyte
PEEK-WC hollow fiber membrane bioreactor.
J Biotechnol 132:65–75
Demetriou AA, Whiting JF, Levenson AM et al (1986)
New method of hepatocyte transplantation and extra-
corporeal liver support. Ann Surg 204(3):259–270
Flendrig LM, La Soe JW, Joerning GGA et al (1997) In
vitro evaluation of a novel bioreactor based on an
integral oxygenator and a spirally wound nonwoven
Membrane Bioreactors for Cell Growth
polyester matrix for hepatocyte culture as small aggre-
gates. J Hepatol 26:1379–1392
Gerlach JC, Schnoy N, Smith MD, Neuhaus P (1994)
Hepatocyte culture between woven capillary net-
works: a microscopy study. Artif Organs 18:226–230
Giorno L, De Bartolo L, Drioli E (2011) Membrane bio-
reactors. In: Moo-Young M (ed) Comprehensive
3
biotechnology, 2nd edn, vol 2. Elsevier, Amsterdam/
Oxford/Walthaman pp 263–288.
Salerno S, Piscioneri A, Morelli S, Al-Fageeh MB,
Drioli E, De Bartolo L (2013) Membrane bioreactor
for expansion and differentiation of embryonic liver
cells. Ind Eng Chem Res 52(31):10387–10395
H
Hollow Fiber Membrane Bioreactor
for Cell Growth
Loredana De Bartolo
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
Hollow fiber membrane bioreactor consists of
hollow fiber membranes parallel-assembled in
an external shell, which is usually in the shape
of a cylinder. The fibers are potted in the shell,
thus creating a medium and a cell compartment
which are separated by the membranes. Hollow
fiber membranes of suitable MWCO separate
cells from the medium compartment allowing
the communication between the compartments
through the pores of fiber wall. Depending on
the pore sizes, the passage of nutrients, metabo-
lites, and catabolites occurs and cells are retained.
The principle of a hollow fiber bioreactor based
on hemodialyzer modules was first described by
Knazek (Knazek et al. 1972). Usually cells are
cultured in suspension or attached to the outer
surface of the membranes in the extracapillary
space. Culture medium containing nutrients
flows in the lumen of the fibers and diffuses out
through the pores of the fiber wall to the cells.
The metabolic species together with waste mole-
cules produced by cells permeates back into the
fibers and is removed from cell compartment
(Fig. 1).
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1191-1
As bioreactors, they are extensively used for
production of biochemicals and for the develop-
ment of bioartificial organs. Recently they found
applications in tissue engineering applications for
the development of tissue constructs, cell ther-
apy, and the expansion and transdifferentiation of
stem cells. Hollow fiber bioreactor offers several
advantages for the culture and growth of adherent
and suspension cells including: (i) an in vivo-like
microenvironment regarding nutrient supply and
metabolic waste removal as each fiber replicates
a blood capillary, (ii) high surface area to volume
ratio, (iii) cells can be grown to high density,
(iv) cells are protected from shear stress, and
(v) support of three-dimensional growth of cells
for the development of tissue-engineered con-
structs. Different types of polymers
(polyethersulfone, polysulfone, polyacryloni-
trile, modified polyetheretherketone, polyamide,
cellulose acetate, etc.), generally hydrophilic
polymers or with moderate wettability, are used
for the development of hollow fiber bioreactors in
order to favor the adhesion of cells or the
exchange of medium. Hydrophobic hollow fibers
(e.g., polypropylene) are included in some
devices for a separate oxygenation of cells
(Flendrig et al. 1997). A major drawback of the
hollow fiber bioreactors is represented by the
mass transfer resistance due to the membrane
because while it separates cells from the medium
compartment, it does reduce diffusion of nutri-
ents and oxygen to the cells. In addition, fouling
due to the adsorption of plasma proteins or the
2 Hollow Fiber Membrane Bioreactor for Cell Growth
a b
Hollow fiber
membranes
Culture
cells medium flow
Hollow Fiber Membrane Bioreactor for Cell Growth,
Fig. 1 Schematic diagram of hollow fiber membrane
bioreactor used for cell culture and growth: (a) cells are
development of biofilms further increases the
resistance to mass transport. In the membrane
bioreactors, mass transfer is determined by the
MWCO or pore diameter of membrane and
occurs by diffusion and/or convection in response
to existing transmembrane concentration or pres-
sure gradients. Most of the bioreactors use mem-
branes with MWCO ranging from 70 to 100 kDa
that allow the transport of small molecules that
are fed or produced by cells but exclude proteins
with high MW such as immunoglobulins and
cells. These membranes provide
immunoprotection, which is important when the
devices are used in the organ replacement therapy
in order to avoid the passage of immunocompe-
tent species present in the patient’s blood. Other
bioreactors use microporous membranes with a
large pore diameter (0.2 mm) that permit the free
passage of proteins, toxins, and clotting factors,
but they exclude the passage of cells. The advan-
tage of using a membrane with large pore diam-
eter is that it increases the fluid convection
improving the mass transfer conditions. Several
hollow fiber membrane bioreactors have been
developed for the culture of cells that grow in
adhesion and/or in suspension. Different config-
urations have been investigated for the culture
and growth of primary cells (e.g., lymphocytes,
Culture medium
flow
Hollow fiber
membranes cells
cultured in the extracapillary space, and the medium flows
in the lumen of fibers; (b) cells are cultured in the lumen of
fiber, and the medium flows in the extracapillary space
hepatocytes, pancreatic islets, neurons, osteo-
blasts, fibroblasts), cell lines, progenitor cells,
and stem cells (De Bartolo and Bader 2013).
Usually cells are cultured in adhesion or suspen-
sion outside the fibers, and the medium flows in
the lumen of fibers (De Bartolo et al. 2007a). In
other bioreactors cells are cultured inside the
lumen of fibers, and the medium flows in the
shell of fiber (Fig. 1) (Nyberg et al. 1994). More
complex devices have been explored for the cul-
ture of hepatocytes, stem cells, and progenitor
cells that include the use of different fibers.
A bioreactor with four interwoven independent
capillary membrane systems that serve different
functions has been developed by Gerlach
et al. (1994). The cells are cultured on the outer
surface and among the capillaries. Each fiber type
exhibits a different function: silastic membranes
for oxygen supply and removal of carbon diox-
ide, polyamide fiber for the plasma inflow,
polyethersulfone fiber for the plasma outflow,
and hydrophilic polypropylene membranes for
the sinusoidal endothelial coculture. A crossed
hollow fiber membrane bioreactor was developed
as an in vitro liver tissue model to study disease,
drugs, and therapeutic molecules alternative to
animal experimentation (De Bartolo
et al. 2009). The bioreactor consists of two
Hollow Fiber Membrane Bioreactor for Cell Growth
types of fibers with different MWCO and physi-
cochemical properties cross-assembled in alter-
nating manner: modified polyetheretherketone
and polyethersulfone used for the medium inflow
and outflow, respectively. The combination of
these two fiber sets produces an extracapillary
network for the adhesion of cells and a high
mass exchange through the crossflow of culture
medium. This bioreactor has been developed for
the culture of human hepatocytes and expansion
and differentiation of liver progenitor cells.
Multibore fiber membrane bioreactor consisting
of modified polyethersulfone fiber has been
developed for the long-term maintenance of
human hepatocytes. Each fiber is composed of
seven compartments that communicate through
a porous foamy support structure that is located in
between the capillaries. Cells have been cultured
inside the lumen of the multibore fibers and
lumen in the shell compartment (De Bartolo
et al. 2007b).
Hollow fiber membrane bioreactors have a
great potential for the expansion and differentia-
tion of embryonic and adult stem cells, which
have ability to either self-renew or differentiate
into multiple cell lineages. These properties make
stem cells attractive as a cell source for cell
therapies, tissue engineering, and model systems
for drug screening. Depending on the application,
hollow fiber membrane bioreactors can be used
for the production of expanded stem cells with
uniform properties and/or for a controlled and
reproducible differentiation into selected mature
cell types (Salerno et al. 2013). They are partic-
ularly advantageous with respect to the other
culture systems because of their capacity to
ensure a more homogeneous environment, to
3
monitor key culture parameters (pH, temperature,
oxygen, etc.), and to guide the transdiffer-
entiation of cells by engineering membranes
with targeted properties.
References
De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy: state of art and vision for the future. CRC
Press, Boca Raton
De Bartolo L, Piscioneri A, Cotroneo G, Salerno S,
Tasselli F, Campana C, Morelli S, Rende M, Caroleo
MC, Bossio M, Drioli E (2007a) Human lymphocyte
PEEK-WC hollow fiber membrane bioreactor.
J Biotechnol 132:65–75
De Bartolo L, Morelli S, Rende M, Campana C, Salerno S,
Quintiero N, Drioli E (2007b) Human hepatocyte mor-
phology and functions in a multibore fiber bioreactor.
Macromol Biosci 7:671–680
De Bartolo L, Salerno S, Curcio E, Piscioneri A, Rende M,
Morelli S, Tasselli F, Bader A, Drioli E (2009) Human
hepatocyte functions in a crossed hollow fiber mem-
brane bioreactor. Biomaterials 30:2531–2543
Flendrig LM, La Soe JW, Joerning GGA et al (1997) In
vitro evaluation of a novel bioreactor based on an
integral oxygenator and a spirally wound nonwoven
polyestermatrix for hepatocyte culture as small aggre-
gates. J Hepatol 26:1379–1392
Gerlach JC, Schnoy N, Smith MD, Neuhaus P (1994)
Hepatocyte culture between woven capillary net-
works: a microscopy study. Artif Organs 18:226–230
Knazek RA, Gullino PM, Kohler PO, Dedrick RL
(1972) Cell culture on artificial capillaries: an
approach to tissue growth in vitro. Science 178:65–66
Nyberg SL, Remmel RP, Mann HJ et al (1994) Primary
outperform hep G2 cells as source of biotransforma-
tion functions in a bioartificial liver. Ann Surg
220:59–67
Salerno S, Piscioneri A, Morelli S, Al-Fageeh MB,
Drioli E, De Bartolo L (2013) Membrane bioreactor
for expansion and differentiation of embryonic liver
cells. Ind Eng Chem Res 52(31):10387–10395
A
Acute Kidney Injury (AKI)
Loredana De Bartolo
National Research Council of Italy, Institute on
Membrane Technology, CNR-ITM, Rende (CS),
Italy
Synonyms
Membrane artificial organs
Acute kidney injury (AKI) or acute renal fail-
ure indicates kidney injury from less severe forms
of injury to more advanced injury when acute
kidney failure may require renal replacement
therapy. Acute kidney failure occurs when kid-
neys loss their functions that include excretion of
wastes, acid-base homeostasis, osmolality regu-
lation, blood pressure regulation, and hormone
secretion (Waikar et al. 2008). When kidneys
lose their filtering ability, dangerous levels of
wastes may accumulate, resulting in an increas-
ingly toxic blood stream and fluid overload.
Acute kidney failure requires replacement ther-
apy that includes: hemodialysis, peritoneal dial-
ysis, hemofiltration, hemodiafiltration, and renal
transplantation. Dialysis treatment involves the
diffusion of solutes through a semipermeable
membrane driven by a concentration gradient.
For the treatment of uremic patients, an artificial
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1192-1
membrane (hemodialysis) or a biological mem-
brane (peritoneal dialysis) can be utilized. The
membrane-based treatments involve pumping
patient’s blood from the body through a mem-
brane device that acts as an artificial kidney by
separating waste products including toxins and
excess water from the blood. The therapies for
the treatment of patients with acute renal failure
are not limited to dialysis but rather include other
modalities. Hemofiltration has been developed
to overcome the reduced efficacy of diffusion
for molecules with middle and large MW. In
this process the driving force is a hydrostatic
pressure gradient that induces a large flux of
water across the membrane from blood side to
the filtrate side. As a result the rate of solute
removal is proportional to the applied pressure.
Hemodiafiltration is the combination of hemodi-
alysis and hemofiltration processes. The high rate
of ultrafiltration is combined with the efficient
diffusion overcoming the disadvantages related
to each single treatment.
References
Waikar SS, Liu KD, Chertow GM (2008) Diagnosis,
epidemiology and outcomes of acute kidney Injury.
Clin J Am Soc Nephrol 3:3844–3861
A
Artificial Lung
Loredana De Bartolo and Sabrina Morelli
National Research Council of Italy, Institute on
Membrane Technology, CNR-ITM, Rende(CS),
Italy
The artificial lung is a medical device used to take
over or supplement the function of the lung which
is to oxygenate the blood and remove carbon
dioxide.
Such a device can replace entirely the pulmo-
nary gas exchange or assist the deficient gas
transfer capacity of the natural organ, either tem-
porarily, with the hope that the healing process
will eventually repair the diseased organ, or per-
manently, when irreversible lung damage leaves
the patient permanently disabled.
Artificial lung can be used as a bridge to lung
transplantation, as a support device immediately
post-lung transplant, and as a rescue and/or sup-
plement to mechanical ventilation during the
treatment of severe respiratory failure (Diaz-
Guzman et al. 2013; Javidfar and Bacchetta
2012).
Current artificial lungs are also known as
blood oxygenators and are modules composed
of bundles of hollow fiber membranes designed
to bring blood and gas phases in intimate contact
separated by only the thin walls of the hollow
fibers.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1195-1
Membrane oxygenators can be used in two
principal modes: to imitate the function of the
lungs in cardiopulmonary bypass (CPB) and to
oxygenate blood in longer-term life support,
termed extracorporeal membrane oxygenation
(ECMO). A membrane oxygenator consists of a
thin gas permeable membrane separating the
blood and gas flows in the CPB circuit; oxygen
diffuses from the gas side into the blood, and
carbon dioxide diffuses from the blood into the
gas for disposal.
Preliminary efforts to design, fabricate, and
test membrane artificial lungs have been reported
since the 1950s. The early artificial lungs used
relatively impermeable polyethylene or Teflon
homogeneous membranes, and when more highly
permeable silicone rubber membranes were
introduced in the 1960s (and as hollow fibers in
1971), the membrane oxygenator became com-
mercially successful. The introduction of micro-
porous hollow fibers with very low resistance to
mass transfer revolutionized the design of mem-
brane modules, as the limiting factor to oxygen-
ator performance became the blood resistance
(Martin and Zwischenberger 2013).
Current designs of oxygenator typically use an
extraluminal flow regime, where the blood flows
outside the gas-filled hollow fibers, for short-term
life support, while only the homogeneous mem-
branes are approved for long-term use.
The key design considerations in blood oxy-
genators include minimizing the resistance to
blood flow, reducing the priming volume,
2 Artificial Lung
ensuring easy debubbling at setup, and minimiz-
ing blood activation and thrombogenicity.
The fabrication or wrapping of the fiber bun-
dle in a blood oxygenator can be important as the
geometry obtained impacts diffusional boundary
layers, secondary flows, and gas exchange
efficiency.
Looking ahead, current challenges in
bioartificial lung engineering include creation of
ideal scaffold materials, differentiation and
expansion of lung-specific cell populations, and
full maturation of engineered constructs to pro-
vide graft longevity after implantation in vivo
(Sond and Ott 2012).
References
Diaz-Guzman E, Hoopes CW, Zwischenberger JB
(2013) The evolution of extracorporeal life support as
a bridge to lung transplantation. ASAIO J 59:3–10
Javidfar J, Bacchetta M (2012) Bridge to lung transplan-
tation with extracorporeal membrane oxygenation
support. Curr Opin Organ Transplant 17:496–502
Martin JT, Zwischenberger JB (2013) Artificial lung and
novel devices for respiratory support. Semin Thorac
Cardiovasc Surg 25:70–75
Song JJ, Ott HC (2012) Bioartificial lung engineering. Am
J Transplant 12:283–288
M
Membrane Biomaterial
Loredana De Bartolo
Institute on Membrane Technology, National
Research Council of Italy, Rende (CS), Italy
Membrane biomaterial is any material consti-
tuted of membrane that is in contact with biolog-
ical fluids, organs, tissues, and cells (Williams
2009). Membranes are used as components of
medical devices and implants, drug delivery sys-
tems, diagnostic assays, and bioreactor and
bioseparation processes. They are employed in
the replacement therapy for acute and chronic
organ failure and in the management of immuno-
logical disease as well as in the tissue engineering
for the realization of tissue-engineered constructs
and defined models supporting investigations on
cell function, tissue development, and drug test-
ing. In many clinical therapeutic blood processes
are used membrane devices for the removal of
endogenous or exogenous toxins from blood
(hemodialysis, hemofiltration, hemodiafiltration,
plasmapheresis) or for the gas exchange with
blood (blood oxygenation) (De Bartolo and
Drioli 1998). Membranes of suitable molecular
weight cutoff are used in bioartificial organs (e.g.,
the pancreas, liver) for compartmentalization of
cells and as selective barriers to prevent immune
system components from getting into contact
with the implant while allowing nutrients and
metabolites to permeate freely to and from cells.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1197-2
Membrane-based biomaterials can be realized
with different properties on the basis of the func-
tions to be performed. Membranes can be porous
or dense, hydrophilic or hydrophobic, natural or
synthetic, biodegradable or not biodegradable,
and stiff or elastic. However, all membranes
properties play an important role in the interac-
tions with cells or biological fluids. Physico-
chemical properties, morphology, roughness,
permeability, and mechanical characteristics
affect the biological response and consequen-
tially the performance of the membrane.
As a result, the biocompatibility and
cytocompatibility of the membrane biomaterial
are dependent on its properties related to the
application in cells, tissues, organs, and blood.
To meet the needs of the biomedical require-
ments, membranes have to be compatible with
biological systems performing their function with
an appropriate host response (Ratner et al. 2012).
The interactions may involve, for example, plate-
let aggregation and blood coagulation in the case
of blood-contacting devices, immune response,
and foreign body reactions when the membrane
biomaterials or devices are implanted in the body.
The interactions with cells may involve a struc-
tural and functional connection or may lead to the
cell death and nonviable tissue-engineered
constructs.
The most common synthetic membranes used
in biomedical applications are made of cellulose
acetate (CA), nitrocellulose (CN), and cellulose
esters (CE), polysulfone (PS), polyethersulfone
2 Membrane Biomaterial
(PES), polyacrylonitrile (PAN), polyamide (PA),
polyimide (PI), polyethylene (PE), polypropyl-
ene (PP), polytetrafluoroethylene (PTFE),
polyvinylidene fluoride (PVDF), polyarylether-
sulfones (PAES), polyvinyl chloride (PVC), eth-
ylene vinyl alcohol (EVAL), polyethyleneimine
(PEI), and polymethyl methacrylate (PMMA)
(Baker 2004). These membranes are used extra-
corporeally connected to the patient’s body
through blood circulation as, for example, in
hemodialysis, hemodiafiltration, blood oxygena-
tion, and bioartificial organs.
In tissue engineering or in implants are used
mainly biodegradable membranes that undergo
hydrolytic or enzymatic degradation. These
membranes are mainly made of polyglycolide or
poly(glycolic acid) (PGA), polylactide (PLA),
poly(lactic-co-glycolic acid) (PLGA),
polycaprolactone (PCL), polycarbonate (PC),
polyurethanes (PU), polyphosphazenes
(PPHOS), polyamide (PA), chitosan (CHT),
hyaluronic acid (HA), collagen, and poly
(p-dioxanone) (PDO). Biodegradable membrane
biomaterials can be implanted in situ into the
body. An example is the commercial collagen
resorbable membrane from highly purified type
I collagen that is used for repairing tears and
wound healing. Specifically, membrane biomate-
rials that are biodegradable provide the
significant advantage of being able to be broken
down and removed after they have served their
function (De Bartolo and Bader 2013).
Responsive membranes are used in the area of
cell sheet engineering for the in vitro tissue
reconstruction. These membranes allow the
adhesion and proliferation of cells at a tempera-
ture above the lower critical solution temperature
of the grafted polymer (a state where in the sur-
face is hydrophobic) and the detachment of cells
when the temperature is lowered below the lower
critical solution, because of spontaneous hydra-
tion of the grafted polymer chains.
References
Baker RW (2004) Membrane technology and applica-
tions. Wiley, Chichester
De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy. CRC Press, Boca Raton
De Bartolo L, Drioli E (1998) Membranes in artificial
organs. In: Haris PI, Chapman D (eds) Biomedical
and health research, vol 16, New biomedical
materials – basic and applied studies. Ios Press,
Amsterdam
Ratner BD, Hoffman AS, Schoen FJ, Lemons JE
(2012) Biomaterials science: an introduction to mate-
rials in medicine, 3rd edn. Elsevier, Amsterdam
Williams DF (2009) On the nature of biomaterials. Bio-
materials 30:5897–5909
B
Biomaterial
Loredana De Bartolo
Institute on Membrane Technology, CNR-ITM,
National Research Council of Italy, Rende (CS),
Italy
A biomaterial is any material in contact with a
biological system. The first nonbiological mate-
rial entered in contact with the human body seem
to date back to the prehistory 9000 years old with
the “Kennewick Man,” who had a spearpoint
embedded in his hip. This spearpoint was the
first foreign material implant, which was “toler-
ated” by the body (Ratner et al. 2012). Although
the use of biomaterials dates back to the ancient
time, the study of biomaterials is about
60 years old.
Biomaterials can be classified on the basis of
its (i) source in natural or synthetic materials if
they are from nature or synthesized in laboratory,
respectively; (ii) chemical nature in organic, inor-
ganic, and composites; and (iii) degradation
properties in biodegradable and nonbiode-
gradable. They can be used in biomedical devices
for the replacement of an organ function or
implanted into the body for the replacement of
tissue, organ, or body parts. Biomaterials are also
used every day in dental applications, surgery,
and drug delivery (Williams 2009).
Natural-based polymers offer the advantage of
being similar to extracellular matrix components,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1198-1
and they have binding sites for cells and adhesion
molecules so that they usually avoid immunolog-
ical reactions and toxicity. Their principal disad-
vantage lies in the development of reproducible
production methods, because their structural
complexity often makes modification and purifi-
cation difficult. Additionally, significant batch-
to-batch variations occur because of their “bio
preparation” in living organism (plants, crusta-
ceans) while their mechanical properties are also
limited. Chemical modification and cross-linking
are common methods for altering mechanical
properties such as elasticity and tensile strength
of natural materials which are often not appropri-
ate for dynamic physiologic environments. The
most frequently used natural biomaterials are the
collagen derived from connective tissues of ani-
mals, fibrinogen obtained from plasma, and other
proteins of ECM. Among natural biomaterials,
polysaccharides are also frequently used. These
natural polymers include agarose, hyaluronan,
chitosan, and alginate. They are derived from
plant (seaweed) or animal origin and are used as
hydrogels to support wound healing and also cell
growth and differentiation (Mano et al. 2007).
Synthetic biomaterials different from natural
materials can be synthesized to give various prop-
erties and have high reproducibility, availability,
lot-to-lot uniformity, and constant quality. They
have a well-known structure and properties so
that mechanical properties, degradation rate,
shape, and composition can be adjusted to the
specific application. However, the
2 Biomaterial
biocompatibility and immune reactions are the
big concern because they often lack sites for cell
adhesion therefore their interactions with cells
could be questionable. Synthetic biomaterials
include biodegradable polymers as poly(lactic-
co-glycolic acid) (PLGA), poly-lactic acid
(PLA), poly-caprolactone (PCL), poly(ethylene
glycol) (PEG), etc. and synthetic polymers (e.g.,
polyurethane, polyetheretherketone, polyethyl-
ene, polyvinylidene fluoride, polyvinyl alcohol,
polymethyl methacrylate, polydioxanone, etc.).
For example, PLGA is one of the most frequently
used biomaterials applied in neural, bone, and
cartilage tissue engineering for its degradation
rate that can be modulated. PLA is fast
reabsorbed and widely used in tissue engineering
applications alone or blended with other poly-
mers. PCL is a very good elastic biodegradable
polymer that finds several applications in tissue
engineering. PEG that is used in pharmaceutical
technology to modulate the degradation and
absorption of bioactive proteins is also frequently
used in bone, cartilage, nerve, liver, and vascular
tissue engineering. Peptide-based biomaterials
(e.g., the tripeptide Arg-Gly-Asp, RGD)
consisting of short amino acid sequences exhibit
cell-binding sequences found in the extracellular
matrix natural proteins. Ceramic-based biomate-
rials that are totally or partly inorganic are
applied in bone tissue engineering. Mostly they
are shaped with heat-forming porous, brittle
materials. Hydroxyapatite and tricalcium phos-
phate owing to their structural similarity to the
mineral phase of bone are used alone or in com-
bination with organic polymers like PLA, PLGA,
collagen, or chitosan in the bone replacement or
regeneration (De Bartolo and Bader 2013;
Morelli et al. 2015). Metals like alumina and
titanium alloys that are bioinert materials are
used as implant materials where implants are
subjected to extreme mechanical load, like artic-
ular prostheses, dental implants, or heart valves.
References
De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy. CRC Press, Boca Raton/New York/Oxon
Mano JF, Silva GA, Azevedo HS, Malafaya PB, Sousa
RA, Silva SS, Boesel LF, Oliveira JM, Santos TC,
Marques AP, Neves NM, Reis RL (2007) Natural ori-
gin biodegradable systems in tissue engineering and
regenerative medicine: present status and some mov-
ing trends. J R Soc Interface 4:999–1030
Morelli S, Salerno S, Holopainen J, Ritala M, De Bartolo
L (2015) Osteogenic and osteoclastogenic differentia-
tion in polylactic acid-nanohydroxyapatite fiber scaf-
folds. J Biotechnol 204: 53–62
Ratner BD, Hoffman AS, Schoen FJ, Lemons JE
(2012) Biomaterials science: an introduction to mate-
rials in medicine, 3rd edn. Elsevier, Amsterdam
Williams DF (2009) On the nature of biomaterials. Bio-
materials 30:5897–5909
C
Cell Culture
Antonietta Messina1 and Loredana De Bartolo2
1
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
2
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende (CS),
Italy
“Cell culture” refers to a homogeneous group of
cells able to grow and proliferate in controlled
artificial environments for many generations.
Generally derived from animal and plant, these
eukaryotic cells are maintained in sterile vessels
where a culture medium reproduces the nutri-
tional and chemical-physical conditions of the
native environment.
Some historiographical notes. The cell culture
technique is only relatively a new science.
Though the 1950s are considered the “cell culture
years,” actually, already in the nineteenth cen-
tury, S. Ringer demonstrated that a beating ani-
mal heart can be maintained in salt solutions.
First attempts of cell cultures are dated 1885,
when W. Roux observed for a week embryonic
chick cells using only a saline solution as
medium. Therefore, it is in 1907 that the father
of the cell culture technique R. Granville Harri-
son published experimental results on the growth
of frog nerve fibers in a lymph clot held by the
hanging drop method. Benefiting from the strict
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1199-1
aseptic culture conditions introduced by
A. Carrel, the nobel prize for medicine and phys-
iology in 1992, this experimentation carried out
for several weeks, leaded the way to the develop-
ment of an enormous variety of cell culture tech-
niques and to the progresses of the sterile
conditions and the employ of culture media
more and more completed and balanced in com-
position (Karp 2010). Cell culture setup. The
specific requirements for a cell culture depend
mainly on the final application the work is fated;
therefore, there are some specific instruments and
parameters that must be used and observed. To
the basic equipment made of cell culture hood,
incubator, water bath, centrifuge, refrigerator and
freezer, cell counter, microscopes, liquid nitro-
gen, cryostorage container, and sterilizer, other
additional supplies are requested, as vessels,
reagents, media, pipettes, and so on. Moreover,
either the working areas or the operators must
ensure the aseptic conditions essential for
avoiding biological and chemical contamina-
tions. Contaminants like bacteria, yeasts, molds,
viruses, and mycoplasma are not easy to eradicate
and may waste the experimentations (Alberts
et al. 2002).
In a living organism, the cells survive due to
the vascular system that brings the nutrients and
removes waste product derived from the metab-
olism. In vitro, this function is entrusted to the
culture medium. Classified in balanced salt solu-
tions (PBS, Hanks’ BSS, DPBS), basic media
(MEM, DMEM), completed media (RPMI
2 Cell Culture
1640, Iscove’s DMEM, Leibovitz’s L-15), and
serum-free media (HAM F10, HAM F12), this
specific isotonic solution is constituted by ele-
mentary substances and nutrients, as glucose,
salts, amino acids, growth factors, carbohydrates,
vitamins, lipids, and proteins, and a supplement
of antibiotics is also requested for the inhibition
of the bacterial growth (penicillin 10,000 ug/ml;
streptomycin 10,000 U/ml). A vitally important
supplement of the medium is also the animal
serum (FBS, NCS, HF). The serum, used in con-
centration of 5–20 %, is the main source of
growth and adhesion factors (PDGF, EGF, IGF),
hormones, lipids, and energetic sources. More-
over, it regulates cell membrane permeability and
protects the cells from mechanical and chemical
stresses, and its buffer power balances the pH
value at 7–7.7. All the cell types need proper
culture medium and supplements that must be
refreshed regularly in aseptic condition to guar-
antee their survival (Alberts et al. 2002; Karp
2010).
Culture conditions. In artificial systems, the
cell is traditionally cultured in plastic or glass
vessels purposely made with different shapes
and properties (flasks, Petri dishes, bottles).
They are put in incubators where a temperature
of 37  C and a controlled atmosphere (95 %
air – 5 % CO2) are set in order to mimic the native
environment. In the field of tissue engineering
and bioartificial organs, isolated cells are cultured
on several types of biomaterials including poly-
meric and composite membranes, extracellular
matrix components, and batch and dynamic sys-
tems. Depending on the cell types, there are two
basic systems for growing cells in culture: the
adherent culture system and the suspension sys-
tem. The adherent culture system has been spe-
cifically developed for the growth of anchorage-
dependent cells that derive from solid tissues and
require to adhere to a substrate in order to survive
and proliferate. On the basis of their morphology
(shape and appearance) or on their functional
characteristics, these cells are divided into two
different typologies: the epithelial-like cells that
appear flattened and polygonal in shape and the
fibroblast-like cells, elongated and bipolar. The
suspension culture, on the contrary, refers to the
culture of anchorage-independent cells, as the
blood or lymphatic cells that survive floating in
suspension and assuming a spherical shape
defined lymphoblast-like (Alberts et al. 2002;
Karp 2010).
Isolation of cells. In order to set up a culture,
the early stage is to acquire an already established
cell line or strain or to isolate the desired cells
from a tissue fragment. When cells are immedi-
ately placed in a suitable culture environment
after mechanical removal from a tissue, the
so-called primary cultures are defined. To
degrade the extracellular matrix responsible of
the cell layer unity and to obtain a cell suspen-
sion, the tissue is enzymatically treated
(collagenase, trypsin, protease), and the highly
heterogeneous cell population is cultured in spe-
cific media able to separate single cell types
interacting with the cytoplasmatic molecules
expressed onto the plasmatic membranes
(antigens). Despite having a finite life span due
to the phenomenon of senescence, these cells
proliferate until they occupy all the substrate
available, reaching the confluence. At this stage,
in order to avoid the degeneration and their death,
the cells are enzymatically removed (e.g., tryp-
sin, papain, collagenase in combination with
EDTA) and transferred into a fresh growth
medium in a new vessel (Hayflick 1998; Karp
2010). This procedure is called subculturing
(passaging or splitting) and transforms primary
cultures in “cell lines” or subclones, where the
cells with the highest growth capacity predomi-
nate resulting in a degree of genotypic and phe-
notypic uniformity in the population. Moreover,
when a subpopulation is further selected, this cell
line becomes “cell strains” able to acquire addi-
tional genetic changes. The survival ability of
normal cell cultures lasts only for a limited num-
ber of passages; however, some cells can become
immortal due to a spontaneous or a viral-/
chemical-induced modification. Acquiring the
ability to proliferate indefinitely like the tumor
cells, the characteristics of these transformed
“continuous cell lines” are (i) the fast growth,
(ii) the ability to grow up to higher cell density,
(iii) reduced serum and anchorage dependence
that allow the culture in suspension more than in
Cell Culture
adherent vessels, (iv) different in phenotypes
from native tissue, and (v) stop expressing
tissue-specific genes (Hayflick 1998; Alberts
et al. 2002; Karp 2010). In order to preserve cell
characteristic from further transformation or con-
taminations and to ensure the reproducibility of
experimentation in time, a surplus of cells,
derived from subculturing, can be treated with a
cryoprotective agent (DMSO or glycerol) and
stored at a temperature below 130  C in liquid
nitrogen directly in the laboratories. Working
stocks of cell lines are reposted in many cryo-
preservation banks including the American Type
Culture Collection (ATCC) and the European
Collection of Cell Cultures (ECACC) (Alberts
et al. 2002).
The cell culture technology opens up new
perspectives in many fields, as the manufacturing
of vaccines and other products of biotechnology,
and above all they became the turning point for
the development of the tissue engineering, sci-
ence entrusted of the study and production of
artificial tissues and the regeneration of tissue
3
and organs, either in 2D or 3D systems. Nowa-
days, the cell cultures are the “model system” and
the perfect instrument for many applications:
(i) production of pharmacological substances
(antibodies, vaccines, growth factors, etc.),
(ii) toxicity testing of drug effects, (iii) study of
basic cell physiology, (iv) cancer research,
(v) genetic engineering, (vi) tissue engineering
and regenerative medicine, and (vii) gene
therapy.
References
Alberts B, Johnson A, Lewis J, et al (2002) Table 8-3:
some landmarks in the development of tissue and cell
culture. In: Molecular biology of the cell, 4th edn.
Garland Science, New York
Hayflick L (1998) A brief history of the mortality and
immortality of cultured cells. Keio J Med
47(3):174–182
Karp GC (2010) Cell and molecular biology: concepts and
experiments, 6th edn. Wiley, New York
U
Ultrafiltration (UF)
Herb Lutz
EMD Millipore Corporation, Playa del Rey, CA,
USA
Ultrafiltration (UF or UF/DF) is a unit operation
that separates large solutes from small solutes and
solvents (see chapter “▶ UF Application”).
Larger pore membranes are referred to as
microfiltration (MF), while smaller pore filters
are referred to as reverse osmosis (RO). There is
some nomenclature confusion as membrane sci-
entists refer to a loose RO charged membrane as a
nanofilter, while bioprocessors refer to a loose UF
membrane as a nanofilter that removes
nanometer-sized viruses.
UF employs thin porous solid UF membranes
as either flat sheets or tubes (see chapter “▶ UF
Membrane”). These perform separations by
retaining and passing solutes primarily based on
their size and secondarily based on solute-surface
interaction by charge or other fields (see chapter
“▶ UF Transport”). Pressures of 0.2–1.0 MPa
drive liquid solvents (primarily water) through
the membrane. Since retained solid buildup can
cause the solute flow to rapidly decline, most UF
systems are run in tangential flow filtration (TFF)
mode with a significant velocity tangent to the
membrane surface. This enhances back transport
away from the surface and leads to steady-state
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1206-2
operation at reasonably economical solvent
fluxes (volumetric flow per unit area).
UF membranes are fabricated into modules
that allow for convenient assembly and operation
in modular systems. Commercial module formats
include hollow fiber bundles, tubular assemblies,
spiral wound assemblies, and cassettes. Stirred
cell devices are commonly used for research
since they require little volume, operate at uni-
form conditions across their surface, and are well
characterized.
Typical UF process operating steps include:
assembly, water flush, integrity testing, buffer
flush, processing, recovery flush, cleaning, sani-
tization, disassembly, and storage. Assembly of
modules into a holder is required for a new oper-
ation or when the filters have reached expiration
and need to be replaced. Water flushing thor-
oughly wets the membrane and removes extract-
ables and antimicrobial or humectant storage
agents. Integrity testing involves measuring
downstream airflow with pressurized air
upstream. Defects or installation leaks will show
up as high air flows. Buffer flush conditions the
membrane to limit product denaturation and
membrane fouling. Processing may follow con-
centration or diafiltration in continuous or batch
operating modes (see chapter “▶ UF Modeling”).
Diafiltration involves adding a new buffer that
displaces the old buffer leaving in the permeate
while retaining the desired solute. Recovering
high value product from batch systems involves
a low pressure air blowdown or reverse buffer
2 Ultrafiltration (UF)
flush through the modules. System cleaning
involves thoroughly flushing out remaining prod-
uct and recirculating a cleaning solution at the
desired time, temperature, and concentration.
Multiple fouling agents may require cleaning
steps with multiple cleaning agents (e.g., NaOH
for proteins, acid for precipitated salts). Cleaning
effectiveness is measured by the restoration of
water permeability. Sanitization involves
recirculating a sanitizing solution at the desired
time, temperature, and concentration. This is fre-
quently done as a separate additional step even if
the chemical is the same as for cleaning. The
rationale is to ensure that no protective biofilm
is present that would prevent sanitization from
being effective. At the end of a production cam-
paign, modules can be stored in a liquid storage
solution. Modules at the end of their life are
discarded. Lifetimes can be set by number of
uses, age, or process performance such as perme-
ability, retention, integrity, and feed channel
pressure drop.
Key UF membrane properties include reten-
tion capability, solvent permeability, chemical
compatibility, mechanical strength for module
fabrication and repeated use, consistency, and
cost. UF membranes come with a nominal molec-
ular weight limit (NMWL) rating of
1.0–5,000.0 KDa. The smaller rating means a
tighter filter able to retain a smaller solute with
a lower molecular weight. While these ratings are
convenient for testing and rough selection, solute
retention is based on effective solute dimensions
and not on molecular weight. Nonspherical sol-
utes will orient themselves under shear so that
their major axis is parallel to the pores. Linear
chain dextrans and DNA show a higher passage
than globular proteins of the same molecular
weight. The effective solute radius can increase
more than four times as a result of surface charge.
Ratings are not standardized among vendors and
depend on the marker solute selected (e.g., pro-
tein, dextran in a particular buffer) and the level
of retention selected for the marker solute (e.g.,
90 %). Retention is also affected by fouling due to
adsorbed components and polarized solutes on
the membrane surface. A rule of thumb for
selecting membrane NMWL is to take 0.2–0.3
of the MW of the solute that is to be retained by
the membrane. This should be taken as a rough
guide to select membranes for testing.
Selected membrane module manufacturers in
2012 include: EMD Millipore (Billerica, MA,
USA), Pall (Port Washington, NY, USA), Sarto-
rius (Germany), Asahi Kasei (Japan), GE Energy
(Raytown, MO, USA), Siemens (Warrendale,
PA, USA), TriSep (Goleta, CA, USA), Aquatech
(Canonsburg, PA, USA), Degremont Technolo-
gies (Richmond, VA, USA), Spintek (Los
Alamitos, CA, USA), Koch Membrane Systems
(Wilmington, MA, USA), Berghof (M€uhlhausen,
Germany), Daicel (Tokyo, Japan), DSS
(Silkeborg, Denmark), Matrix (Oceanside, CA,
USA), and Nitto Denko Hydranautics
(Oceanside, CA, USA).
References
Ho WS, Sirkar K (1992) Membrane Handbook, Van
Nostrand Reinhold, NY
Lutz H (2008) Membrane Separation Procsses in Perry’s
Chemical Engineer’s Handbook, 8th ed., McGraw-
Hill, NY
Lutz H (2015) Ultrafiltration for Bioprocessing,
Woodhead Publishing, Cambridge UK
Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
filtration, Marcel Dekker, NY
U
Ultrafiltration Applications
Herb Lutz
EMD Millipore Corporation, Playa del Rey, CA,
USA
UF membranes perform separations based on
solute size. They have retention ratings of
1–5,000 K for roughly spherical solutes and can
retain solutes of 10–1,000 Å or larger in diameter
(roughly 300–1,000 KDa) such as colloids, large
molecules, and nanoparticles. Smaller solutes
and solvents pass through the ultrafilter. UF
membranes retain smaller solutes than
microfiltration membranes and larger solutes
than reverse osmosis membranes.
Most commercial operations are run as tan-
gential flow filtration (TFF), but dilute solutions
such as water treatment or small-scale sample
preparation are run as normal flow filtration
(NFF). Virus-retaining filters, sometimes referred
to as nanofilters, are on the most open end of UF
and can be run as NFF or TFF. The first large
commercial application of UF was paint
recycling, followed by dairy whey recovery in
the mid-1970s. Applications can be described as
clarification of a permeate product (e.g., water
purification), concentration of a retentate product
(e.g., paint, dairy, and pharmaceuticals), or solute
purification (e.g., virus/protein separation and
buffer exchange). UF applications are enabled
by low temperature and low-cost operation,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1207-2
particularly with membrane reuse. UF processes
can vary significantly between applications due
to differing requirements and relative costs.
Automobiles used to rust due to paint
nonuniformity. Electrodeposition of cationic
paint resin on automobiles (connected to the cath-
ode) was developed to provide a uniform, defect-
free coating with high corrosion resistance. This
process deposits about 50 % excess paint on the
surface that must be washed off. UF is used to
retain and recover the washed paint to maintain a
high paint concentration in the paint bath. The
paint-free permeate is used for washing. Paint
recovery to reduce losses and lower system
costs makes the process economical.
During cheese making, the coagulated milk or
curd is used to make cheese, while the superna-
tant whey is a waste product rich in salts, pro-
teins, and lactose. UF retains whey proteins while
passing water, sugars, and salts. The retentate
proteins are used as soft cheese products and
animal feed supplements. The MMV process
concentrates the milk by UF after centrifugation
removes the cream and before coagulation to
improve yields and reduce disposal costs.
UF is used in biopharmaceutical purification
to retain proteins, viruses, bacterial vaccines, and
nucleic acids. Water and buffers pass through the
membrane. Initial UF concentration of clarified
fluids or lysates reduces process volumes to
decrease subsequent column sizes and increase
binding. Diafiltration UF changes buffer condi-
tions (for loading on to columns) and to
 Ultrafiltration Applications

Ultrafiltration Applications, Table 1 Ultrafiltration applications

Paint Whey Biopharmaceutical Water Juice
Application recovery processing purification treatment processing
Membrane PES PES Cellulose, PES, PVDF PES PES, PVDF
Module Fibers Spirals Cassette Fibers Tubes
System Continuous Continuous Batch, NFF Continuous Batch
Performance Cost, Cost Recovery Cost Plugging,
drivers plugging cost

concentrate and change buffers (for final formu-
lation into a storage buffer). For drug products
with potential viral contaminants (sourced from
mammalian cells or human and animal blood
plasma), virus removal filters employed in either
a TFF or NFF mode retain the viruses, while the
drug product is recovered in the permeate. UF has
displaced size exclusion chromatography (SEC)
for buffer exchange due to its lower cost and
ability to run higher protein concentrations.
These applications require high yields,
maintaining high purity, consistent operation,
and scale-up of the valuable product.
UF is used to clarify various fruit juices (apple,
grape, pear, pineapple, cranberry, orange, and
lemon) which are recovered as the permeate. UF
has also been used to remove pigments and
reduce browning in wine production. Low-cost
operation is required.
Wastewater treatment and water purification
applications employ UF in a TFF or NFF mode to
produce permeate product with reduced colloids,
pyrogens, and viruses. Oil droplets in wastewater
are retained by UF for recycle or disposal at
significantly reduced volumes (Table 1).
References
Ho WS, Sirkar K (1992) Membrane Handbook, Van
Nostrand Reinhold, NY
Lutz H (2015) Ultrafiltration for Bioprocessing,
Woodhead, Cambridge, UK
Lutz H (2008) Membrane Sepataion Processes in Perry’s
Chemical Engineering Handbook, 8th ed, McGraw-
Hill, NY
Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
filtration, Marcel Dekker, NY
U
UF Modeling
Herb Lutz
Millipore Corporation 6309, Playa del Rey, CA,
USA
Basic membrane process configurations include
single-pass, batch, fed-batch, and continuous
operation (Fig. 1). Single-pass operation involves
a single pass of feed through the module feed
channel where it exists as sufficiently concen-
trated retentate. This requires a long residence
time in the modules using long feed channels
and/or low feed flow rates. Component concen-
trations change along the length of the retentate
channel. Analysis starts with the steady-state
component and solvent mass balances as shown
in the Table 1. These consider an incremental
area element, dA, in the axial or flow direction
for a feed channel, module, or membrane assem-
bly of constant width. Constant density is also
assumed. Combining the balance equations and
integrating yields a relation between concentra-
tions, volume reduction, and solute passage. The
area required for processing is obtained by inte-
grating the solvent balance. The Cheryan flux
approximation J ¼ 0:33 J initial þ 0:67 J final is
useful. Flux decreases along the feed channel
due to a reduction in pressure by friction, a reduc-
tion in crossflow due to permeate losses, and an
increase in osmotic pressure due to concentration
increases in the retained solute. Eventually,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1208-1
conditions in the feed channel reach an osmotic
pinch point where there is no net driving force for
the flow. Beyond this point, the flow may run in a
reverse direction. To solve for details of the flow,
one needs an appropriate flux model relating flux
to cross flow, concentration, and pressure and a
hydraulic model showing how retentate pressure
profiles vary with flow for feed spacer-filled
channels. One can use simplified linear or gel
flux models as an approximation.
Continuous operation (also called feed and
bleed) is similar to single-pass operation but
involves partial recycle of the retentate. This
configuration allows a higher crossflow and
higher membrane fluxes compared to single
pass for concentrated systems running in the
polarized region of the flux curve. Compared to
batch operation, setup and cleaning times
between batches are significantly reduced so
there is higher productivity on invested capital.
As a result, continuous systems are common for
large-scale processing. Continuous operation is
frequently performed as a multistage operation
where the retentate from one system becomes the
feed for the next system. Each stage runs at a
different concentration and the total area require-
ments are less than for a single stage. After about
four stages, the system approaches batch opera-
tion as a minimum area. The residence time and
number of pump passes is in-between single-pass
and batch operation, depending on the fraction of
retentate recycled.
2 UF Modeling
UF Modeling, Fig. 1 UF
Modeling
Retentate R
Feed F
Single-pass
Recycle Tank
Fed-Batch
Batch operation involves recycling the
retentate to the feed tank to create a multipass
flow of the feed through the module. The compo-
sitions in batch systems change over time. High
flow rates generate better fluxes but recycling is
necessary to generate either the desired permeate
flow or a concentrated retentate. Multipass oper-
ation increases residence times and pump passes
that may degrade retentate components. For sys-
tems requiring high pressures to generate perme-
ate flow, it is useful to run the entire system at
high pressure to save energy. As before,
unsteady-state solvent and component mass bal-
ances can be written for batch operation and
combined and integrated to yield concentration
behavior. TFF systems have a maximum volume
reduction capability, typically about 40x. This
arises because tanks must be large enough to
hold the batch volume while allowing operation
at a minimum working volume. The minimum
working volume may be limited by air entrain-
ment into the feed pump, mixing in the feed tank,
or level measurement capabilities.
Fed-batch operation extends the volume
reduction capability to 100x and provides some
flexibility in processing a variety of batch
Diafiltrate D
Permeate P
Batch
Continuous
volumes in a single skid. For a fed-batch opera-
tion, the retentate is returned to a smaller recycle
tank, not the large feed tank. Feed is added to the
recycle tank as permeate is withdrawn to main-
tain a constant recycle tank volume. The recycle
tank can allow a smaller working volume without
entrainment. Reducing the size of the recycle
tank results in just a section of the pipe or bypass
line that returns the retentate directly into the
pump feed. Fluid from the feed tank is added
slowly into this recirculation loop. This allows a
holdup volume consisting of just the recirculation
loop. This configuration can be problematic to
flush, vent, and drain leading to cleaning and
product recovery issues. Fed-batch retentate con-
centrations exceed the batch concentrations until
the curves intersect and any further concentration
would proceed in batch mode. The benefits
sought from higher concentrations can lead to
other problems such as reduced fluxes, larger
area and pumps, possible denaturation, and
extra lines that may have issues with cleaning
and product recovery. This has not only caused
significant commissioning and validation delays
but also led to the scrapping of a process skid as
unworkable. The number of pump passes will
 UF Modeling

UF Modeling, Table 1 UF Modeling

Batch concentration and Continuous (feed and bleed) concentration and
Single pass diafiltration Fed-batch concentration diafiltration
Solvent balance dR dV dV Fn þ Dn ¼ Rn þ Pn
dA ¼ J dt ¼ JA  D dt ¼ J
per stage n
Component balance dMi dMi dMi Fn Cin1 ¼ Rn Cin þ Pn Cin Sin
dA ¼ JCi Si dt ¼ JACi Si dt ¼ JACi Si
per stage n
Volume reduction FR F/R F/R Fn/Rn
J
factor X= per stage n
h 1
i
Retentate Ci0 Xð1Si Þ Ci0 Xð1Si Þ eSi N ½Cio =Si  1  ð1  Si ÞeSi rð1XÞ Cin1 fXn =½1  Sin þ Sin Xn ð1 þ Nn Þg
concentration Ci= per stage n
h 1
i
Retentate mass Mi= Mi0 Xð1Si Þ Mio eSi ðNþlnXÞ ½Mio =Si  1  ð1  Si ÞeSi rð1XÞ
Area sizing A= ðFRÞ F11=X N=X F11=X Pn =Jn ¼ Fn ð1 þ Nn  1=Xn Þ=Jn
J t J conc
þJ
diaf t J conc per stage n
Comments Simplest system and control Limited to X < 40 Limited to X < 100 For multistage Fn = Rn1
scheme Smaller area or process time Minimize fed-batch ratio to
minimize area
Where F feed volume (batch) or feed flow (continuous), R retentate, P permeate, D diafiltrate, V batch retentate volume, A membrane area, t process time, J flux (volumetric flow
per unit area), J = average flux over step, Ci solute i concentration, Mi mass of solute i, Si solute i observed passage through the membrane (Cpermeate/Cfeed), r fed-batch ratio (feed
volume/ recycle tank volume = F/VR), X volume reduction factor (F/R), N diavolumes (D/R for batch or D/F for continuous), n stage number n of multistage continuous system
3
4 UF Modeling

also be higher, leading to more potential solute diavolumes. It is common to add an extra 1–2
degradation. Fed batch and bypass should be used diavolumes as a safety factor to ensure complete
only when necessary. buffer exchange. For final formulation pharma-
Diafiltration mode involves adding a new ceutical applications, 8–10 diavolumes are
buffer to the system while withdrawing permeate standard.
at the same rate so the tank level remains con- Diafiltration usually takes much more time
stant. Over time, the retained solute sees a buffer than concentration. When a fully retained solute
change. This is characterized by the controls the flux by the gel model, the batch
diavolumes N, the ratio of buffer volume added diafiltration time is given by
0 1
to tank volume for batch systems, and the ratio of
buffer flow to feed flow for continuous systems. V B N=X C
0 B   C, where C and X are related
t¼ A @
Table 1 shows how solute concentrations change Cg A
kln
with N. A fully retained solute (Si = 0) maintains C
its retentate concentration constant at the initial as in Table 1. This equation shows that more
value. For fully passing solutes, >4.5 diavolumes initial volume reduction and higher concentration
are needed to achieve a specification of <1 % of lead to reduced batch volume and lower
the original buffer components. Incomplete diafiltration fluxes. A minimum time solution
mixing (due to dead legs and liquid droplets on exists when C = Cg/e.
tank walls) becomes significant at high
U
UF Transport
Herb Lutz
Millipore Corporation 6309, Playa del Rey
CA, USA
UF membranes are porous solids that selectively
retain large solutes and pass liquid solvent and
small solutes. The interconnected porous network
is sometimes described as a percolating foam
structure. It is commonly described by a lognormal
distribution of parallel cylindrical pores. Laminar
flow of pure solvent through an incompressible
membrane follows Darcy’s law J = Lm ∙ TMP
where J is the flux or volumetric flow per unit
membrane area, TMP is the transmembrane pres-
sure difference across the membrane, and Lm is the
constant membrane permeability. For parallel
cylindrical pores of the same radius r, the perme-
ϵr2
ability is Lm ¼ 8ml where e is the membrane poros-
ity, m is the fluid viscosity, and l is the membrane
thickness. Any retained solute will accumulate on
the upstream membrane surface causing an
osmotic pressure P. Membrane fouling reduces
the membrane permeability to Lf. Process flow is
described by the osmotic model
J ¼ Lf ðTMP  s0 DPÞ where s0 is the osmotic
or Staverman reflection coefficient. For a totally
retained solute, s0 = 1, and for a totally passing
solute, s0 = 0. When TMP<DP, reverse flow is
observed.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1209-2
Retained solute will continue to accumulate
for flow normal to the membrane surface
J (normal flow filtration or NFF) but will reach a
steady state when flow tangential to the surface v
is added (tangential flow filtration or TFF). Most
UF is run in TFF mode to maintain high fluxes for
economical operation. For steady state where
back diffusion balances entrained solute
convected to the surface, the wall concentration
Cw ¼ Cb expðJ=kÞ for bulk concentration Cb,
flux J, and mass transfer coefficient k. Retained
solutes are reversibly held in a polarization or
“gel” layer at the membrane surface at ~1 g/m2.
The solute concentration at the membrane sur-
face or “wall” operation at low concentrations
(linear region) follows Darcy’s law, but operation
at high concentrations (polarized region) results
in a flux that is independent of TMP but depen-
dent on tangential flow v and solute bulk concen-
tration C. This is empirically

described
 by the gel
flux model J ¼ kv  ln Cg =C where kvn is the
n
mass transfer coefficient and Cg is a constant “gel
point” wall concentration. An actual gel is not
formed. The osmotic model describes the flux
across the linear and polarized regions. These
models strictly apply to a uniform upstream,
while in membrane modules, properties change
along the upstream channel. The models can be
integrated along the feed channel but are com-
monly used with an average TMP across the feed
channel and feed velocities and concentrations.
2 UF Transport
A hydrodynamic analysis of steady-state solute
flux by diffusion and convection along a pore yields
a net solute flux of N ¼ ½fKc J=e ½Cwall expðPem Þ
Cpermeate =½expðPem Þ  1. The membrane Peclet
number is Pem ¼ ½Jl=D1  ½fKc =efKd  for solute-
free solution binary diffusivity D1, partitioning
coefficient f, convective hindrance coefficient Kc,
and diffusive hindrance coefficient Kd. Pore shapes
fall in-between cylindrical and slit geometries in
terms of solute and pore wall interactions. For a
spherical solute in a cylindrical pore, Cpore =Cwall
¼ f ¼ ð1  lÞ2 where l ¼ rsolute =rpore , while
h i
asymptotic analysis yields Kc  2  ð1  lÞ2


exp 0:7146l2 and Kd  ð1  lÞ13=2 . For a
spherical solute in a slit pore, steric considerations
imply an equilibrium partitioning Cpore =Cwall ¼
f ¼ ð1  lÞ where l ¼ rsolute =rpore, while asymp-
totic analysis yields Kc  ð3  fÞ2 1=2  l2 =6


and Kd  1  1:004l þ 0:418l3 þ 0:21l4  0:619l5 :
The “actual” solute sieving coefficient becomes
Sa ¼ Cpermeate =Cwall ¼ S1 expðPem Þ=½S1 þ expðPem Þ
1 where S1 ¼ fKc ¼ 1  s0 is the asymptotic
sieving coefficient for large Pem where convection
dominates. The presence of surface charges reduces
both membrane permeability and solute sieving
coefficients. Average sieving across a membrane
thickness from the wall to the permeate requires
integration across the pore size distribution. Mea-
sured sieving coefficients from the bulk feed to the
permeate requires accounting for polarization. Sol-
utes are diluted within pores, but multicomponent
interaction is required within the polarization layer
where large solute polarization reduces the sieving
of smaller solutes. Sieving along devices requires
integration along the feed channel.
U
UF Membranes
Herb Lutz
EMD Millipore Corporation, Playa del Rey
CA, USA
UF membranes are thin porous solids that
perform separations by retaining and passing
solutes primarily based on their size. Key mem-
brane properties include retention capability,
solvent permeability, chemical compatibility,
mechanical strength for module fabrication and
repeated use, consistency, and cost. They have
nominal molecular weight limit (NMWL) ratings
of 1–5,000 kDa to retain solutes such as macro-
molecules, nanoparticles, and colloids while
passing smaller solutes and solvents. UF mem-
branes retain smaller solutes than microfiltration
membranes and larger solutes than reverse osmo-
sis membranes. Food and medical applications
require extractable testing, adsorption, shedding,
and United States Pharmacopeia (USP) class VI
toxicity testing. In addition, these applications
require high consistency membranes with vendor
quality programs (e.g., International Organiza-
tion for Standardization (ISO), current good
manufacturing practices (cGMP)). With reuse,
membrane cost is significantly reduced.
UF membranes primarily consist of polymers
(polyethersulfone, regenerated cellulose,
polysulfone, polyamide, polyacrylonitrile, or
various fluoropolymers) formed by immersion
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1210-2
casting on a web or as a composite cast on an
MF membrane. A multicomponent, high
polymer concentration (5–25 %) viscous solution
(lacquer) is well mixed, degassed, and filtered to
remove particles or trap air. The lacquer contains
a nonsolvent which separates into droplets and
becomes the pores of the UF membrane. Hollow
fibers are formed by metering the lacquer through
a die into an immersion bath. Flat sheet
membrane is formed by metering the lacquer
through a precisely controlled slot to coat a sup-
port web lying on a casting drum. Early UF
immersion cast membranes cast on a solid web
had thin surface retentive layers with an open
structure underneath. These membranes were
prone to defects and showed poor retention and
consistency. Newer composite membranes use a
MF membrane as the support web with the UF
layer cast on top. These composites demonstrate
consistently high retention and can be integrity
tested using air diffusion in water.
The web coat or extruded fiber is fed into an
immersion liquid bath that causes the lacquer
solvent to diffuse out of the lacquer coat
(desolvation). Then solubility limits are reached
(demixing) where the nonsolvent phase nucleates
and grows (spinoidal decomposition) and the
solid polymer phase nucleates and grows
(gelation). The polymer structure then coalesces
into its final structure (phase transformation).
The membrane structure is formed rapidly at
nonequilibrium conditions, but the trajectory is
commonly plotted on a ternary phase diagram.
2 UF Membranes

UF Membranes, Table 1 UF membranes

Material Advantages Disadvantages
Polyethersulfone Resistance to temperature, Cl2, pH, easy Hydrophobic
(PES) fabrication
Regenerated Hydrophilic, low fouling Sensitive to temperature, pH, Cl2,
cellulose microbial attack, mechanical creep
Polyamide Sensitive to Cl2, microbial attack
Polyvinylidene Resistance to temperature, Cl2, easy Hydrophobic, coating sensitive to high pH
fluoride (PVDF) fabrication
Inorganic Resistance to temperature, Cl2, pH, high Cost, brittleness, high cross-flow rates
pressure, solvents, long life

UF Membranes, Fig. 1 Regenerated cellulose ultrafiltration membrane side view SEM. (a) Conventional UF,
(b) Composite UF (Courtesy of Millipore Corporation)

Foam or nodular structures form depending on
the formation path. Asymmetry or skin structures
can form depending on the kinetics of diffusive
transport and nucleation. The key control
parameters are the composition of the lacquer,
composition of the immersion bath, coating or
extrusion thickness, casting speed, bath tempera-
ture, and bath flow velocity.
Residual solvent and anti-solvent are washed
out of the polymeric membrane structure in
separate extraction baths. Hydrophobic polymers
are surface modified to render them hydrophilic
and thereby reduce fouling, reduce product
losses, and increase flux.
Inorganic UF membranes (alumina, glass, and
zirconia) are formed by sintering. Layers of
spherical particles are deposited on a substrate
and heated to fuse them together. Pores are
formed in the gaps between the spherical parti-
cles. Successive layers of smaller and smaller
particles can be deposited to make tighter
membranes. These membranes find use in corro-
sive applications where their high cost can be
justified (Table 1, Fig. 1).
References
Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
filtration, Marcel Dekker, NY
A
Alkane Oxidative Dehydrogenation
by Membrane Reactor
Miguel Menendez
Department of Chemical and Environmental
Engineering, University of Zaragoza, Zaragoza,
Spain
Alkanes are converted to olefins in the chemical
industry because of the high demand of polyole-
fins, such as polypropylene or polybutadiene, and
also because olefins are the starting materials for
many other chemicals. These reactions can be
represented as
Cn H2nþ2 ! Cn H2n þ H2
A common characteristic of these reactions is the
achievable conversion being limited by thermo-
dynamic equilibrium. Two options to increase the
conversion are
– Using a membrane reactor where H2 is
removed from the reactor. This will increase
the achievable conversion according to the Le
Chaterlier’s principle. Any material which can
remove hydrogen selectively can be used, but
Pd and Pd alloys are the most employed. The
preparation of this kind of membranes has
been widely described (Basile and Gallucci
2011).
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1211-3
– Adding an oxidizing agent (e.g., oxygen) to
the reaction, in order to form water instead of
hydrogen, the resulting reaction would be:
Cn H2nþ2 þ 1=2 O2 ! Cn H2n þ H2 O
This approach has the advantage of being
thermodynamically favored but has the problem
that simultaneous formation of carbon oxides
reduces the selectivity.
A way to improve the selectivity is to use a
membrane reactor, where the membrane distrib-
utes oxygen along a packed bed of catalyst. This
improvement is based on the favorable effect of
low oxygen partial pressure on the selectivity. In
fact, for many catalysts the observed reaction
order respect to oxygen for the above reaction is
lower than for the formation of CO and CO2. This
observation implies that low partial pressure of
oxygen increases the selectivity to olefins.
This general principle has been applied for the
oxidative dehydrogenation of ethane, propane,
and butane, with successful results in all cases
(Coronas and Santamaría 1999). Details of the
results obtained with membrane reactors with
propane and butane (▶ oxidative dehydrogena-
tion and oxidation to maleic anhydride) are
described in specific chapters.
A general scheme of a membrane reactor for
this kind of reactions is shown in Fig. 1.
The oxygen containing feed is usually intro-
duced through the shell side. A porous membrane
distributes this oxygen along the catalyst bed,
2 Alkane Oxidative Dehydrogenation by Membrane Reactor

Alkane Oxidative
Dehydrogenation by
Membrane Reactor,
Fig. 1 Scheme of a
membrane reactor for the
selective oxidation of
hydrocarbons with a
distributed feed of oxygen

keeping a low partial pressure of oxygen in all the References

beds. A feed containing the hydrocarbon is fed to
the tube side, i.e., to the catalyst bed. The reaction
products are removed at the exit of the
catalyst bed.
As an alternative to porous membranes, dense
ceramic membranes can provide an additional
advantage: the separation of oxygen-nitrogen
mixtures (Hashim et al. 2011). This would
decrease the cost of oxygen separation.
Basile A, Gallucci F (eds) (2011) Membranes for mem-
brane reactors. Preparation, optimization and selec-
tion. Wiley, Chichester
Coronas J, Santamaría J (1999) Catalytic reactors based on
porous ceramic membranes. Catal Today 51:377–389
Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep-
aration from air using ceramic-based membrane tech-
nology for sustainable fuel production and power
generation. Renew Sustain Energy Rev 15:1284–1293
M
Maleic Anhydride Production by
Membrane Reactor
Miguel Menendez
Department of Chemical and Environmental
Engineering, University of Zaragoza, Zaragoza,
Spain
Maleic anhydride is a valuable intermediate
product in the manufacture of polyester fiber,
succinic acid, tetrahydrofuran, tartaric acid, and
several other chemicals. Most of the maleic anhy-
dride is produced by the oxidation of butane with
VPO catalyst. This reaction is unique because no
other commercial process achieves the insertion
of three oxygen atoms in one paraffin molecule in
a single step using molecular oxygen. The cata-
lyst is a complex mixture of vanadium and phos-
phorous oxides, which is often close to the
chemical composition of vanadyl pyrophosphate,
but in fact the oxidation degree of vanadium
varies between +4 and +5 depending on the oper-
ating conditions.
Industrial operation is limited by need to avoid
explosive atmospheres, which requires low
butane or low oxygen concentration. In conven-
tional reactors a low oxygen concentration would
imply a too low butane conversion, which would
be economically unsuitable. Therefore the indus-
trially employed approach, both for fixed and
fluidized bed reactors, is to feed a low butane
concentration (typically below 2 %) in air. This
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1212-1
approach implies the use of large feed and prod-
uct flows, increasing the operating and capital
costs. The use of a membrane reactor allows the
operation with a large butane concentration (up to
10 % butane) but avoiding the coexistence in a
given point of large butane and oxygen concen-
trations (Mallada et al. 2000), in a similar way as
when membrane reactors are used for oxidative
dehydrogenation. A critical point in this kind of
reactor is to avoid too low oxygen concentrations,
since a reducing atmosphere changes the oxida-
tion degree of vanadium, with a catastrophic
decrease in selectivity.
A way to decrease the risk of vanadium reduc-
tion is using CO2 as inert gas. In fact, there are
experimental proofs that under reaction condi-
tions, CO2 is not fully “inert” but can contribute
to achieve a more oxidized catalyst (Mallada
et al. 2002; Xue et al. 2001).
Another factor that may contribute to improve
the maleic anhydride yield in a membrane reactor
is the catalyst bed configuration. If the catalyst
bed is located around the membrane, instead of
inside, the achievable yield increases.
A mathematical model of both reactors explains
this result by the differences in radial partial
pressure profiles (Pedernera et al. 2000).
Finally, in order to apply a membrane reactor
industrially, the temperature control is critical.
While fixed bed reactors use a bath of fused
salts to keep the catalyst bed temperature under
control, this approach would not be feasible in
membrane reactors. A method proposed to
2 Maleic Anhydride Production by Membrane Reactor
control the temperature in a membrane reactor is
to surround the reactor with a fluidized bed. The
high isothermicity and excellent heat exchange
are well-known characteristics of fluidized beds,
and the same oxygen containing stream that is
permeated through the membrane can be used to
keep the bed fluidized. This configuration has
been employed in a pilot plant (Alonso
et al. 2001).
References
Alonso M, Lorences MJ, Pina MP, Patience GS
(2001) Butane partial oxidation in an externally fluid-
ized bed-membrane reactor. Catal Today 67:151–157
Mallada R, Menéndez M, Santamarı́a J (2000) Use of
membrane reactors for the oxidation of butane to
maleic anhydride under high butane concentrations.
Catal Today 56:191–197
Mallada R, Menéndez M, Santamarı́a J (2002) On the
favourable effect of CO2 addition in the oxidation of
butane to maleic anhydride using membrane reactors.
Appl Catal A Gen 231:109–116
Pedernera M, Mallada R, Menéndez M, Santamaria
J (2000) Simulation of an inert membrane reactor for
the synthesis of maleic anhydride. AIChE
J 46:2489–2498
Xue E, Ross JR, Mallada R, Menendez M, Santamaria J,
Perregard J, Nielsen PEH (2001) Catalytic oxidation of
butane to maleic anhydride enhanced yields in the
presence of CO2 in the reactor feed. Appl Catal
A Gen 210:271–274
N

N-Butane Oxidative oxidant (Ge et al. 2003). The use of catalytic

Dehydrogenation by Membrane membrane has also been proposed (Alfonso
Reactor et al. 2002). Mathematical modeling of those
reactors has shown that the reactor performance
Miguel Menendez agrees well with the predictions of mathematical
Department of Chemical and Environmental models both for the inert membrane reactor
Engineering, University of Zaragoza, Zaragoza, (Téllez et al. 1999) and for the catalytic mem-
Spain brane reactor (Pedernera et al. 2002).

Introduction
Modifications in the Reactor
Configuration
Butene, isobutene, and butadiene are mainly
obtained from steam crackers, but the increased
This approach has been employed by several
use of natural gas as feedstock has decreased the
researchers with a variety of modification in the
availability of C4 olefins. Therefore, these olefins
configuration:
are increasingly produced by the dehydrogena-
tion of the corresponding alkane. Since that is an
– Pure butane in the feed to the bed entry and
equilibrium-limited reaction, oxidative dehydro-
homogeneous oxygen distribution along the
genation has been proposed as an alternative that
bed using a membrane.
has raised much interest (Mamedov and Cortés-
– Butane diluted with inert gas and/or oxygen
Corberán 1995; Madeira and Portela 2002). As it
diluted with inert gas. In comparison with the
happens in many selective oxidations, the
previous approach, safety is increased and
undesired formation of carbon oxides (CO and
often the achieved selectivity is better, but
CO2) is a serious problem. As in other selective
the industrial application would require the
oxidations, membrane reactors have been also
separation of inert gases from the reaction
proposed for this reaction. Significant improve-
products, increasing the process operation
ment of yield has been observed when the oxygen
costs.
is distributed to a fixed bed of catalyst enclosed in
– Nonhomogeneous distribution of oxygen feed.
a porous membrane (Téllez et al. 1997).
In order to obtain a greater reaction rate at the
A progressive distribution has been found to be
reactor entry, a larger permeation of oxygen
advantageous (Ge et al. 2001). An interesting
near the propane entry may be useful.
alternative is the use of CO2 instead of O2 as
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1213-2
2 N-Butane Oxidative Dehydrogenation by Membrane Reactor
– Combination of a conventional fixed-bed
reactor with a membrane reactor. In such
case, the feed to the fixed-bed reactor contains
a small amount of oxygen.
– Use of a catalytic membrane. In this case, part
of the membrane is loaded with catalyst, pref-
erentially in the side where propane is feed.
The operation principle is the same as when a
packed bed of catalyst enclosed in a mem-
brane is employed: the lower oxygen partial
pressure in the reaction zone increases the
selectivity to the desired product.
Types of Membrane
The membrane employed for this reaction does
not need to be selective for oxygen, i.e., a
mesoporous membrane may be employed. In
such case, the back permeation of hydrocarbon
to the shell side must be avoided. This usually
requires a significant pressure drop of oxygen.
Examples of membranes employed include
microfiltration ceramic membranes with the
pores filled with silica, nanofiltration ceramic
membranes with enamel trips to reduce the per-
meation, or zeolite membranes.
Alternatively dense ceramic membranes, i.e.,
oxygen selective, can be employed. In such case,
in addition to the improvement in butene selec-
tivity provided by the oxygen distribution and the
avoidance of back permeation problems, the pre-
vious step of oxygen separation from air may be
avoided.
Catalysts
Although in principle any catalyst suitable for
oxidative dehydrogenation of butane could be
tested in a membrane reactor, the most employed
are the simplest ones: vanadium oxide supported
on alumina or on magnesium oxide.
References
Alfonso MJ, Menéndez M, Santamaría J (2002) Oxidative
dehydrogenation of butane on V/MgO catalytic mem-
branes. Chem Eng J 90:131–138
Ge SH, Liu CH, Wang LJ (2001) Oxidative dehydrogena-
tion of butane using inert membrane reactor with a
non-uniform permeation pattern. Chem Eng
J 84:497–502
Ge S, Liu C, Zhang S, Li Z (2003) Effect of carbon dioxide
on the reaction performance of oxidative dehydroge-
nation of n-butane over V-Mg-O catalyst. Chem Eng
J 94:121–126
Madeira LM, Portela MF (2002) Catalytic oxidative dehy-
drogenation of n-butane. Catal Rev 44:247–286
Mamedov EA, Cortés Corberán V (1995) Oxidative dehy-
drogenation of lower paraffins on vanadium-oxide-
based catalysts: the present state of art and
outlooks – a review. Appl Catal A Gen 127:1–40
Pedernera M, Alfonso MJ, Menéndez M, Santamaría
J (2002) Simulation of a catalytic membrane reactor
for the oxidative dehydrogenation of butane. Chem
Eng Sci 57:2531–2544
Téllez C, Menéndez M, Santamaría J (1997) Oxidative
dehydrogenation of butane using membrane reactors.
AIChE J 43:777–784
Téllez C, Menéndez M, Santamaría J (1999) Simulation of
an inert membrane reactor for the oxidative dehydro-
genation of butane. Chem Eng Sci 54:2917–2925
P

Propane Oxidative the reaction zone. For many catalysts, a low par-
Dehydrogenation by Membrane tial pressure of oxygen implies a better selectivity
Reactor to propene (Ziaka et al. 1993; Pantazidis et al.
1995; Tonkovich et al. 1996). The use of porous
Miguel Menendez membranes has been reviewed by Coronas and
Department of Chemical and Environmental Santamarı́a (1999) and Julbe et al. (2001).
Engineering, University of Zaragoza, Zaragoza,
Spain
Modifications in the Reactor
Configuration
Propene is industrially obtained in naphtha crack-
ers, in FCC units, and in a growing proportion, by
This approach has been employed by several
dehydrogenation of propane. Propane dehydro-
researchers with a variety of modification in the
genation is an endothermic reaction, and the
configuration:
maximum achievable conversion is limited by
thermodynamic equilibrium. An alternative to
– Pure propane and homogenous oxygen distri-
propane dehydrogenation is the oxidative dehy-
bution along the bed.
drogenation of propane. In such case, the reaction
– Propane diluted with inert gas and/or oxygen
is irreversible, but the inconvenience is the
diluted with inert gas. In comparison with the
appearance of nonselective oxidation reactions
previous approach, safety is increased and
of propane and propene to carbon oxides
often the selectivity achieved is better, but the
(CO and CO2). The success of propane oxidative
industrial application would require the separa-
dehydrogenation will be linked to the achieve-
tion of inert gases from the reaction products,
ment of high selectivity to propene and high
increasing the process operation costs.
enough conversion (Cavani et al. 2007). A large
– Nonhomogenous distribution of oxygen feed.
amount of research has been devoted to the opti-
In order to obtain a greater reaction rate at the
mization of the catalyst, and this is obviously a
reactor entry, a larger permeation of oxygen
key factor, but the selection of a suitable reactor
near the propane entry may be useful.
may be another factor contributing to achieve a
– Combination of a conventional fixed bed reac-
successful result. A packed bed membrane reac-
tor with a membrane reactor. In such case, the
tor in which propane is fed at the catalyst bed
feed to the fixed bed reactor contains a small
entry and oxygen is permeated along the mem-
amount of oxygen.
brane provides a low partial pressure of oxygen in
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1215-2
2 Propane Oxidative Dehydrogenation by Membrane Reactor
– The use of a catalytic membrane. In this case,
part of the membrane is loaded with catalyst,
preferentially in the side where propane is fed.
The operation principle is the same as when a
packed bed of catalyst is employed: the lower
oxygen partial pressure in the reaction zone
increases the selectivity to the desired product
(Alfonso et al. 1999; Julbe et al. 2000).
Types of Membrane
The membrane employed for this reaction does not
need to be selective for oxygen, i.e., a mesoporous
membrane may be employed. In such case, the
back permeation of hydrocarbon to the shell side
must be avoided. This usually requires a significant
pressure drop of oxygen. Examples of membranes
employed include microfiltration ceramic
membranes with the pores filled with silica,
nanofiltration ceramic membranes with enamel
trips to reduce the permeation or zeolite mem-
branes. In an alternative configuration, the mem-
brane has catalytic activity (Alfonso et al. 1999).
Alternatively dense ceramic membranes, i.e.,
oxygen selective, can be employed (Wang
et al. 2003; Czuprat et al. 2010). In such case, in
addition to the improvement in propene selectivity
provided by the oxygen distribution and the avoid-
ance of back permeation problems, the previous
step of oxygen separation from air may be avoided.
Catalysts
Although in principle any catalyst suitable for
oxidative dehydrogenation of propane could be
tested in propane dehydrogenation, the most
employed are the simplest ones: vanadium oxide
supported on alumina or on magnesium oxide.
References
Alfonso MJ, Julbe A, Farrusseng D, Menendez M,
Santamarı́a J (1999) Oxidative dehydrogenation of
propane on V/Al2O3 catalytic membranes. Effect of
the type of membrane and reactant feed configuration.
Chem Eng Sci 54:1265–1272
Cavani F, Ballarini N, Cericola A (2007) Oxidative dehy-
drogenation of ethane and propane: how far from com-
mercial implementation? Catal Today 127:113–131
Coronas J, Santamarı́a J (1999) Catalytic reactors based on
porous ceramic membranes. Catal Today 51:377–389
Czuprat O, Werth S, Caro J, Schiestel T (2010) Oxidative
dehydrogenation of propane in a perovskite membrane
reactor with multi-step oxygen insertion. AIChE
J 56:2390–2396
Julbe A, Farrusseng D, Jalibert JC, Mirodatos C, Guizard
C (2000) Characteristics and performance in the oxi-
dative dehydrogenation of propane of MFI and V-MFI
zeolite membranes. Catal Today 56:199–209
Julbe A, Farrusseng D, Guizard C (2001) Porous ceramic
membranes for catalytic reactors-overview and new
ideas. J Membr Sci 181:3–20
Pantazidis A, Dalmon JA, Mirodatos C (1995) Oxidative
dehydrogenation of propane on catalytic membrane
reactors. Catal Today 25:403–408
Tonkovich ALY, Zilka JL, Jimenez DM, Roberts GL, Cox
JL (1996) Experimental investigations of inorganic
membrane reactors: a distributed feed approach for
partial oxidation reactions. Chem Eng Sci 51:789–806
Wang H, Cong Y, Zhu X, Yang W (2003) Oxidative
dehydrogenation of propane in a dense tubular mem-
brane reactor. React Kinet Catal Lett 79:351–356
Ziaka ZD, Minet RG, Tsotsis TT (1993) Propane
dehydrogenation in a packed-bed membrane reactor.
AIChE J 39:526–529
P
Plasma Etching
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier, France
Plasma etching (Yasuda 1985; d’Agostino 1990;
Biederman and Osada 1992; Inagaki 1996) is one
of the major effects caused by the interaction
between a cold plasma (defined in the article
entitled “Vapor plasma membrane treatment”)
and a material placed within it. It is due to com-
bination of reactive species of the gas phase with
atoms or groups of atoms of the substrate leading
to the creation of active sites on the surface of the
substrate (ablation of surface) and to the forma-
tion of volatile species which diffuse in the gas
phase. Plasma etching is prevalent on the other
plasma treatments (plasma functionalization,
PECVD/plasma polymerization) in the case of
inert gases such as rare gases (argon (Ar), helium
(He)), O2, SF6, or CxFy used as gaseous phases.
Plasma etching is mainly used for the surface
modification of polymers or metals. In the case of
a polymeric substrate, plasma etching is system-
atically coupled with substrate cross-linking due
to opening (under the action of the reactive spe-
cies of plasma) of the bonds between atoms of the
surface of the substrate allowing them to reorga-
nize (by bridging between the macromolecular
chains). The main application of plasma etching
is certainly the preparation of MEMs in
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1224-4
microelectronics. In the field of membranes, the
implementation of plasma etching has appeared
in the last decade. Plasma etching has been
applied for modulating the membrane transport
properties (by cross-linking the surface chains,
increasing the pore size, or etching the polluted
surface) or reinforcing their mechanical, thermal,
and chemical stability (essentially under the
effect of cross-linking) (Bryjak et al. 1996;
Gancarz et al. 1999; Reinholdt et al. 2012). How-
ever, it is generally known that, in the case of
some specific polymer membranes, the effect
gained in such modifications may disappear or
significantly diminish during storage. Moreover,
plasma etching can sometimes alter the physico-
chemical properties of material and particularly
polymer surfaces.
References
Biederman H, Osada Y (1992) Plasma polymerization
processes. Elsevier, Amsterdam
Bryjak M, Gancarz I, Krajciewicz A, Piglowski J (1996)
Evaluation of terpolymers of 2-hydroxyethyl methac-
rylate, dodecyl methacrylate, and ethylene glycol
dimethacrylate as matrices for hydrophobic interaction
chromatography. Angew Makromol Chem 234:21–29
d’Agostino R (1990) Plasma deposition, treatment and
etching of polymers. Academic, New York
Gancarz I, Pozniak G, Bryjak M (1999) Modification of
polysulfone membranes 1. CO2 plasma treatment. Eur
Polym J 35:1419–1428
Inagaki N (1996) Plasma surface modification and plasma
polymerization. Technomic Publishing Co, Lancaster
2 Plasma Etching

Reinholdt M, Ilie A, Roualdes S, Frugier J, Schieda M, for potential application in solid alkaline fuel cells.
Coutanceau C, Martemianov S, Flaud V, Beche E, Membranes 2:529–552
Durand J (2012) Plasma membranes modified by Yasuda H (1985) Plasma polymerization. Academic,
plasma treatment or deposition as solid electrolytes Orlando
P
Plasma Functionalization
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier Cedex 5, France
Plasma functionalization (Yasuda 1985;
d’Agostino 1990; Biederman and Osada 1992;
Inagaki 1996) is one of the major effects caused
by the interaction between a cold plasma (defined
in the article entitled “Vapor plasma membrane
treatment”) and a material placed within it. It is
due to fixing of reactive species of the gas phase
on active sites of the surface of the substrate.
Plasma functionalization is prevalent on the
other plasma treatments (plasma etching,
PECVD/plasma polymerization) in the case of
chemically reactive gases such as ammonia
(NH3), nitrogen (N2), oxygen (O2), carbon diox-
ide (CO2), water vapor (H2O), tetrafluor-
omethane (CF4) . . . used as gaseous phases.
More precisely, plasma functionalization consists
in grafting of amine-type or amide-type func-
tional groups in the case of NH3 or N2, grafting
of peroxide or hydroxide functions in the case of
O2 or H2O, grafting of C=O, C-OH, C(=O)OH
functions in the case of CO2, and grafting of CFx
functions in the case of CF4. In the case of a
polymeric substrate, plasma functionalization is
systematically coupled with substrate cross-
linking due to opening (under the action of the
reactive species of plasma) of the bonds between
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1225-4
atoms of the surface of the substrate allowing
them to reorganize (by bridging between the
macromolecular chains).
Plasma functionalization is mainly used for
the surface modification of polymers or metals.
In the field of membranes, the implementation of
plasma functionalization has grown rapidly in the
last decade. Plasma functionalization has been
especially applied for improving the wettability,
printability, adhesion, or biocompatibility of con-
ventional polymer membranes, modulating their
transport properties (by changing the hydro-
philic/hydrophobic balance, providing the
grafting of specific functional groups or cross-
linking the surface chains), or reinforcing their
mechanical, thermal, and chemical stability
(essentially under the effect of cross-linking)
(Roualdes et al. 2010).
However, it is generally known that, in the
case of some specific polymer membranes, the
effect gained in such modifications may disap-
pear or significantly diminish during storage.
Moreover, plasma functionalization can some-
times alter the physicochemical properties of
material and particularly polymer surfaces. An
efficient way to overcome this limitation is the
implementation of a process named plasma-
induced graft polymerization or plasma grafting.
In this process, plasma is used only to create on
the polymer surface functionalities that are able
to initiate conventional polymerization of mono-
mers containing multiple bonds. The reaction
may be carried out in two ways: in the vapor
2 Plasma Functionalization
phase of monomer or in solution. Its principle is
the following. Plasma treatment can induce radi-
cal formation on polymers surface through ion
bombardment and UV radiation. The radicals
formed on the surface of the treated polymers
can be very stable in vacuum but react rapidly
on exposure to a reactive gas. So if the vapor
phase of an unsaturated monomer is introduced
into a plasma reactor just after the surface treat-
ment of a polymer substrate, the radicals formed
on the surface of the polymer substrate immedi-
ately cause the polymerization of the monomer.
The process can also be implemented in solution.
In this case, the polymer substrate is released
from the reactor after the plasma treatment and
then exposed to atmosphere. In the presence of
oxygen or air, peroxides and hydroperoxides are
created on the polymer surface; such functions
may initiate the polymerization of a desired
monomer in solution. In both cases (vapor phase
route or solution route), grafting density and
length of grafted brush can be regulated to some
extent by plasma and grafting parameters. One
primary advantage of this technique is the ability
to modify surface properties of the polymer sub-
strates permanently without affecting the bulk
mechanical and chemical properties. There have
been several reports on hydrophilization of
polysulfone surface after plasma treatment by
plasma-induced graft polymerization (Inagaki
et al. 1997; Muller et Oehr 1999; Liu et al. 2005).
References
Biederman H, Osada Y (1992) Plasma polymerization
processes. Elsevier, Amsterdam
d’Agostino R (1990) Plasma deposition, treatment and
etching of polymers. Academic, New York
Inagaki N (1996) Plasma surface modification and plasma
polymerization. Technomic Publishing Co, Lancaster
Inagaki N, Tasaka S, Goto Y (1997) Surface modification
of poly(tetrafluoroethylene) film by plasma graft poly-
merization of sodium vinylsulfonate. J Appl Polym Sci
66:77–83
Liu ZM, Xu KZ, Wan LS, Wu J, Ulbricht M (2005)
Surface modification of polypropylene microfiltration
membranes by the immobilization of poly(N-vinyl-2-
pyrrolidone): a facile plasma approach. J Membr Sci
249:21–31
Muller M, Oehr C (1999) Plasma amino functionalization
of PVDF microfiltration membranes: comparison of
the in plasma modifications with a grafting method
using ESCA and an amino-selective fluorescent
probe. Surf Coat Technol 116–119:802–807
Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
membrane science and engineering, vol 1. Academic,
Oxford, pp 159–197
Yasuda H (1985) Plasma polymerization. Academic,
Orlando
P
Plasma-Enhanced Chemical Vapor
Deposition (Plasma Polymerization)
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier, France
PECVD is the main effect caused by the interac-
tion between a cold plasma (defined in the article
entitled “Vapor Plasma Membrane Treatment”)
and a material placed within it, in the case of
condensable gases (organic, inorganic, or organ-
ometallic compounds) used as gaseous phases.
PECVD is due to recombination of the reactive
species adsorbed on the surface of the substrate
and results in the formation, on the surface of the
substrate, of a deposit made up of a three-
dimensional matrix formed from fragments of
the reagent gas combined in a random way.
The PECVD process is mainly used for the
preparation of inorganic, hybrid, or polymer-
like thin layers. In the field of membranes, most
of the plasma deposits are prepared from organic
precursors; in that case, one calls the deposition
process plasma polymerization preferentially to
PECVD. Among the numerous PECVD parame-
ters, the ones having a direct effect on the frag-
mentation of the precursor are logically the most
influent. Three parameters have a particularly
pronounced effect: the nature of the precursor
represented by its molecular weight M, the
power of the electric discharge W, and the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1226-4
precursor flow rate F. The energy-input level
manifested by W/FM (given in units of J/kg, or
energy per mass of monomer), introduced by
Yasuda (1985), is the predominantly important
factor determining the extent of fragmentation.
Low W/FM values are related to operating con-
ditions where the activated species have a far
lower concentration than precursor molecules
introduced into the plasma; in such a range of
W/FM values, called precursor sufficient region,
the number of activated species, and conse-
quently the plasma film deposition rate, increases
with W/FM. For medium W/FM values,
corresponding to the competition region, the
quantity of precursor molecules introduced into
the plasma is exactly the quantity likely to be
activated; in that case, the film deposition rate is
invariable as a function of W/FM. For high values
of W/FM, corresponding to the precursor defi-
cient region, the material deposition rate
decreases with W/FM because of the lack of
precursor molecules likely to be activated.
Plasma deposits are disorganized thin films,
with short and branched chains (randomly termi-
nated with frequent cross-links) often not
reminding the precursor(s) they come from. In
terms of material properties, plasma deposits pre-
sent a great number of advantages when com-
pared to films synthesized, on the one hand, by
other techniques of vacuum deposition, and, on
the other hand, by liquid-route synthesis
methods:
2 Plasma-Enhanced Chemical Vapor Deposition (Plasma Polymerization)
– Like all the vacuum deposition techniques,
PECVD makes it possible to work out very
thin films with thicknesses of a few nanome-
ters to a few microns, which is impossible with
liquid-route synthesis methods. The deposi-
tion rate can be high (several mm min 1)
(Storgaard-Larsen and Leistiko 1997) making
the process ideal for industrial applications.
– One of the major interests of this technique is
the possibility of depositing materials at ambi-
ent temperature on substrates sensitive to heat
such as conventional organic polymers (which
is not possible with conventional chemical
vapor deposition (CVD): chemical plating in
pyrolytic phase vapor). The polymeric sup-
ports constitute, with glasses, semiconductors,
ceramics, and metal surfaces, the large variety
of substrates on which the plasma deposits
have a good adherence.
– The materials deposited by PECVD are gen-
erally dense, amorphous, strongly cross-
linked, and present a low density of defects
and holes compared with those obtained by the
other vacuum deposition techniques such as
evaporation or sputtering.
– The three-dimensional and highly cross-
linked structure of the plasma deposits is at
the origin of a number of very specific prop-
erties of these materials, properties that one
does not find in their counterparts worked out
by conventional ways: chemical inertia, good
thermal stability, anticorrosive character, and
barrier properties with respect to oxygen and
water vapor in particular.
– PECVD makes it possible to adjust the chem-
ical composition and the microstructure of
deposited materials and thus to modify the
physical and chemical properties of these
materials by the simple variation of the param-
eters of the process, and this in a field much
broader than the other deposition techniques.
If, from a technological point of view, this
requires a rigorous control of the parameters
of the process, the complexity and variety of
active species and reaction steps directly
related to the plasma parameters offer a high
degree of flexibility in prepared materials
properties.
References
Storgaard-Larsen T, Leistiko O (1997) Nitrogen doped
germania glasses with enhanced optical and mechani-
cal properties. J Electrochem Soc 144:1505–1513
Yasuda H (1985) Plasma polymerization. Academic,
Orlando
P
Plasma Membrane
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier, France
Plasma membrane names either a conventional
membrane which has been modified on the sur-
face by a plasma treatment (plasma etching,
plasma functionalization, PECVD/plasma poly-
merization), called plasma-treated membrane, or
a plasma polymer deposited on a highly porous
substrate (which plays the role of mechanical
support) having specific separation properties,
called plasma-polymerized membrane (see arti-
cle “plasma polymerized membrane” for more
details).
The first developed plasma membranes have
been intended to gas permeation or retention and
also pervaporation. As a striking example relative
to plasma-treated membrane for gas permeation,
Kumazawa et al. studied the gas perm-selectivity
of polyethylene (Nakata and Kumazawa 2006)
and polypropylene (Teramae and Kumazawa
2007) membranes after a 5 min long N2 or NH3
plasma treatment. They found that nitrogen was
not significantly incorporated to the polymer net-
work and that CO2 permeability coefficients
slightly increased after the plasma treatment,
whereas N2 ones were not affected, which places
these plasma-treated polymer membranes over
classical glassy polymers like polyimides, in
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1227-4
terms of CO2 separation factor. Vilani
et al. (2007; Weibel et al. 2007) studied poly-
urethanes membranes used to separate methanol
from methyl-t-butyl ether by pervaporation after
an acrylic acid vapor plasma treatment. They
showed that a short-time modification with a
high plasma input power (100 W) allowed to
increase the selectivity factor from 5 to 30 and
also the permeate flux (Vilani et al. 2007). They
attributed these evolutions to an increase of C=C
contribution and a loss of C–N content that might
result in a cross-linking at the surface due to
decreases of the surface-free volume and chain
flexibility. Upadhyay and Bhat (2004) proved the
strong efficiency of a nitrogen plasma treatment
compared to oxygen or air plasma treatments of
nonporous polyvinyl alcohol-based membranes.
The extremely high selectivity of the nitrogen-
treated membranes toward water molecules (over
1,200 in isopropyl alcohol (IPA) – water mixture
with IPA weight fraction below 0.8) could be
attributed to the surface cross-linking, whereas
air and oxygen plasma-etched amorphous regions
decrease the swelling of the treated membranes
and their selectivity to water.
More recently, plasma membranes have been
prepared for liquid separation processes. A lot of
works have been devoted to polysulfone (PSU)
membranes widely used in microfiltration or
ultrafiltration processes, in particular for
low-protein adsorption in serums and plasma.
There have been several reports on hydrophi-
lization of PSU surface after plasma treatment
2 Plasma Membrane
by noncondensable gases, plasma-induced graft
polymerization, or plasma polymerization
(Roualdes et al. 2010). Selective membranes for
the separation of water from hydrophobic liquids
can be obtained by depositing a hydrophobic
plasma-polymerized thin layer on porous mate-
rials such as filter paper or polyester textile
(Bankovic et al. 2004). The development of
plasma membranes has been more recently
applied to fields using ion-conducting mem-
branes such as electromembrane processes
(electrodialysis in particular), electrochemical
sensors, or, more broadly, the energy production
devices (fuel cells, Li-ion batteries, etc.)
(Roualdes et al. 2010).
References
Bankovic P, Demarquette NR, da Silva MLP
(2004) Obtention of selective membranes for water
and hydrophobic liquids by plasma enhanced chemical
vapor deposition on porous substrates. Mater Sci Eng
B112:165–170
Nakata M, Kumazawa H (2006) Gas permeability and
permselectivity of plasma-treated polyethylene mem-
branes. J Appl Polym Sci 101:383–387
Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
membrane science and engineering, vol 1. Academic,
Oxford, pp 159–197
Teramae T, Kumazawa H (2007) Gas permeability and
permselectivity of plasma-treated polypropylene
membranes. J Appl Polym Sci 104:3236–3239
Upadhyay DJ, Bhat NV (2004) Pervaporation studies of
gaseous plasma treated PVA membrane. J Membr Sci
239:255–263
Vilani C, Weibel DE, Zamora RRM, Habert AC, Achete
CA (2007) Study of the influence of the acrylic acid
plasma parameters on silicon and polyurethane sub-
strates using XPS and AFM. Appl Surf Sci
254:131–134
Weibel DE, Vilani C, Habert AC, Achete CA (2007) Sur-
face modification of polyurethane membranes using
acrylic acid vapor plasma and its effects on the
pervaporation processes. J Membr Sci 293:124–132
P
Plasma Polymerization
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier, France
Plasma polymerization is the other name of
PECVD in the case of vapors of organic com-
pounds as gaseous phases (the most case in the
field of membranes). Plasma polymerization has
little in common with classical polymerization.
Many side reactions occur during film deposition.
This can be understood by the poor selectivity of
the breaking up of chemical bonds in a plasma.
The mechanism of deposition is not yet well
understood. This difficulty arises from the com-
plexity and variety of active species, reaction
steps, and dependences on plasma parameters.
Several kinetic models of plasma polymerization
have been proposed. The most popular are the
models of Lam et al. (1976), Poll et al. (1976),
and Yasuda (1985). These models involve a com-
petitive ablation and polymerization (CAP)
mechanism which gives an account of the rather
complicated and interrelated influences of
fragmented elements in the deposition of plasma
polymers. It is important to mention that chain-
growth polymerization cannot occur under vac-
uum. This is simply because there are too many
chain-carrying species but not enough monomer
with a well-defined chemical structure capable of
chain-growth polymerization. With the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1228-5
occurrence of fragmentation of the monomer
structure, the situation becomes even worse.
The way in which a plasma polymer is formed
in plasma has been explained by the rapid step-
growth polymerization mechanism. The essential
elementary reactions are stepwise recombination
of reactive species (free radicals) and stepwise
addition or intrusion via hydrogen abstraction by
impinging free radicals. It is important to recog-
nize that these elementary reactions are essen-
tially oligomerization reactions that do not form
polymers by themselves. To form a polymeric
deposition, a certain number of steps must be
repeated at the surface. As the plasma polymeri-
zation proceeds, the activated species may attack
the growing polymer layer. This attack can
decompose the polymer, extend the cross-linking
of the polymer, or cause the elimination of depos-
ited polymer (ablation process). These polymer-
ization and ablation processes proceed
competitively, and the overall plasma deposition
rate is dependent on the plasma polymerization
parameters.
Plasma polymers, noted PP-X (X being the
monomer), are not formed by the repetition of a
monomer unit like classical polymers. They are
disorganized thin films, with short and branched
chains (randomly terminated with frequent cross-
links) often not reminding the monomers they
come from. In terms of material properties,
plasma polymers present a great number of
advantages when compared to films synthesized,
on the one hand by other techniques of vacuum
2 Plasma Polymerization
deposition, on the other hand by liquid-route syn-
thesis methods (see article entitled “PECVD”).
The microstructural properties of plasma
polymers depend mostly on the parameters of
plasma polymerization and more particularly on
the W/FM parameter. In the monomer-sufficient
region (low W/FM values), monomer molecules
are subjected to less fragmentation to be plasma
polymerized, and plasma polymers with less
arrangement and small loss of some groups such
as hydrogen, methyl, hydroxyl, and carbonyl
groups are formed. Under such soft synthesis
conditions, plasma polymerization retains more
the molecular structure of the monomer; plasma
polymers are more organic and less highly cross-
linked and thus resemble more conventional
polymers; they are said to be polymer-like mate-
rials. In the monomer-deficient region (high
W/FM values), monomer molecules are
subjected to heavier fragmentation, and plasma
polymers with much more rearrangements and a
larger loss of some groups (especially carbon-
based ones) are formed. Under such drastic syn-
thesis conditions, plasma polymers are harder,
more inorganic, and more highly cross-linked;
they are said to be ceramic-like. For intermediate
values of W/FM, a wide range of hybrid materials
can be manufactured. Let us consider the case of
hexamethyldisiloxane (HMDSO), widely used as
monomer in plasma polymerization (Ayral
et al. 2008). In soft plasma conditions, the plasma
film synthesized from HMDSO has a structure
close to those of the HMDSO monomer and
also the polydimethylsiloxane (PDMS), which is
the closest conventional polymer, as shown by
Fourier transform infrared (FTIR) spectroscopy;
this plasma film is thus called PDMS-like plasma
polymer; its density is quite low, equal to 1.1. In
hard plasma conditions, the obtained plasma film
is similar to amorphous hydrogenated silica with
a density of 2.2; it is noted a-SiO2:H (“a” for
amorphous, “:H” for hydrogenated); the dilution
with an oxidative gas as O2 or N2O in the plasma
reactor can enable to achieve this silica structure
at lower W/F values. Mass spectrometry (MS) is
a very useful technique to reveal the low frag-
mentation of the monomer in soft plasma condi-
tions and, on the contrary, the formation of many
light species due to strong fragmentation in
highly energetic plasmas.
Although considered as dense materials,
plasma polymers are characterized by a free vol-
ume comparable to ultramicroporosity (spaces
between chains lower than 0.7 nm). Changing
the plasma parameters in the preparation of
films can enable to tune this free volume as well
as the chains flexibility. The approaches that may
achieve enhanced free volume and chain flexibil-
ity can be summarized as follows: (1) minimiza-
tion of the W/FM parameter, (2) pulsing of the RF
field to reduce the plasma-on time, (3) use of a
Faraday cage around the substrate, (4) positioning
the sample downstream from the plasma zone
(post-discharge configuration), (5) use of mono-
mers containing polymerizable double bonds,
and (6) use of a cold substrate. It is possible to
further increase the free volume and change it
into micro- (pores diameter between 0.7 and
2 nm) or meso- (pores diameter of some nanome-
ters) porosity by adding a porogen in the plasma
reactor as comonomer and then eliminating it
from the prepared film by thermal or UV
posttreatment (Favennec et al. 2004; Rouessac
et al. 2006). The porogen approach is mainly
applied to polymer-like plasma films. Indeed,
ceramic-like plasma materials are usually
required for their highly dense structure; never-
theless, they sometimes naturally contain some
microporosity because of chain breakings due to
very high cross-linking degrees (Roualdes
et al. 2002).
For membrane applications, plasma polymer-
ization is usually performed on a highly porous
substrate whose only role is to mechanically sup-
port the thin plasma polymer, called plasma-
polymerized membrane in this case. Neverthe-
less, plasma polymerization can also be applied
on a dense or poorly porous substrate being
already an active membrane; in this case, it
could achieve the same effect as plasma etching
or plasma functionalization (i.e., modification of
surface characteristics of the membrane sub-
strate) with additional advantageous characteris-
tic features of the nanometer film of plasma
polymer. Moreover, a special kind of plasma
polymerization that has received increased
Plasma Polymerization
attention in recent years is the preparation of
plasma polymers by radio-frequency sputtering
from polymeric targets. Most attention is paid to
fluorocarbon plasma polymer films sputtered
from polytetrafluoroethylene (PTFE) using mag-
netrons (Finsterwalder and Hambitzer 2001). The
main advantage of this innovating process is that
the deposition rate and the organization of the
chains of the material structure are much higher
than in the case of classical plasma polymers.
While the activation mechanism is very different
from that of the classical plasma polymerization,
the deposition mechanism is not.
References
Ayral A, Julbe A, Rouessac V, Roualdes S, Durand
J (2008) Microporous silica membrane – basic princi-
ples and recent advances, Chapter 2. In: Malada R,
Menendez M (eds) Membrane science and technology,
vol 13. Elsevier, Amsterdam, pp 33–79
3
Favennec L, Jousseaume V, Rouessac V, Fusalba F,
Durand J, Passemard G (2004) Porous extreme low
k(ELk) dielectrics using a PECVD porogen approach.
Mater Sci Semicond Process 7:277–282
Finsterwalder F, Hambitzer G (2001) Proton conductive
thin films prepared by plasma polymerization.
J Membr Sci 185:105–124
Lam DK, Baddour RF, Stancell AF (1976) A mechanisms
and kinetics study of polymeric thin-film deposition in
glow discharge. J Macromol Sci Chem
A10(3):421–450
Poll HU, Arty M, Wickleder KH (1976) Reaction kinetics
in the polymerization of thin films on the electrodes of
a glow-discharge gap. Eur Polym J 12:505–512
Roualdes S, Sanchez J, Durand J (2002) Gas diffusion and
sorption properties of polysiloxane membranes pre-
pared by PECVD. J Membr Sci 198(2):299–310
Rouessac V, Puyrenier W, Broussous L, Rebiscoul D,
Ayral A (2006) How ellipsometry can characterize a
gas diffusion barrier. In: Bredesen R, Raeder H (eds)
Proceedings of the 9th international conference on
inorganic membranes (ICIM9), Lillehammer,
25–29 June, pp 484–487
Yasuda H (1985) Plasma polymerization. Academic,
Orlando
P
Plasma Polymerized Membrane
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier cedex 5, France
Plasma-polymerized membrane names a plasma
polymer deposited on a highly porous substrate
(which plays the role of mechanical support)
having specific separation properties.
The high degree of flexibility in free volume
and chemical structure of plasma-polymerized
membrane (see entry “▶ Plasma Polymeriza-
tion”) makes them good candidates as membrane
materials. Plasma polymers have been used as
membrane materials since the 1980s; the first
reported study was from Yasuda (Yasuda 1984).
Their main advantages in such an application
field are their high cross-linking degree giving
them high separation efficiency as well as high
chemical and thermal stabilities and their small
and easily tunable thickness enabling a modula-
tion of their permeation ability. As plasma poly-
mers are not self-supported, they must be
deposited onto symmetric or asymmetric support
with a surface pore size and a surface roughness
that should be in agreement with the deposited
thickness. This support primarily acts as a
mechanical support. The plasma polymerization
technique cannot deposit thin films on the pore
walls inside porous substrates like it can be done
by counter diffusion CVD, but plasma
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1229-4
polymerization is able to modify the mouth of
the pores at the surface of substrates, especially
if the latter is macroporous (pores diameter above
50 nm). In that case, the final membrane proper-
ties depend both on the plasma polymer and on
the starting support as the applied plasma poly-
merization process duration is not enough to
make a complete and homogeneous layer. In the
case of a complete homogeneous layer, the trans-
port properties will be mainly governed by the
intrinsic separation properties of the plasma
polymer.
The first developed plasma-polymerized
membranes have been intended to gas permeation
or retention (Inagaki and Tsutsumi 1986; Inagaki
et al. 1990; Roualdes et al. 2002; Julbe
et al. 2008) and also pervaporation; more
recently, plasma-polymerized membranes have
been prepared for liquid separation processes
(nanofiltration and ultrafiltration essentially)
(Roualdes et al. 2010). For gas or liquid separa-
tion, membranes providing high fluxes of pene-
trants are required. Polymer-like plasma films are
more suitable in this case. If the plasma film does
not totally plug the porosity of its support, the
transport properties across the membrane will be
controlled by the viscous flow. If the plasma film
constitutes a complete homogeneous layer at the
surface of its support, the transport properties of
the membrane will be mainly governed by the
solution diffusion, microporous surface diffu-
sion, or molecular sieving mechanisms inherent
to the plasma polymer. Being highly cross-linked
2 Plasma Polymerized Membrane
in essence, polymer-like plasma materials are
generally not as permeable as conventional mem-
branes. In order to enhance their permeability, the
easiest solution consists in reducing their thick-
ness, to the detriment of their mechanical stabil-
ity. Another solution is to increase their free
volume and/or chain flexibility to make them
resemble more conventional polymers. For gas
retention (packaging application essentially),
membranes providing low fluxes of penetrants
are required. Ceramic-like plasma films are
more suitable in this case; their transport proper-
ties are rather controlled by the molecular sieve
mechanism as for classical crystallized ceramics.
The development of polymer-like plasma
films has been more recently applied to fields
using ion-conducting membranes such as
electromembrane processes (electrodialysis in
particular), electrochemical sensors, or, more
broadly, the energy production devices (fuel
cells, Li-ion batteries, etc.) (Roualdes
et al. 2010). Such applications require the use of
materials having a good swelling in water and
containing specific functions, often charged, dis-
tributed in an ordered manner in order to form
effective channels of ionic conduction. Obtaining
such materials by plasma polymerization is par-
ticularly challenging and requires a delicate
research task in the choice of the precursor
(s) and the adjustment of plasma parameters.
References
Inagaki N, Tsutsumi D (1986) Plasma-polymerization of
F-propene/acetylene and F-propene/ethylene mixtures
and their gas permeability. Polym Bull 16:131–136
Inagaki N, Tasaka S, Park MS (1990) Gas separation
membrane made by plasma polymerization of
1,3-ditrifluoromethylbenzene/CF4 mixture. J Appl
Polym Sci 40:143–153
Julbe A, Rouessac V, Durand J, Ayral A (2008) New
approaches in the design of ceramic and hybrid mem-
branes. J Membr Sci 316:176–185
Roualdes S, Sanchez J, Durand J (2002) Gas diffusion and
sorption properties of polysiloxane membranes pre-
pared by PECVD. J Membr Sci 198(2):299–310
Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
membrane science and engineering, vol 1. Academic,
Oxford, pp 159–197
Yasuda H (1984) Plasma polymerization for protective
coatings and composite membranes. J Membr Sci
18:273–284
V
Vapor Plasma Membrane Treatment
Stephanie Roualdes
IEM/UM II – CC 047, Place Eugene Bataillon,
Montpellier, France
Plasma processes (Yasuda 1985; d’Agostino
1990; Biederman and Osada 1992; Inagaki
1996) were initially developed for microelectron-
ics in the 1950s. They represent a clean
(producing few or not effluents) and also
extremely flexible technology whose basic equip-
ment, well adapted to automation, makes it pos-
sible to achieve goals as various as singular in
terms of specific properties of use; their costs of
operation are moreover relatively weak. Based on
these advantages, they are used today in many
fields of the materials chemistry (in particular the
membranes field) even if their industrialization
still remains not very developed, because of the
high cost of the equipment necessary to their
implementation and of a certain conservatism of
the industrialists reticent to introduce this new
technology, however so promising.
Defined by Crookes in 1879 as the fourth state
of the matter, a plasma is a partially ionized and
overall neutral medium generated by the applica-
tion of an electric field to a gas phase at low
pressure (<10 Torr). The energy of the applied
electric field is transferred to free electrons which
collide with the gas molecules. Such inelastic
impacts make electrons achieve enough energy
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1230-3
(up to 50 eV) to induce the ionization of gas
molecules. Such ionized species (acquiring ener-
gies typically in the range of 0–2 eV) initiate a
high number of complex reactions (ionization,
excitation, neutralization, recombination,
deexcitation, etc.) constituting what is called a
glow discharge. A glow discharge implies a
high variety of species: electrons, negative and
positive ions, radicals, neutral atoms and mole-
cules, and also photons (emitted by radiative
deexcitation) whose mixture constitutes the
plasma state. A plasma is essentially character-
ized by its energy and its electronic density.
Depending on the values of both microscopic
parameters, different kinds of natural or artificial
plasmas can be distinguished, being classified in
two categories: hot plasmas and cold plasmas.
Artificial plasmas, generated by a low frequency
(25–450 kHz), radio frequency (1–500 MHz), or
microwave (500 MHz–some GHz) continue or
alternative discharge at rather low pressure
(10–2–10 Torr), are cold plasmas. Cold plasmas
are characterized by energy and electronic den-
sity equal to 1–10 eV and 1,010 cm 3, respec-
tively. Their ionization degree is lower than 10 3
so that the gas phase is mainly made up of neutral
species in an excited state (radicals).
A characteristic of these plasmas is the absence
of thermodynamic balance between the elec-
tronic temperature (several thousands of degrees)
and that of gas (near to the ambient).
The interaction between a cold plasma and a
material placed within it (substrate) results in
2 Vapor Plasma Membrane Treatment
several types of effects occurring simultaneously
or consecutively. Four major effects are generally
distinguished: plasma etching, plasma functiona-
lization, plasma cross-linking, and/or formation
of a deposit on the surface of the substrate
(PECVD/plasma polymerization). The preva-
lence of one of these effects on the others is
directly related to the nature of the gas subjected
to the electric discharge. In the case of plasmas
involving noncondensable gases (monoatomic or
diatomic gases), the three principal effects are
etching, functionalization, and cross-linking; the
substrate undergoes surface modifications only.
In the case of plasmas involving condensable
gases (organic, inorganic, or organometallic
compounds), the dominating effect is the forma-
tion, on the surface of the substrate, of a deposit
made up of a three-dimensional matrix formed
from fragments of the reagent gas combined in a
random way. The related plasma process is called
plasma-enhanced chemical vapor deposition
(PECVD) or plasma polymerization in the partic-
ular case of gases of organic compounds.
For details about plasma treatment applied to
membrane materials, see the articles entitled
“plasma etching,” “plasma functionalization,”
“PECVD,” “plasma polymerization,” “plasma
membrane,” and “plasma polymerized
membrane.”
References
Biederman H, Osada Y (1992) Plasma polymerization
processes. Elsevier, Amsterdam
d’Agostino R (1990) Plasma deposition, treatment and
etching of polymers. Academic, New York
Inagaki N (1996) Plasma surface modification and plasma
polymerization. Technomic Publishing, Lancaster
Yasuda H (1985) Plasma polymerization. Academic,
Orlando
A
Artificial Brain Model: Biohybrid
Membrane System
Sabrina Morelli
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende, CS,
Italy
Artificial brain, in membrane operation, is a
biohybrid membrane system which provides suit-
able conditions for the creation of a biomimetic
microenvironment for neuronal tissue engineer-
ing resembling in vivo neuronal tissue properties
and functions.
In the last decade, neuronal cell behavior on
biomaterial such as membrane has become of
great interest since it offers the advantage of
developing neuronal tissue that may be used for
the in vitro simulation of human brain function
substitute. This could provide further insights not
only into the cell but also in developing therapies
in neurodegenerative disorders such as
Parkinson’s or Alzheimer’s diseases.
A biohybrid system using neurons could also
represent a useful instrument for predictive drug
testing or constitute a future model of a
bioneuronal network device. To accomplish this
task the artificial membrane must exhibit a spe-
cific micro-architecture able to stimulate neuro-
nal regeneration, therefore supporting axonal
regrowth and affecting cellular orientation and
differentiation in a positive way.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1231-2
This biohybrid artificial system consisting of
neurons and membranes offers a valuable tool for
studying neuronal cell behavior and fundamental
questions in neuroscientific research, and it also
could be used in a wide range of biotechnological
applications.
Several works in the literature show evidence
that semipermeable polymeric membranes in flat
and hollow fiber configurations, thanks to their
highly selective structural, physicochemical, and
transport properties, allow the successful in vitro
reconstruction of neuronal tissue reproducing a
tissue model for studying metabolic diseases and
drug effects (De Bartolo et al. 2008; Zhang
et al. 2005 Morelli et al. 2014; Piscioneri et al.
2015).
For typical neuronal tissue-engineered con-
structs, the properties of the material components
relevant to the tissue response include the surface
microgeometry, the MWCO, the electrical prop-
erties, possibly the bioactive factors that are
loaded and sustainedly released through the chan-
nel wall, and the degradation rate for biodegrad-
able materials. The wettability of the membrane
surface has proved to be a factor that affects the
growth of neurons modulating the adsorption of
adhesion proteins contained in the culture
medium or secreted by cells that mediate the
adhesion of cells to the substrate.
Advances in polymer chemistry have facili-
tated the engineering of synthetic membranes
that can be specifically manipulated with regard
2 Artificial Brain Model: Biohybrid Membrane System
to their physical and mechanical characteristics,
which may affect the interactions with cells.
The influence of topographical features on
neuronal cell adhesion and differentiation has
been studied by using patterned adhesive areas
that provide only a fraction of the surface for cell
adhesion while the rest is cell repellent or by
using contact guidance cues in combination
with also nerve growth factors or an electric
field. Topographic guidance of neuritis out-
growth has been explored in vitro with a culture
substrate containing etches, microchannels,
nanotubes, or microgrooves. Micro-patterned
biodegradable poly(L-lactic acid) membranes
directly improved the guidance of neurite exten-
sion and thereby enhanced their orientation with
a consequently highly ordered neuronal cell
matrix, which may have strong bearings on the
elucidation of regeneration mechanisms (Morelli
et al. 2010).
Hippocampal neurons exhibited a different
morphology in response to varying the properties
of the membrane surface. Indeed, cells grown on
the smoother membranes such as fluorocarbon
(FC) and PES membranes displayed a large num-
ber of neuritis with consequent formation of bun-
dles. The density of axonal network increases the
neurites to become more elaborate and highly
branched on the smoother surfaces.
The importance of FC membrane culture sub-
strates toward the highlighting of the effects of
highly preferred GABAAR a2,5 agonists and
inverse agonists on the successful elongation of
neuronal processes and transcriptional activities
of hamster hippocampal Gluergic cells was dem-
onstrated for the first time (Giusi et al. 2009).
A biohybrid system composed of neuronal
cells and silicon-supported nanoporous mem-
branes has been designed to facilitate control of
the biochemical environment of neuronal net-
works with cellular resolution. Nanoporous
membranes may be used to interface with biolog-
ical materials in a biohybrid system, for example,
as an artificial chemical synapse interface
(Wolfrum et al. 2006).
Compared to traditional two-dimensional
(2D) culture systems, 3D in vitro cultures of
neuronal cells appear to better mimic in vivo
neuronal microenvironments representing a
great potential for building 3D neuronal circuits
as well as for creating tissue-based biosensors
and for promoting systemic restoration of severe
nerve injuries. In this context, several studies
have been performed toward the determination
of differences between 2D and 3D environments
for neuronal function in order to provide great
benefit to neuroengineering efforts. Recently, a
complete 3D neural tissue-like structure has been
assembled in vitro using primary hippocampal
cells and PAN HF membranes. As a conse-
quence, this advanced model system could
allow the mimicking of hippocampal neuronal
events in order to study natural neurobiological
properties of these cells, such as memory and
learning processes, or the induction of disease
pathologies, allowing testing of new therapies
on the resolution of these states (Morelli
et al. 2012).
In the last decade, with rapid advances in
biomaterial technology, several types of natural
and synthetic biodegradable polymer, including
collagen, chitosan, poly(glycolic acid), poly
(L-lactic acid), poly(L-lactide-co-glycolide),
poly(caprolactone), and polyurethane, have
been reported as suitable for nerve regeneration,
although the ideal physicochemical composi-
tions, surface structure, and functionalization of
such materials have not yet been found. It was
recently reported that polycaprolactone-based
membranes successfully supported outgrowth
and differentiation of human neuronal cells
(Morelli et al. 2015).
References
De Bartolo L, Rende M, Morelli S, Giusi G, Salerno S,
Piscioneri A, Gordano A, Di Vito A, Canonaco M,
Drioli E (2008) Influence of membrane surface prop-
erties on the growth of neuronal cells isolated from
hippocampus. J Membr Sci 325:139–149
Giusi G, Facciolo RM, Rende M, Alo R, Di Vito A,
Salerno S, Morelli S, De Bartolo L, Drioli E, Canonaco
M (2009) Distinct a subunits of the GABAA receptor
are responsible for early hippocampal silent neuron-
related activities. Hippocampus 19:1103–1114
Morelli S, Salerno S, Piscioneri A, Papenburg BJ, Di
Vito A, Giusi G, Canonaco M, Stamatialis D,
Artificial Brain Model: Biohybrid Membrane System
Drioli E, De Bartolo L (2010) Influence of micro-
patterned PLLA membranes on outgrowth and orien-
tation of hippocampal neurites. Biomaterials
31:7000–7011
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C,
Tasselli F, Di Vito A, Giusi G, Canonaco M, Drioli E,
De Bartolo L (2012) Flat and tubular membrane sys-
tems for the reconstruction of hippocampal neuronal
network. J Tissue Eng Regen Med 6:299–313
Morelli S, Piscioneri A, Messina A, Salerno S, Al-Fageeh
MB, Drioli E, De Bartolo L (2015) Neuronal growth
and differentiation on biodegradable membranes.
J Tissue Eng Regen Med. 9:106–117
Morelli S, Piscioneri A, Salerno S, Al-Fageeh M, Drioli E,
De Bartolo L (2014) Neuroprotective Effect of
3
Didymin on H2O2-Induced Injury in Neuronal Mem-
brane System. Cells Tissues Organs 199:184–200
Piscioneri A, Morelli S, Mele M, Canonaco M, Bilotta E,
Pantano P, Drioli E, De Bartolo L (2015)
Neuroprotective effect of human mesenchymal stem
cells in a compartmentalized neuronal membrane sys-
tem. Acta Biomaterialia 24:297–308.
Wolfrum B, Mourzina Y, Sommerhage F, Offenhausser
A (2006) Suspended nanoporous membranes as inter-
faces for neuronal biohybrid systems. Nano Lett
6:453–457
Zhang N, Yan H, Wen X (2005) Tissue-engineering
approaches for axonal guidance. Brain Res Rev
49:48–64
A
Artificial Kidney
Sabrina Morelli
Institute on Membrane Technology, ITM-CNR,
National Research Council of Italy, Rende CS,
Italy
Artificial kidney, a ▶ synonym for
▶ hemodialyzer, is an extracorporeal device
through which blood may be circulated for
removal of elements that normally are excreted
in the urine.
The artificial kidney is used to rid the blood of
metabolic products, to correct electrolyte-water
and acid-alkaline balances in acute and chronic
renal insufficiency, to remove dialyzing toxic
substances in cases of poisoning, and to remove
excess water in cases of edema. In 1913 the
American scientist Abel created an apparatus
for dialysis that was the basis for the artificial
kidney; Dr. Willem Kolff, a Dutch physician,
constructed the first functioning artificial kidney.
He treated his first patient in 1943, and in 1945 he
was first able to save a patient’s life with hemo-
dialysis treatment.
The artificial kidney operates on the principle
of the dialysis of substances through a semiper-
meable membrane. Dialysis is a result of the
differences in the concentrations of substances
in the blood and in the dialyzing solution, which
contains glucose and the principal electrolytes of
the blood in nearly physiological concentrations
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1232-2
without containing any of the substances that
must be removed from the body (urea, creatinine,
uric acid, sulfates, phosphates). Proteins, formed
elements of the blood, bacteria, and substances
with a molecular weight of more than 30,000, do
not pass through the membrane. During hemodi-
alysis the patient’s blood is drawn off through a
catheter by a pump from the inferior vena cava
and passed inside the chambers of membranes of
the dialyzer; these chambers are washed outside
by the dialyzing solution, which is supplied by
another pump. Partially purified, the blood is
returned to one of the surface veins.
The membrane used during hemodialysis has
evolved significantly since the earliest reports.
Early membranes were natural materials, such
as cellulose, or simple synthetic compositions,
such as polysulfone, with symmetric structures
and good performance for small solute passage
(Fleming 2011).
However, these membranes include signifi-
cant interactions with the complement pathway
and immune response. Modifying the hydroxyl
groups on cellulose membranes gives similar per-
formance characteristics and less bioactivity and
includes cellulose diacetate and hemophan mem-
branes. With improvements in chemical engi-
neering and manufacturing, cellulose-based
membranes have yielded to synthetic mem-
branes. The most popular membranes in use
today are polyacrylonitrile and polysulfone; how-
ever, polyamide, polycarbonate, and polymethyl-
methacrylate are available. These materials have
2 Artificial Kidney
improved biocompatibility and reduce comple-
ment activation; however, they may enhance pro-
tein adsorption to the membrane in the absence of
further modification. Despite the improved com-
patibility of synthetic membranes, the most
recent large review does not demonstrate benefits
conveyed by biocompatibility. The ultrastructure
of membranes is predominantly the capillary
design, or hollow fiber structure, in which blood
flows through a series of small tubes held together
in a bundle. This allows for a low-resistance, high
surface area membrane. Membrane properties
such as charge, wall thickness, and pore size
affect function. The radius of the pore is related
to the ultrafiltrate flow through the membrane,
but overall fluid transfer is a function of the
mean pore size. The number or density of pores
and the radius of the pore affect solute transfer in
diffusive clearances. Membrane characteristics
such as flux and permeability to water are deter-
minants of pore characteristics and wall thickness
(Vigano et al. 2008).
As dialysis membrane technology has
improved, high-flux membranes with larger pore
sizes have been developed to allow greater clear-
ances of larger retention molecules with reduced
induction of inflammatory mediators. While
observational studies suggest that high-flux
hemodialysis is associated with lower and
dialysis-related amyloidosis, individual random-
ized controlled trials have not confirmed that
high-flux hemodialysis improves clinical out-
comes. High-flux dialysis membranes have larger
pore sizes that may increase transportation of
dialysate impurities or contaminants from the
dialysate to the bloodstream even when the dial-
ysate quality complies with acceptable standards,
although some evidence suggests that high-flux
membranes may actively absorb endotoxins and
impede their back transfer from dialysate into the
bloodstream (Palmer and Strippoli 2013).
Although dialysis is currently an available
treatment for chronic renal disease, it replaces
only the filtration function of the kidneys, and
thus, it is associated with a number of complica-
tions and is not a permanent solution. Kidney
transplantation performed in a heterotopic loca-
tion is the only definitive solution for end-stage
renal failure. A potential solution to ease the
demand for donor kidneys may be the use of
tissue engineering techniques that could be used
to develop functional kidneys. A primary chal-
lenge in renal tissue engineering, however, is the
production of tissues with the functional com-
plexity required for kidney transplantation. The
first step in achieving this aim could be to pro-
duce acellular kidney matrices for use as biolog-
ical scaffolds that support cell growth and
facilitate new tissue formation by potentiating
cell–cell interaction. Several groups have used
different perfusion-based decellularization proto-
cols to produce naturally derived kidney scaf-
folds (Arenas-Herrera et al. 2013).
In the last decade, several studies have been
performed on the development of the implantable
artificial kidneys, but these studies reported only
developmental concepts, in vitro or in vivo stud-
ies using small animals. It is difficult to control
certain research aspects of an implantable artifi-
cial kidney to a preclinical level, and these
aspects include long-term maintenance of the
antithrombogenic properties of the systems and
each of its components, and the function of an
implanted, miniaturized system, whose function
must be maintained for a year’s duration. Further
progress in nanotechnology and biotechnology is
required to realize a treatment with an implant-
able kidney (Saito et al. 2011).
New directions in dialysis research include
cheaper treatments, home-based therapies, and
simpler methods of blood purification. These
objectives may be probably obtained with inno-
vations in the field of artificial kidney through the
utilization of new disciplines such as miniaturi-
zation, microfluidics, and nanotechnology. This
research may lead to a new era of dialysis in
which the new challenges are transportability,
wearability, and why not the possibility to
develop implantable devices (Ronco et al. 2011).
References
Arenas-Herrera JE, Ko IK, Atala A, Yoo JJ
(2013) Decellularization for whole organ
Artificial Kidney
bioengineering. Biomed Mater 8:014106.
doi:10.1088/1748-6041/8/1/014106
Fleming GM (2011) Renal replacement therapy review.
Past, present and future. Organogenesis 7:2–12
Palmer SC, Strippoli G (2013) High-flux versus low-flux
haemodialysis membranes for end-stage kidney dis-
ease. Nephrology 18:313–314
Ronco C, Davenport A, Gura V (2011) The future of the
artificial kidney: moving towards wearable and mini-
aturized devices. Nefrologia 31:9–16
3
Saito A, Sawada K, Fujimura S (2011) Present status and
future perspectives on the development of bioartificial
kidneys for the treatment of acute and chronic renal
failure patients. Hemodial Int 15:183–192
Vigano SM, Di Filippo S, Manzoni C, Locatelli F (2008)
Membrane characteristics. In: Ronco C, Cruz DN (eds)
Hemodialysis-from basic research to clinical trials,
vol 161, Contribution of nephrology. Karger, Basel,
pp 162–167
E
Emulsification by Membrane
Operations
Emma Piacentini1 and Lidietta Giorno2
1
Institute on Membrane Technology (ITM-CNR)
c/o University of Calabria, Rende (CS), Italy
2
Institute on Membrane Technology
(ITM-CNR), National Research Council of Italy,
University of Calabria, Rende (CS), Calabria,
Italy
Emulsions can be generated using membrane
operations by: (i) direct membrane emulsifica-
tion, where a microporous membrane is used to
disperse one of two immiscible liquids as a form
of droplets into another liquid or by (ii) premix
membrane emulsification, where a course emul-
sion is extruded through the membrane pores in
order to generate fine droplet emulsion.
A pressure is required to cause the dispersed
phase to permeate through the membrane. If any
shear is applied on the membrane surface, drop-
lets can be spontaneously detached from the pore
outlets on the action of the interfacial tension
when they reach a certain size. The method is
referred as static membrane emulsification
(Kukizaki 2009). The shear on the membrane
surface can be generated by moving the continu-
ous phase or using moving membranes. The
method is referred as dynamic membrane emulsi-
fication. The shear stress is generated by the
continuous phase flowing tangentially to the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1233-1
membrane surface (cross-flow membrane emulsi-
fication) (Williams et al. 1998) or stirred (stirred
membrane emulsification) (Stillwell et al. 2007).
The use of static turbulence promoters in cross-
flow membrane emulsification allows increasing
the shear stress at the membrane surface while
maintaining a low value along the circuit out of
the membrane (Koris et al. 2011). Alternatively, a
periodic flow pulsation is generated in the con-
tinuous phase without recirculation (pulsed-flow
membrane emulsification) (Holdich et al. 2013).
Moving membranes can be used instead of the
commonly used stationary membranes. The drop-
let detachment from the membrane surface is
controlled by rotating (Vladisavljević and Wil-
liams 2006) or vibrating (Holdich et al. 2010) the
membrane within an otherwise static continuous
phase. Membrane operations used for the produc-
tion emulsion droplets are described in Table 1.
Emulsification by membrane operation is con-
trolled by:
• Membrane parameters, including porosity,
mean pore size, pore geometry, pore distance,
and membrane surface wettability
• Phase parameters, including interfacial ten-
sion, emulsifier type and concentration, vis-
cosity and density of dispersed and
continuous phases, phase composition, pH,
and ionic strength
• Process parameters, including wall shear
stress, transmembrane pressure, membrane
module configuration, and temperature
2 Emulsification by Membrane Operations

Emulsification by Membrane Operations, Table 1 Different membrane operations used for the production
emulsion droplets
Advantages Disadvantages
Dynamic membrane emulsification
Stirred ME Suitable for low volumes of continuous Emulsion production at batch scale
phase
Useful to study the effect of different The shear stress at the membrane surface is
experimental conditions on the emulsion nonuniform and depends on the cell geometry
preparation

Cross-flow ME Constant shear stress at the membrane Emulsion droplet breakup as a consequence
surface of the recirculation
Suitable for large-scale production and High dispersed phase concentration is
continuous or semicontinuous operation obtained after a long time of operation

Cross-flow ME with Constant shear stress at the membrane High dispersed phase concentration is
static promoter surface obtained after a long time of operation
Suitable for large-scale production and
continuous or semicontinuous operation
Suitable to prevent droplet breakup

Pulsed-flow ME Suitable for large-scale production and –

continuous or semicontinuous operation
Able to prevent droplet breakup
High dispersed phase concentrations
obtained in a single pass

Rotating ME Suitable for large-scale production and Complicated and more expensive design
continuous or semicontinuous operation Higher power consumption
Able to prevent droplet breakup
High dispersed phase concentrations
obtained in a single pass

Vibrating ME Suitable for large-scale production and
continuous or semicontinuous operation
Able to prevent droplet breakup
Complicated and more expensive design
Higher power consumption
Nonuniform temporal distribution of shear
stress on the membrane surface

(continued)
Emulsification by Membrane Operations
Emulsification by Membrane Operations, Table 1 (continued)
Advantages
Static membrane emulsification
Simple experimental setup
Low energy input
Able to prevent droplet breakup
Comparing to the conventional emulsification
processes, emulsification by membrane operation
permits to obtain a better control of droplet size
and droplet size distribution, low energy and
material consumption, and modular and easy
scale-up. Nevertheless, productivity (m3/day) is
much lower, and therefore the challenge in the
future is the development of new membranes and
innovative membrane operations to keep the
known advantages and maximize the
productivity.
References
Holdich RG, Dragosavac MM, Vladisavljevic GT,
Kosvintsev SR (2010) Membrane emulsification with
oscillating and stationary membranes. Ind Eng Chem
Res 49:3810–3817
Holdich RG, Dragosavac MM, Vladisavljevic GT,
Piacentini E (2013) Continuous membrane
3
Disadvantages
Emulsion production at batch scale
The production of uniform droplets is
possible only at low dispersed phase flux with
low productivity
emulsification with pulsed (oscillatory) flow. Ind Eng
Chem Res 52:507–515
Koris A, Piacentini E, Vatai G, Bekassy-Molnar E,
Drioli E, Giorno L (2011) Investigation on the effects
of a mechanical shear-stress modification method dur-
ing cross-flow membrane emulsification. J Membr Sci
371:28–36
Kukizaki M (2009) Shirasu porous glass (SPG) membrane
emulsification in the absence of shear flow at the
membrane surface: influence of surfactant type and
concentration, viscosities of dispersed and continuous
phases, and transmembrane pressure. J Membr Sci
327:234–243
Stillwell MT, Holdich RG, Kosvintsev SR, Gasparini G,
Cumming IW (2007) Stirred cell membrane emulsifi-
cation and factors influencing dispersion drop size and
uniformity. Ind Eng Chem Res 6:965–972
Vladisavljević GT, Williams RA (2006) Manufacture of
large uniform droplets using rotating membrane emul-
sification. J Colloid Interface Sci 299:396–402
Williams RA, Peng SJ, Wheeler DA, Morley NC,
Taylor D, Whalley M, Houldsworth DW (1998) Con-
trolled production of emulsions using a crossflow
membrane, part II: industrial scale manufacture.
Chem Eng Res Des 76:902–910
C
Controlled Drug Release
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Controlled drug release is defined as delivery of a
drug to a specific site, in specific time and release
pattern. Controlled drug release eliminates over-
or underdosing, maintains drug levels in desired
range, needs less dosing, prevents side effects,
and increases patient compliance. Most of the
commercially available systems for controlled
release of drugs rely on membranes where drug
release is generally controlled by (1) osmotic
pumping or (2) solution–diffusion mechanism.
Pills, implants, and patches are commonly used
dosage forms to deliver drugs where drug release
is controlled by diffusion through a rate-limiting
membrane. Pills are prepared by pressing the
drug into a tablet and then coating with a water-
insoluble or water-soluble polymeric membrane,
such as hydroxylpropyl methylcellulose,
ethylcellulose, povidone, or polyethylene glycol.
Tablets are also coated with a membrane to pro-
tect drugs against decomposition in the acid envi-
ronment of the stomach. Commonly used
polymers for this purpose are cellulose acetate
trimellitate (CAT), hydroxypropylmethyl-
cellulose phthalate (HPMCP), polyvinyl acetate
phthalate (PVAP), and cellulose acetate phthalate
(CAP). Implants are used to deliver drug at a
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1234-2
particular site and contain drug in liquid or pow-
der form in a reservoir surrounded by a semiper-
meable membrane to allow slow release of the
drug. The membrane can be made from a degrad-
able or nondegradable polymer, and the release is
controlled by rate of diffusion and degradation.
Patches are typical membrane-controlled reser-
voir systems and frequently used for controlled
drug delivery. In ocular patches, a drug is
enclosed by two release-controlling polymer
membranes, and through diffusion, drug is deliv-
ered to the target area. Transdermal patches are
used to deliver drugs with low solubility since the
skin has a large surface area. The simplest patch
consists of a drug-containing reservoir placed
between an impermeable backing layer and a
membrane. The total resistance to drug perme-
ation is controlled by sum of the resistances in the
membrane and the skin. In the case of passive
drug transport where the drug concentration dif-
ference between the patch and the skin is main
driving force, the release rate of the drug may
vary significantly from patient to patient due to
strong variations in skin permeability. In order to
provide an effective rate control and to ensure
that drug delivery does not depend on patient or
patch position, the permeability of membrane
should be less than that of the skin, i.e., the
release rate should be controlled by the mem-
brane. To expand the spectrum of transdermally
deliverable drugs, chemical permeation
enhancers, microneedles, ultrasound, heat, or
short- or high-voltage bursts of electricity are
2 Controlled Drug Release
temporarily applied to the skin to disrupt its bar-
rier function. Alternatively, drugs can be deliv-
ered by iontophoresis, in which small amounts of
electrical current are applied through the skin to
allow delivery of charged drug molecules into the
body. The device consists of two patches: one of
them contains a drug reservoir, while the other
patch contains reference electrolyte or gel. The
drug placed in the patch electrode which has the
same charge as the drug is delivered into the skin
by electrostatic repulsion when electric current is
applied. The rate of transport of a charged drug
during iontophoresis is controlled by passive dif-
fusion, migration due to electric current applied,
and electroosmosis due to bulk fluid flow in the
same direction as the flow of the counter ions. In
addition to classical polymers, intelligent,
stimuli-responsive polymers are also used as
membrane material for controlling the release
rate of drugs through the membrane. For exam-
ple, hydrogel membranes manufactured from
glucose-containing copolymers could respond to
the dynamic changes in external glucose concen-
tration, and this response can be used to control
the release of insulin through the hydrogel mem-
brane (Obaidat and Park 1997).
Reference
Obaidat AA, Park K (1997) Characterization of protein
release through glucose-sensitive hydrogel mem-
branes. Biomaterials 18:801
C
Controlled Delivery
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
The benefit of a drug can be enhanced when
controlled delivery of a drug to a targeted tissue
becomes possible. After release, the drug enters
the systemic circulation and distributes according
to its relative affinities to all tissues, and only a
small fraction of the drug is delivered to the target
site. Accumulation in tissues not associated with
drug causes side effects. Controlled delivery to
the target tissue eliminates side effects and allows
to reduce drug dosing to reach the desired effect.
The need for controlled targeted delivery is obvi-
ous in chemotherapy, for example, where painful
side effects of the drugs on healthy cells can be
eliminated by directly delivering the drug to the
target cells. Other examples include drug deliv-
ery to the eye, lung, brain, and coronary arteries
and release of growth and angiogenesis factors
from surgically implanted tissue-engineered
constructs.
The eye cavity is used to deliver antibiotics
and drugs. Ophthalmic inserts made from solu-
ble, insoluble, and bioerodible polymers are cur-
rently available. Insoluble inserts can be
categorized as diffusional, osmotic, and contact
lens. Polyvinyl alcohol, hydroxypropylcellulose,
polyvinylpyrrolidone, and hyaluronic acid are
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1235-2
commonly used for constructing degradable
inserts, while nondegradable inserts are
manufactured from ethylene-vinyl acetate copol-
ymers and styrene-isoprene-styrene block copol-
ymers. The contact lenses are not only used for
correcting vision but also act as potential drug
delivery device by presoaking them in drug solu-
tions. Conventional eye drops are not efficient
since most of it is lost due to overflow. To
increase drug retention in the cavity and bioavail-
ability, drug delivery product Ocusert ® was
developed. In this system, a reservoir filled with
a saturated concentration of drug was placed
between two membranes that can control release
of drug by the partition/diffusion mechanism.
This product was placed under the lower eyelid
and released drug at constant rate into the tear
fluid for up to 1 week. Another commercial prod-
uct, Lacrisert ® is a soluble insert used for the
treatment of dry eye syndrome. The device is
composed of hydroxypropyl cellulose and slowly
dissolves over 6–8 h to stabilize and thicken the
tear film.
In addition to the eye, inserts are also used for
targeted controlled delivery of drugs to various
tissues. ATRIDOX™ is an FDA-approved product
designed for the treatment of periodontal disease.
Upon injection into the periodontal cavity, drug
delivery depot is formed and delivers the antibi-
otic to the cavity. DUROS® implants are
nondegradable, osmotically driven systems and
used for the delivery of small drugs, peptides,
proteins, and DNA for up to 1 year. Viadur ® is
2 Controlled Delivery
another commercial implant used for treatment of
advanced prostate cancer.
Drug-eluting stents were developed to prevent
restenosis or reclosing of coronary arteries. In
these systems, the implantable metal stents are
coated with small amounts of anti-inflammatory
and antiproliferative drugs that are released
directly into the arterial tissue by dissolution,
partitioning, and diffusion. The release rate is
influenced by the thickness of the coating, type
of the coating material, and diffusivity and solu-
bility of drug in the coating material.
Nanocarriers are alternative systems for
targeted controlled drug delivery since they are
less cleared than free drugs and they may also
have favorable distribution properties into target
tissues. Targeting ligands can be incorporated
into the nanoparticles, and they permit particles
to bind specific cells and promote the cell uptake
and release of drug into the cells. Drug-loaded
nanoparticles can easily reach to target tumor
tissues since tumors have leaky capillaries that
permit the passage of nanoparticulates.
Microemulsions, liposomes, dendrimers, block
polymer micelles, and solid lipid and polymer
nanoparticles are typical examples of
nanocarriers.
C
Controlled Release
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Controlled-release technologies are developed to
deliver drugs, proteins, pesticides, fragrances,
and other bioactive agents at a controlled rate
for a desired time period to maintain a constant
and effective level of an active ingredient.
Controlled-release formulations provide greater
efficacy, convenience, and improved safety by
maintaining optimal concentrations of the active
ingredient. Many controlled-release technologies
operate by diffusion of the active ingredient or
water through a rate-controlling membrane and
can be classified into four categories: (1) reservoir
types, (2) matrix systems, (3) swelling-controlled
systems, and (4) osmotic systems.
In reservoir (membrane) systems, the bioac-
tive agent is either encapsulated by two semiper-
meable membranes or core containing the active
ingredient is surrounded by a semipermeable
membrane. Diffusivity and solubility of the
active ingredient in the membrane are two key
parameters that influence the rate of diffusion
through the membrane. The size and shape of
the active ingredient, the packing density, and
the flexibility and crystallinity of polymer chains
affect the diffusivity in the membrane. Solubility
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1236-1
of the active ingredient in the polymer depends
on its interaction with the membrane material.
In matrix (monolithic) systems, the bioactive
agent is incorporated in a polymer either in
dissolved or dispersed form. When the active
ingredients are in liquid form, they are typically
dissolved in polymer matrices, while solid ingre-
dients are dispersed in the polymer. Release of
the agent occurs by diffusion through the polymer
matrix and solubility of the agent becomes a
controlling factor.
Osmotic controlled-release systems are
reservoir-type systems except that the release of
the active agent depends on the diffusion of water
into the membrane. In these systems, a semiper-
meable membrane that is much more permeable
to water than to the active agent separates a core
with high osmotic pressure from a solution with
low osmotic pressure. Water penetration into the
core generates a hydrostatic pressure within the
core that forces the solution containing the active
ingredient out through the membrane. Water per-
meability of the rate-controlling membrane
determines the release rate of the active agent.
Swelling-controlled-release systems are simi-
lar to the design of matrix systems and usually
consist of an active ingredient dispersed through-
out a swellable polymer. In these systems, the
active ingredient is not released until the polymer
matrix is swollen since the diffusivity of the
active ingredient in the swollen matrix is several
orders of magnitude higher than its diffusivity in
the unswollen polymer.
2 Controlled Release
Controlled-release systems that are not depen-
dent on diffusion have also been developed. For
example, in the case of bioerodible systems, the
release rate is controlled by either polymer dis-
solution or a chemical reaction at the polymer
surface; therefore, geometric shape of the release
system is important. In pendant chain systems,
the active agent is bound to a polymer backbone
chain chemically and is released by hydrolytic or
enzymatic cleavage. The agent can be attached
directly or via a spacer group. The spacer group
can be used to affect the release rate and hydro-
philicity of the system. In a magnetically
controlled-release system, the active agent is uni-
formly dispersed within a polymer matrix. The
system releases the agent in a way typical of
diffusion-controlled matrix systems upon expo-
sure to aqueous media. On other hand, when the
system is exposed to an oscillating external mag-
netic field, the release rate becomes much higher.
Various types of polymers have been used in
the design of controlled-release systems. The
choice of polymer can affect diffusion and parti-
tion coefficients in diffusion-controlled systems,
the rate of erosion or hydrolysis in chemically-
controlled systems, permeation rates of solvents
in swelling-controlled systems, and mechanical
forces in magnetically controlled systems.
C

Controlled Release Kinetics K = partition coefficient of the active agent

through the membrane
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir When the concentration of the active ingredi-
Institute of Technology, Urla, Izmir, Turkey ent within the reservoir is less than its saturation
value, then the concentration difference through
the membrane decreases with time, and first-
The release of an active agent from controlled order release kinetics is observed which can be
release systems can be categorized into three expressed as follows:
types: (1) zero-order release kinetics, (2) t
1/2
 
kinetics, and (3) first-order kinetics. In reservoir dMt Cs ADK ADKt
(membrane) systems, the active ingredient is usu- ¼ exp
(2)
dt L VL
ally encapsulated between two semipermeable
membrane, and the release rate is controlled by where Cs is the saturation concentration of the
diffusion through the membrane. Reservoir sys- agent and V is the volume of the reservoir and
tems generally provide a zero-order release t is time.
where the release rate remains constant until all In matrix systems, active ingredients are
of the active ingredient has been delivered. The dissolved or dispersed through a polymer and
release kinetics from reservoir systems in the release rates from these systems decrease with
form of a flat sheet is described by the following time. Release kinetics from matrix systems
equation: containing dissolved active agents is described
by a combination of first-order and t
1/2 kinetics
dMt DC as follows (Baker and Londsdale 1974):
¼ ADK (1)
dt L
 
Mt dMt D 1=2
where ≺0:6 ¼ 2M1
M1 dt pL2 t
 2 
Mt = mass of the active agent released up to time t Mt dMt 8DM1 p Dt
 0:6 ¼ exp
2 (3)
A = surface area M1 dt L2
L
L = thickness of the rate-controlling membrane
D = diffusivity of the active agent through the where M1 is the total amount of active ingredient
membrane initially loaded into the matrix. When active
agent is dispersed throughout the polymer, t
1/2

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1237-1
2 Controlled Release Kinetics
kinetics is observed and the release rate is
predicted by Eq. 4 (Baker and Londsdale 1974):
 
dMt A DCms ð2C1
Cms Þ 1=2
¼ (4)
dt 2 t
where Cms is the saturation concentration of the
active ingredient in the polymer and C1 is the
concentration of active ingredient initially loaded
into polymer matrix.
Osmotic-controlled release which is usually
reservoir-type systems follow zero-order release
kinetics as long as the osmotic pressure gradient
through the membrane is constant. The release
rate of the active agent from these types of sys-
tems is defined with the following equation
(Theeuwes et al. 1983):
dMt APw DpCsa
¼ (5)
dt L
where Pw is the permeability of water through the
membrane, Dp is the osmotic pressure difference,
and Csa is the solubility of the active agent in the
membrane.
In swelling-controlled release systems, the
release rate depends on the degree of swelling
of the matrix which is influenced both by the
diffusion of solvent into the polymer and relaxa-
tion of the polymer chains. When diffusion is the
rate-controlling step, t
1/2 kinetics is observed
and the release controlled by relaxation follows
zero-order release kinetics (Alfrey et al. 1966).
References
Alfrey T, Gurnee EF, Lloyd WG (1966) Diffusion in
glassy polymers. J Polym Sci C 12:249
Baker RW, Londsdale HK (1974) Controlled release:
mechanisms and rates. In: Tanquary AC, Lacey RE
(eds) Controlled release of biologically active agents.
Plenum Press, New York, pp 15–72
Theeuwes F, Swanson D, Wong P (1983) Elementary
osmotic pump for ındomethacin. J Pharm Sci 72:253
C
Controlled Release by Membrane
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Many controlled-release systems commercially
available now are based on membrane technol-
ogy. These systems consist of a core containing
the drug surrounded by a thin polymer membrane
and transport of drug through membrane occurs
by a solution-diffusion mechanism. Drug mole-
cules first dissolve in the membrane and then
diffuse from interior part of the membrane to its
surface. The diffusive flux through the membrane
is described by Fick’s first law of diffusion.
@Cm
J ¼ D
@x
where D is the diffusivity of drug in the mem-
brane, J is the flux of the drug, and Cm is the
concentration of drug in the membrane. At the
membrane surface, drug molecules choose to
partition into either membrane or surrounding
medium. The partition coefficient gives a mea-
sure of the preference of drug molecules between
two phases. Defining the partition coefficient, K,
as the ratio of the concentration in the membrane
to the concentration in the solution, flux in Eq. 1
is rewritten as follows:
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1238-1
@C
J ¼ DK (2)
@x
where C is the concentration of drug in the sur-
rounding medium. Under steady-state conditions,
flux through the membrane is obtained by inte-
grating Eq. 2.
DC
J ¼ DK (3)
L
Controlled-release systems based on membranes
usually provide constant release rate as long as
the concentration of drug within core is at satu-
ration concentration. Deviations from constant
release kinetics occur depending on the storage
history of the release device. Time lag is observed
when the system is used shortly after being
manufactured while migration of the agent from
the core into the membrane due to long-term
(1)
storage causes initial burst effect. Equation 3
clearly shows that the release rate of drug is
controlled by diffusivity and solubility of drug
in the membrane as well as the thickness of the
membrane. Diffusivity of drug in the membrane
is influenced by the size and shape of the drug
molecules, flexibility, packing density, or crys-
tallinity of polymer chains. Flexibility of polymer
chains depends on glass transition temperature
and degree of crosslinking of the polymer. Diffu-
sivities are higher in rubbery polymers than those
in glassy polymers and decrease as crosslinking
density in the polymer increases. Diffusion takes
2 Controlled Release by Membrane
place in the amorphous phase of the polymers;
therefore, diffusivities are lower in more-
crystalline polymers than in less-crystalline
ones. Solubility of drugs in the membrane
depends on the interaction between the polymer
and drug. Simply, solubility of drug is higher in
polymers containing similar functional groups
with those of drug, in addition, solubility
decreases with an increase in crystallinity of the
polymer. Design of membrane-based controlled-
release system for a particular drug requires to
choose an appropriate polymer as a membrane
material and appropriate thickness to adjust the
release rate at a desired level.
Diffusion-controlled release systems are com-
monly used in commercial products and the most
successful example is in transdermal
applications. These devices contain the drug
either in a reservoir surrounded by a membrane
or dispersed in a polymeric matrix and deliver
drugs directly through the skin and into the blood-
stream. The flux of the drug through the skin is
enhanced by using penetration enhancers or elec-
tric current. Osmotic controlled-release systems
also depend on diffusion of water across a semi-
permeable membrane. These systems for oral
delivery of drugs are prepared by compressing
an osmotically active agent into a tablet, coating
the tablet with a semipermeable membrane, and
drilling a small hole through the coating. As
water permeates through the membrane into the
tablet, a solution of the agent is pumped out of the
hole. Such a device provides a constant rate of
release as drug traverses the gastrointestinal tract.
C
Controlled Release Dose
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Controlled release dosage forms are designed to
deliver optimum dose of drug at the right time
and right place. For an efficient and nontoxic
therapy, the drug concentration in plasma should
lie within the therapeutic range which is bounded
below by the minimum effective concentration
(MEC) and above by the minimum toxic concen-
tration (MTC) as shown in Fig. 1. Conventional
doses lead to a rapid rise and fall in the drug
concentration; therefore, several doses at regular
intervals are required to maintain effective levels.
After an initial rise, controlled release dosage
forms maintain a constant concentration in
plasma between MEC and MTC. As a result,
several benefits are achieved with these systems
including a prolonged therapeutic effect, increas-
ing short half-life of drugs, reduction in dosing
frequency and side effects, and improved patient
compliance. As shown in Fig. 1, zero-order
release allows the best control of plasma concen-
tration and controlled release dosage forms fol-
lowing zero-order release kinetics are usually
achieved by using a rate-limiting membrane that
is permeable to both drug and water. Osmotic
pumping and solution-diffusion mechanism con-
trol drug release from membrane systems. In an
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1239-1
elementary osmotic pump, a table or capsule
containing drug in the core is surrounded by a
membrane that is permeable to water but not
drug. After swallowing, water permeated into
the core through the membrane dissolves drug,
and a constant osmotic pressure gradient
established pumps the drug through a hole drilled
into the membrane. Zero-order release kinetics
are observed so long as a constant osmotic pres-
sure gradient between core and surrounding
medium is maintained. When drug concentration
falls below its solubility, then rate of drug release
starts to decay. To improve the efficiency of
osmotic systems, excipients such as water-
soluble polymers are added into core, or drug
formulation is placed between the water-soluble
polymer and the exit orifice. A majority of the
coated dosage forms are controlled by solution-
diffusion mechanism where the driving force for
the diffusional drug release is the drug concen-
tration gradient across the rate-controlling mem-
brane. The drug release rate can be manipulated
by varying the membrane thickness and mem-
brane permeability. Permeability can be modified
by incorporating soluble additives or pore-
forming agents in the membrane material which
allows the drug release not only by diffusion but
also by osmotic pumping.
To develop a controlled release dosage form,
relevant pharmacokinetic parameters for the
absorption, distribution, and elimination of a
drug as well as its in vivo release profile from
the dosage form should be considered. The
2 Controlled Release Dose
Controlled Release Dose,
Fig. 1 The change in drug
concentration in blood
during drug delivery
dosage form should deliver the drug within 24 h
which corresponds to the total gastrointestinal
tract (GI) transit time in humans. To protect
drug from hydrolysis in acidic environment of
the stomach, dosage forms are prepared with
membranes made from pH-sensitive polymers
that are insoluble in acid but dissolve in the neu-
tral or slightly alkaline environment of the gut.
Drug is released rapidly if the molecular weight
of the polymer is low. If a high molecular weight,
water-soluble polymer is used for coating, ini-
tially it swells into a gel through which drug
diffuses. Following ingestion, the rate of swelling
and diffusion through the membrane affect the
time for passage of the dosage form through the
stomach to the small intestine.
R
Release of Antimicrobial Agent
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Antimicrobial packaging is produced by adding
active ingredients in the packaging system or
coating/immobilizing active agent onto the sur-
face and/or using actively functional polymers
that satisy conventional packaging requirements.
The use of antimicrobial packaging has received
great attention since these types of systems pro-
vide high food quality, safety, and long shelf-life
by reducing, inhibiting, or retarding the growth of
microorganisms. Traditionally, antimicrobial
agents are directly mixed into the initial food
formulations in an excess amount since this
approach may result in a decrease in the concen-
tration of the antimicrobial agent on the food
surface due to its diffusion into the interior parts
of the food. Antimicrobial packaging offers an
alternative way to overcome these limitations.
Controlled release of the antimicrobial agent
from the film to the food surface is one of the
most important desired properties of the antimi-
crobial packaging materials. A rapid release
causes fast consumption of the agent in a short
period of time; thus, protection of the food
ceases, on the other hand, spoilage reactions on
the food surface may start if the release rate of the
antimicrobial agent from the film is too slow.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1240-1
Controlled release of the antimicrobial agent
can overcome this limitation by continuously
replenishing it to the food surface, compensating
for the consumption or degradation of active
compounds. Controlled release of drugs has
been used for some time, and procedures for
achieving desirable rates are well established,
on the other hand, research on the development
of food packaging films with controlled release
properties are limited. Strategies used to control
the release rate of antimicrobial agent from the
packaging are mainly based on changing the
degree of cross-linking (Buonocore et al. 2004)
or asymmetric structure of the film (Gemili
et al. 2009) or forming multilayer structured
films (Han and Floros 1998). The release of the
antimicrobial agent from the film involves first
diffusion within the film toward the film/food
interface, mass transfer across the interface, and
dispersion into the bulk food. In most cases, dif-
fusion in the film is the slowest and the rate-
controlling step. In laminated multilayer systems,
the outer layer is generally used to prevent loss of
the antimicrobial agent to the environment. The
matrix layer contains antimicrobial agent and has
usually amorphous structure to provide space for
entrapping large amount of the antimicrobial
agent and fast diffusion of the antimicrobials.
The inner layer is the key layer to control the
initial lag period and the flux of the antimicrobial
agent. Therefore, the thickness of this layer and
its structural characteristics are optimized to con-
trol the release rate of the antimicrobial agent.
2 Release of Antimicrobial Agent
When highly swellable polymers are used as
packaging material, in addition to diffusion of
the antimicrobial agent, diffusion of water into
the matrix and the rate of swelling of the matrix
are also important factors that control the release
rate of the antimicrobial agent. In cases where the
characteristic diffusion time is lower than the
relaxation time of the polymer, relaxation
becomes the limiting phenomena controlling the
solvent uptake, consequently the release of the
antimicrobial agent. Food packaging materials
based on proteins or polysaccharides are usually
charged at the pH of the release medium. When
both the antimicrobial agent and the food pack-
aging material are charged, then the release rate
depends on the pH of the release medium. In this
case, the release of the agent occurs only if both
the agent and the polymer are similarly charged
since this condition promotes repulsion between
them. Thus, the choice of the polymer matrix for
the charged antimicrobial agent should be done
based on the pH of the target food.
References
Buonocore GG, Sinigaglia M, Corbo MR, Bevilacqua A,
La Notte E, Del Nobile MA (2004) Controlled release
of antimicrobial compounds from highly swellable
polymers. J Food Prod 67:1190
Gemili S, Yemenicioglu A, Altınkaya SA (2009) Devel-
opment of cellulose acetate based antimicrobial
food packaging materials for controlled release of
lysozyme. J Food Eng 90:453
Han JH, Floros JD (1998) Simulating diffusion model and
determining diffusivity of potassium sorbate through
plastic to develop antimicrobial packaging films.
J Food Proc Preserv 22:107
U
Urease Immobilization
on Membranes
Sacide Alsoy Altinkaya
Department of Chemical Engineering, Izmir
Institute of Technology, Urla, Izmir, Turkey
Enzyme immobilization within membrane pores
or onto membrane surface has gained growing
interest due to controllable transport of reaction
substrates and products through the membrane.
This is particularly important when the product
acts as an inhibitor. Also, high surface area of the
membranes offers a potentially higher enzyme
loading. Urease is an enzyme most extensively
studied for immobilization and catalyzes the
hydrolysis of urea to ammonium and carbon
dioxide. Nonenzymatic urea hydrolysis requires
high temperatures and pressures and biological
conversion of urea nitrogen to dinitrogen suffers
from instabilities of microbial bed. The method
based on the hydrolysis of urea by urease
immobilized on a suitable support material is an
attractive and an alternative removal method.
The choice of a support material for enzyme
immobilization is important to minimize the loss
of enzyme activity. The membrane material
should have high affinity to proteins, available
reactive functional groups for direct enzyme
attachment or for chemical modification,
mechanical stability, and regenerability. The
membranes from natural polymers may have
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1241-2
restricted applications since the abundance in
hydrogen bonding among the polymer chains
may result in a decrease in flexibility, the excel-
lent affinity to proteins may make them easily
eroded by bacteria, and high hydrophilicity may
cause the membranes to swell in a wet atmo-
sphere. Due to these drawbacks, synthetic mem-
branes were preferred as enzyme carriers because
of their low cost, easy surface modification, resis-
tance to biodegradation, and thermal and chemi-
cal stabilities.
Urease was immobilized onto various sup-
ports and a detailed review of these studies has
been published by Krajewska (2009). The mem-
branes used as a support material were made from
nylon, silk cloth, polypropylene fabric, poly
(hydroxyethyl methacrylate-co-glycidyl methac-
rylate), polyacrylonitrile, methoxypolyethylene
glycol 5000, poly(N-isopropylacrylamide-co-
N-acrylosuccinimide-co-2-hydroxyethyl methac-
rylate), poly(2-hydroxyethylmethacrylate),
chitosan-poly(glycidylmethacrylate) copolymer,
ethylene-vinyl alcohol, nylon 6/6, acrylamide-
grafted poly(ethylene terephthalate) fibers, tris
(hydroxymethyl)phosphine polyetheramine
copolymer, chitosan, collagen-glycidyl methac-
rylate graft polymer, cyanuric chloride DEAE-
cellulose ether, poly(acrylonitrile)-chitosan com-
posite, expanded PTFE, polyethylene, polyam-
ide, polyaniline, poly(ethylene terephthalate)
fibers, and aminated polysulfone. In these studies,
urease was immobilized by covalent attachment
where reactive functional groups on the surface
2 Urease Immobilization on Membranes
of the membrane were generated by different
surface modification techniques and by cross-
linking with multifunctional, low molecular
reagents. In recent years, the layer-by-layer
assembly technique was shown to be an efficient
method for enzyme immobilization (Smuleac
et al. 2006). The method involves layer-by-layer
deposition of oppositely charged polyelectrolytes
by consecutive, alternating immersion of a
charged substrate into aqueous solutions of an
anionic and a cationic polyelectrolyte. Since
enzymes are multiply charged molecules, the
layer-by-layer (LBL) assembly offers a simple
method to perform the immobilization. In some
cases, electrostatic interactions in the assembly
help stabilize the enzymes to maintain their activ-
ity. The LBL method was used to immobilize
urease on polystyrene particles, silicon
microchannels, or NH3 electrode (Krajewska
2009). Guedidi et al. (2010) immobilized urease
on polyacrylonitrile-based membranes using
LBL assembly. The optimum pH for both native
and immobilized urease was found to be at about
seven. Immobilized form of urease retained
higher activity at lower pH than the soluble coun-
terpart. Immobilization onto a polyelectrolyte
layer (urease forms the last layer of the assembly)
resulted in a higher catalytic activity than that of
enzyme directly immobilized on the membrane
which clearly indicates the beneficial effect of a
polyelectrolyte environment. Immobilization of
urease in between two polyelectrolyte layers
decreased the activity compared to the previous
case most probable due to the diffusion-limited
accessibility of the catalytic site. Adsorption of
negatively charged urease directly onto nega-
tively charged support resulted in a loss of
enzyme activity in a short period of time. On
the other hand, immobilization of urease between
two polyelectrolyte layers appeared to bring bet-
ter environment to ensure long-term enzyme
stability.
References
Guedidi S, Yurekli Y, Deratani A, Dejardin P, Innocent C,
Altinkaya SA, Roudesli S, Yemenicioglu A (2010)
Effect of enzyme location on activity and stability of
trypsin and urease immobilized on porous membranes
by using layer-by-layer self-assembly of polyelectro-
lyte. J Membr Sci 365:59
Krajewska B (2009) Properties and their customizing by
enzyme immobilizations: a review. J Mol Catal
B Enzym 59:22
Smuleac V, Butterfield DA, Bhattacharyya D (2006)
Layer-by-layer-assembled microfiltration membranes
for biomolecule immobilization and enzymatic catal-
ysis. Langmuir 22:10118
H
Hemodialysis (HD) Membranes
Michel Jaffrin
Department of Biological Engineering,
Technological University of Compiegne,
BP 20529, Compiegne cedex, France
Introduction
Hemodialysis (HD) consists in recirculating the
patient’s blood into a hemodialyzer with an ultra-
filtration membrane which permits to remove
uremic toxins mainly by diffusion, while excess
water is removed by ultrafiltration. The treatment
of chronic renal disease requires three dialysis
sessions of 4 h per week, as well as dietetic
restrictions to limit potassium intake. In 2008,
1.58 millions of patients were treated by HD
worldwide. Without reuse, assuming a mean
membrane area of 0.9 m2 per hemodialyzer,
they would have consumed 213 106 m2 of mem-
brane per year. If 75 % of dialysis centers reuse
dialyzers 2.54 times (Chuang et al. 2008), this
consumption is reduced to 116 106 m2, which is
still the biggest application of membranes. The
first disposable hemodialyzers were commercial-
ized in 1950, but it is the arteriovenous shunt
invented by Dr. Scriber from Seattle which per-
mitted modern dialysis by connecting the dia-
lyzer inlet to an arm artery and the outlet with
an arm vein, permitting a blood flow rate of
200–300 ml/min into the dialyzer.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1242-5
Physiological Requirements
Dialysis must reproduce the four main functions
of kidney:
– Elimination of uremic toxins, urea, creatinine,
uric acid, phosphates, and sulfates
– Removal of excess body water by ultrafiltra-
tion, 1–3 L per run
– Control of plasma electrolytes concentrations
Na+, Cl , K+, Ca++, by adjusting dialysate
ionic concentration
– Maintaining blood pH to 7.2 through an ace-
tate or bicarbonate buffer in dialysate
In regular hemodialysis, only the excess water
is removed by ultrafiltration, while in
hemodiafiltration (HDF) about 10–20 L of water
is removed from blood per session to eliminate
toxins and middle molecules by convection in
addition to diffusion, and it is replaced by a sterile
dialysate except for the part corresponding to
excess water. Figure 1 illustrates the difference
between HD and HDF. In predilution mode, the
sterile dialysate is reinjected in blood at dialyzer
inlet, while it is reinjected at outlet in
postdilution. Hemofiltration (HF) is analogous
to HDF with up to 25 L water removal, but
without feeding dialysate in the dialyzer as
toxin, removal by diffusion is not necessary.
2 Hemodialysis (HD) Membranes
Hemodialysis (HD) and Hemodiafiltration (HDF)
HD HDF
Post dilution
Pre dilution
Blood Dialysis
fluid Blood Dialysis
fluid
Membrane
Diffusion + Increased
Diffusion convective transport
Hemodialysis (HD) Membranes, Fig. 1 Difference
between HD and HF modes
Dialysis Membranes
They are divided into two categories, low and
middle permeability cellulosic membranes and
high permeability polymeric membranes, which
are listed in Table 1. They are generally of hollow
fiber geometry (200 mm diameter), but some flat
sheet membranes are also available. Cuprophan
membranes are now replaced by cellulose acetate
or triacetate which is more biocompatible, even
though they activate complement and leukocytes,
leading to inflammatory reaction (Bouré and
Vanholder 2004). Masking hydroxyl groups
increases their biocompatibility. High permeabil-
ity membranes permit to carry out
hemodiafiltration and hemofiltration treatments
with high water removal, partially replaced by
sterile dialysate. In addition, polymeric mem-
branes are often more biocompatible than cellu-
losic ones. They are also superior for patient
quality of life, reducing b2-M amyloidosis, infec-
tions, and loss of residual kidney function. High-
flux membranes with larger pores increase
removal of middle molecules such as b2-
microglobulin, cytokines, resistin, immunoglob-
ulins, parathyroid hormones, and dinucleoside
polyphosphates. Their removal protects the
patient against cardiovascular problems and
other side effects of uremic syndrome
(Vanholder et al. 2011).
Characteristics of Recent European
Hemodialyzers
Hospal Gambro (Meyzieu, France) commercial-
izes three high-flux hollow fibers dialyzers: the
Evodial with heparin grafted to AN membrane,
giving very good hemocompatibility; the Nephral
ST with PEI, a biopolymer grafted on AN69; and
the Revaclear with a Poractron membrane per-
mitting to reduce its area. Gambro (Sweden)
sells, for HF and HDF, the polyflux H with a
polyamide–polyacrylether sulfone membrane.
Fresenius Medical Care (Germany) commercial-
izes high-flux dialyzers with a Helixone mem-
brane, the FX60, 800, and 1,000 with urea
clearances of up to 278 ml/min at a blood flow
of 300 ml/min, and other dialyzers with
polysulfone membrane, both at high flux (F 40S
to F80S with area from 1 to 1.8 m2) and at low
flux (F4HPS to F8HPS with area from 0.7 to
2.4 m2 according to patient weight).
Hemodialysis (HD) Membranes 3

Hemodialysis (HD) Membranes, Table 1 Hemodialysis membranes

Type Plane Fiber Manufacturer Permeability ml/h-mmHg
Membrane Dialyzer m2
Low and middle permeability,
Cuprophan X X AKZO Baxter, Bellco, Gambro 2–3.5
Cuprophan HDF X AKZO Gambro 8
Cuprophan TAF X Terumo Terumo
Hemophan X AKZO CD Medical
Cellulose acetate X 5
Cellulose triacetate X Baxter, Nipro
High permeability
PMMA X Toray Toray 14
Polyacrylonitrile X X Hospal Hospal, Asahi 25
PAN
PAN S X Hospal Hospal 40
Polysulfone X Fresenius Fresenius 30–40
Polysulfone X Amicon (HF) Amicon 50
Polyamide X Gambro Gambro 30
(HF)

References
Bouré T, Vanholder R (2004) Which dialyser membrane
to choose? Nephrol Dial Transplant 19:293–296
Chuang FR, Lee CH, Chuang HW, Lee CN, Chen TC
(2008) A quality and cost benefit analysis of dialysers.
Ren Fail 30:521–526
Vanholder R, Glorieux G, Van Biesen W (2011) Advan-
tages of new hemodialysis membranes and equipment.
Nephron Clin Pract 114:c165–c170
H

Hollow Fibre Enzymatic Reactor, the axial space coordinate, m. The momentum
Modeling of equations are as


Endre Nagy @u @u @p
r u þu ¼
Research Institute of Chemical and Process @r @z @z
Engineering, University of Pannonia, Veszprèm,    
@ 1 @ ðruÞ @2u
Hungary þm þ 2
@r r @r @z
(2)
Modeling of hollow fiber enzymatic reactor.

@u @u @p
The complete description of the transport of r u þu ¼
fluid in hollow fiber capillary membrane requires @r @z @z
   
that the local transport equations that describe the @ 1 @ ðruÞ @2u
þm þ 2
flow and transport conditions should be solved. @r r @r @z
The starting Navier-Stokes flow models (Bird (3)
et al. 1960) are very complex; significant simpli-
fication is needed to obtain applicable model for and for solute concentration in case of constant
engineering points of view. In a capillary mem- density
brane with permeable wall, three regions of flow


should be considered: flow in lumen, within @c @c @ @c 1 @ ðDcÞ
membrane matrix, and in the extracapillary u þu ¼ D þ
@z @r @r @r r @r
space (Nagy 2011, p. 179). Let us consider a

@ @c
steady-state, laminar, incompressible, isother- þ D (4)
mal, fully developed flow in vertically oriented @z @z
tube; thus the Navier-Stokes equations (Bird
et al. 1960) will be as the continuity equation: where r is the density, p is the pressure, m is
dynamic viscosity, and g is gravitational
1 @ @u acceleration.
ðrur Þ þ ¼0 (1) Equations 2 and 3 may be reduced by consider-
r @r @z
ing the fact that for a small wall Reynolds number,
where u is the axial convective velocity, m/s; ur is the inertial terms can be negligible. In most viscous
the transverse convective velocity, m/s; and z is flows, normal stress effects,@ 2 u=@z2, are negligible
when the ratio, ro/L (L is length of capillary, ro is

# Springer-Verlag Berlin Heidelberg 2012

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1243-1
2 Hollow Fibre Enzymatic Reactor, Modeling of

lumen radius), is less than 102, a condition that is Replacing Eq. 10 into Eq. 5, one can get for the
satisfied in almost all hollow fiber membrane radial convective velocity in the lumen side (for
devices. Depending on the transmembrane convec- distinction for the membrane’s velocity, f sub-
tive velocity, the axial velocity often can be much script denotes the fluid phase here in the lumen
larger than that of the permeation rate. Due to its side)
large values, the axial diffusion term can be
(
)
neglected. The radial convective velocity is rather r3o r 1 r 3 d2 pt
low; accordingly, momentum equation of the trans- ut ¼  (11)
m8 ro 2 ro dz2
verse velocity can be neglected. Accordingly,
Eqs. 2 to 4 can be simplified as
From Eq. 11 the wall velocity, uw, can be given as


@p 1 @ @u
0¼ þm r (5) r3o @ 2 pt
@z r @r @r uw ¼ (12)
16m @z2
The component balance will be as:
The radial convective velocity through the mem-

 brane can also be expressed by the next equation
@ci @ @c
u ¼D r (6) ▶ Biocatalytic membrane reactor: mass transport
@z @r ℑ r
as
When Eq. 6 is integrated twice with respect to r,
k r o pt ð z Þ  pe ð z Þ
one can get as uM ðr, zÞ ¼ (13)
em r lnð1 þ d=ro Þ
dp r2
u¼ þ Alnr þ B (7) From equality of Eqs. 12 and 13, a second-order
dz 4 differential equation can be obtained neglecting
For the hydrodynamic analysis in the lumen and the radial pressure gradient (Nagy 2011, p. 187).
in the shell, the continuity Eq. 1 and the momen- Solving this equation the p(z) and uw(z) functions
tum Eq. 5 have to be solved with suitable bound- can be obtained (Nagy 2011). This convection
ary conditions. In the lumen (t) these are velocity can then be replaced in the mass balance
equation for the membrane (see “▶ Biocatalytic
@u Membrane Reactor: Mass Transport).
at r ¼ 0 then ¼ 0, u ¼ 0; (8)
@z

at r ¼ r0 then u ¼ 0 (9) References

Consequently it can be get Bird RB, Stewart E, Lightfoot EN (1960) Transport phe-
nomena. Wiley, New York
 2 ! Nagy E (2011) Basic equations of the mass transport
r2o r dpt through a membrane layer. Elsevier, Amsterdam
u¼ 1 (10)
4m ro dz
S
Spacer Arm Length
Jiahui Shao
School of Environmental Science and
Engineering, Shanghai Jiao Tong University,
Shanghai, People’s Republic of China
The spacer arm length refers to the length of
hydrocarbon chain between the solid support
and the functional ligand.
For ion exchange and affinity chromatogra-
phy/membrane, studies have demonstrated that
the spacer arm length can affect the overall sys-
tem performance. In general, when the
immobilized ligand is a small molecule, such as
a receptor substrate or a chemical antigen, steric
hindrance occurs between the immobilization
support and the substance to be isolated. This
phenomenon may cause a reduction or complete
lack of specific binding (Zou et al. 2001). To
overcome this problem, it is often necessary
either to select a different support (i.e., one with
a spacer arm already attached) or to bind a spacer
molecule to the support prior to attaching the
ligand. An optimal spacer arm ensures that the
functional groups are placed a suitable distance
from the surface of the solid support and are
easily accessible to the macromolecules. An
ideal spacer arm should have (1) proper length
(at least three atoms), (2) no active center that
could cause nonspecific adsorption, and (3) at
least two functional groups, one to react with
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1244-2
the base support and one to serve as the chro-
matographic ligand (Zou et al. 2001).
For charge-modified membranes with differ-
ent spacer arm lengths, recent researchers dem-
onstrated that the spacer arm length can have a
strong effect on the performance characteristics
of electrically charged membranes by electro-
static exclusion effects. Even though the hydrau-
lic permeabilities of these membranes were
essentially identical, membranes with larger
spacer arm length have greater retention of a
like-charged molecule. The greater retention
with larger spacer arm length is directly related
to the effective surface charge or apparent zeta
potential (Rohani and Zydney 2010; Shao et al.
2013). The permeability-selectivity trade-off plot
for the charge-modified membranes with differ-
ent spacer arm length demonstrated that the
electro-static interactions led to much better
ultrafiltration performance of enhanced selectiv-
ity and permeability than could be obtained with
conventional (neutral) membranes. Figure 1
shows a plot of the selectivity (or separation
factor) as a function of the permeability for cyto-
chrome c for unmodified and positively charged
versions of composite regenerated cellulose
ultrafiltration membranes. The format for plot-
ting the data is analogous to the classical Robeson
plot used to analyze the behavior of gas separa-
tion membranes. High-performance membranes
would lie in the upper right hand corner of the
plot, having both large selectivity and large per-
meability. Unmodified and po. For example, at a
2 Spacer Arm Length
Spacer Arm Length,
Fig. 1 Permeability-
selectivity trade-off for
cytochrome c using
unmodified and positively
charged Ultracel™
Selectivity, 1/Sa
membranes. The solid and
dashed curves represent
model calculations for an
uncharged membrane and a
positively charged
membrane consisting of a
parallel array of cylindrical
pores with a log-normal
pore size distribution
(Rohani and Zydney 2010)
hydraulic permeability of about 6.0  10 10 m/s/
Pa (15 L/m2/h/psi), the selectivity for the posi-
tively charged membrane is more than three
orders of magnitude larger than that of the
unmodified membrane. The charge-modified
membranes with different spacer arm lengths
can be well exploited to enhance the performance
of ultrafiltration processes for real applications.
Mehta and Zydney (2008) generated a series of
positively-charged membranes with different
spacer arm length by activation of base cellulose
membrane with epichlorohydrin followed by
reaction with diamines having different numbers
of alkyl groups between the two amines. Experi-
mental data showed that at low ionic strength
(5 mM), the observed sieving coefficient for cyto-
chrome c through the 30 kDa membrane made
with 1,10-diaminodecane (n = 10) was more than
an order of magnitude smaller than that for a
similar membrane made using 1,2-diaminoethane
(n = 2) even though these membranes had very
similar hydraulic permeabilities and pore size
distributions, where n is the number of alkyl
groups between the amine functionalities. This
large reduction in the protein sieving coefficient
was found to be consistent with the observed
increase in the membrane zeta potential, which
was most likely due to the increase in net charge
associated with the reduction in electrical inter-
actions between the two amine groups in the
10000
Steric Interactions
Quaternary Amine
1000
100
10
1
0 5 10 15 20 25 30
Permeability, ¥ 10–10 (m/s/Pa)
diaminodecane in combination with the greater
displacement of the charge functionality into the
interior of the membrane pore for the larger
ligand. Later, Shao et al. (2013) generate a series
of negatively charged ultrafiltration membranes
that differed in spacer arm length by covalent
attachment of negatively charged group to a com-
mercially available regenerated cellulose mem-
brane. Results indicated that the membrane with
larger spacer arm length has better rejection of
humic acid and less membrane fouling compared
to that with smaller spacer arm length, which is
also consistent with the larger charge of the mem-
brane having larger spacer arm length.
References
Mehta A, Zydney AL (2008) Effect of spacer arm length
on the performance of charge-modified ultrafiltration
membranes. J Membr Sci 313:304–314
Rohani MM, Zydney AL (2010) Role of electrostatic
interactions during protein ultrafiltration. Adv Colloid
Interf Sci 160:40–48
Shao J, Zhao L, Chen X, He Y (2013) Humic acid rejec-
tion and flux decline with negatively charged mem-
branes of different spacer arm lengths and charge
groups. J Membr Sci 435:38–45
Zou H, Luo Q, Zhou D (2001) Affinity membrane chro-
matography for the analysis and purification of pro-
teins. J Biochem Biophys Methods 49:199–240
U
UV Irradiation
Jiahui Shao
School of Environmental Science and
Engineering, Shanghai Jiao Tong University,
Shanghai, People’s Republic of China
UV radiation energy waves are the range of elec-
tromagnetic waves 100–400 nm long (between
the X-ray and visible light spectrums),
corresponding to photon energies from 3 to
124 eV. It is so named because the spectrum
consists of electromagnetic waves with frequen-
cies higher than those that humans identify as the
color violet. The division of UV radiation may be
classified as Vacuum UV (100–200 nm), UV-C
(200–280 nm), UV-B (280–315 nm), and UV-A
(315–400 nm). UV irradiation occupies only
about 3–5 % of the total solar irradiance at the
Earth’s surface.
UV irradiation has many technical applica-
tions through the use of particular wavelength,
including security, forensics, spectrophotometry,
photolithography, sterilization, disinfecting
drinking water, removing persistent organic com-
pounds via photocatalyst, and initiating chemical
reactions and others.
UV irradiation linked to membrane science
and technology is manifested in three aspects.
1. UV irradiation for preparation, modification,
and stimulation of polymeric membranes. For
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1246-2
de novo preparation of membranes from low
molar mass or soluble precursors, photo-
initiated polymerization and photo cross-
linking are the main pathways, while
photodegradation for pore formation is only
rarely applied (He et al. 2009). For membrane
modification, “grafting-from” and “grafting-
to” are two commonly used strategies. The
“grafting-from” method utilizes active species
existing on a membrane surface to initiate the
polymerization of monomers from the surface.
For “grafting-to” method, polymer chains car-
rying reactive anchor groups at the end or on
the side chains are covalently coupled to the
membrane surface. Photostimulation of bar-
rier properties is an attractive concept to create
stimuli-responsive membranes and various
ways to use photochromic moieties.
Photoirradiation-based methods can be very
versatile enabling technologies to improve
the performance of polymeric membranes in
technical separations (e.g., in gas separation,
pervaporation, ultrafiltration, and
microfiltration or as membrane adsorbers)
and other processes (e.g., for controlled
release or in sensor systems), and they will
contribute to the development of entirely
novel membrane-based materials
(He et al. 2009).
2. The combination of photocatalysis utilizing
UV irradiation with membrane separation,
which is often called photocatalytic mem-
brane reactors (PMRs). PMRs can be
2 UV Irradiation
generally classified into two main configura-
tions: (a) reactors with photocatalyst particles
suspended in feed solution and (b) reactors
with photocatalyst immobilized on/in the
membrane. The major disadvantage of the
configuration with photocatalyst in suspension
is deterioration of the permeate flux and mem-
brane fouling. PMRs with photocatalyst on/in
membrane are one solution for this problem.
In this configuration, oxidation by hydroxyl
radicals occurs on the external surface and
within the pores of the membrane, while reac-
tants are permeating in a one-pass flow. How-
ever, fixation of the photocatalyst often results
in a loss of photoactivity and might cause
destruction to the membrane structure
(Mozia 2010).
3. UV irradiation for membrane fouling/biofoul-
ing control and membrane clean. UV irradia-
tion integrated in membrane system is able to
mitigate membrane biofouling, which is
caused by deposition or growth of microor-
ganisms on membrane causes. For the
membrane with photocatalyst (such as TiO2)
on the surface or entrapped in, the fouling can
be effectively controlled because the pollut-
ants can be effectively degraded by the
photocatalyst with UV irradiation during fil-
tration process. The fouled membranes after
membrane filtration can also be cleaned with
only UV irradiation, which provides the
photocatalyst-doped membrane self-cleaning
property (Song 2012).
References
He D, Susanto H, Ulbricht M (2009) Photo-irradiation for
preparation, modification and stimulation of polymeric
membranes. Prog Polym Sci 34:62–98
Mozia S (2010) Photocatalytic membrane reactors
(PMRs) in water and wastewater treatment.
A review. Sep Purif Technol 73:71–91
Song H, Shao J, He Y, Liu B, Zhong X (2012) Natural
organic matter removal and flux decline with PEG-
TiO2-doped PVDF membranes by integration of ultra-
filtration with photocatalysis. J Membr Sci 405: 48–56
P
Pore Forming Agent
Jiahui Shao
School of Environmental Science and
Engineering, Shanghai Jiao Tong University,
Shanghai, People’s Republic of China
High porosity, suitable pore size, and pore size
distribution are essential for the usefulness of the
membranes. In order to improve the membrane
permeation properties, a commonly adopted
approach is adding pore-forming agents
(additives) in casting solution through adjusting
the membrane structure. Based on the fundamen-
tal concept that the sublayer of asymmetric poly-
meric membrane is strongly influenced by the
additives and that of their aggregates which are
in the casting solution, there is always an ongoing
research in exploring new suitable additives for
membrane making (Mohanty and Purkait 2011).
It is generally believed that pore-forming agents
increase the polymer dope viscosity, create a
spongy membrane structure by prevention of
macrovoid formation, enhance the pore intercon-
nectivity when added in appropriate amounts, or
speed up the displacement of solvent with
non-solvent in the coagulation bath, that is,
enhance the liquid-liquid demixing process dur-
ing precipitation of the dope solution, and there-
fore the formation of larger pores is favored.
However, the mechanical strength of these mem-
branes normally decreases, and pore-forming
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1253-2
agents may eventually leach out from the
resulting membrane due to their relative small
sizes and their high affinity to the water (Liu
et al. 2011).
Pore-forming agents are mainly divided into
three categories: (1) low molecular weight inor-
ganic salts; (2) high molecular weight additives,
known as polymeric additives; and (3) other types
of additives. Sometimes, mixture of more than
one agent is used to provide the membrane with
appropriate permeation properties:
1. Low molecular weight inorganic salts: These
inorganic salts include lithium chloride (LiCl),
zinc chloride (ZnCl2), magnesium chloride
(MgCl2), calcium chloride (CaCl2), lithium
perchlorate (LiClO4), magnesium perchlorate
(Mg(ClO4)2), calcium perchlorate (Ca
(ClO4)2), and others. Currently, lithium chlo-
ride (LiCl) is commonly used. It is generally
believed that ion-dipole interactions between
metal ions and membrane polymers enhance
the demixing process and form more and
larger pores (Mohanty and Purkait 2011).
With these inorganic salts added, the mem-
brane porosity increases while the mean pore
size is almost constant, which causes the water
flux to significantly increase without causing
an obvious drop in solution rejection.
2. Polymeric additives: Polymeric additives are
normally hydrophilic in nature. These addi-
tives not only enhance the permeation proper-
ties of the membrane but also increase its
2 Pore Forming Agent
hydrophilicity. Polyvinylpyrrolidone (PVP)
and poly(ethylene glycol) (PEG) are com-
monly used and studied. The addition of poly-
meric membranes promotes non-solvent flux
upon immersion in the coagulation bath, thus
favoring the formation of large finger-like
macrovoids. The membrane permeation prop-
erties change with the concentration and
molecular weight of the polymer added. Gen-
erally, as the concentration of adding polymer
increases, the membrane porosity and perme-
ation flux increase. The membrane porosity
and permeation flux normally also increase
with increasing molecular weight of the poly-
mer (Mohanty and Purkait 2011); Liu
et al. 2011). However, the solute rejection
decreases but normally does not have signifi-
cant reduction.
3. Other types of additives: Other frequently
used pore-forming agents include glycerol,
water, alcohol, formamide, and polyethylene
oxide (PEO) or the mixture of them.
References
Liu F, Hashim NA, Liu Y, Abed MRM, Li K (2011)
Progress in the production and modification of PVDF
membranes. J Membr Sci 375:1–27
Mohanty K, Purkait MK (2011) Membrane technologies
and applications. CRC Press, New York
S

Solubility Parameter enthalpy, DH ~ MIX , by the following expression

valid for a binary mixture:
Maria Grazia De Angelis
Dipartimento di Ingegneria Civile, Chimica, ~ EX ¼ F1 F2 ðx1 v~1 þ x2 v~2 Þðd1  d2 Þ2
G
Ambientale e dei Materiali, Università di
~ MIX
¼ DH (3)
Bologna, Bologna, Italy

The ▶ solubility parameter d is a thermodynamic
quantity introduced by Hildebrand and Scatchard
(HS) to describe the behavior of the so-called
regular solutions. Such solutions have a negligi-
ble mixing volume and excess entropy of mixing,
so that the excess Gibbs free energy coincides
with the mixing enthalpy. The HS model uses
the idea of cohesive energy density (CED), that
is, the difference between the internal energy of
the system and that of the corresponding system
in the ideal gas state, per volume of liquid sub-
stance, estimated as follows: (Sandler 2006)


~ VAP
DU
CED ¼ L!IG
v~L


~ VAP
DH  RT
¼ L!IG
v~L
And the solubility parameter d is defined as:
pffiffiffiffiffiffiffiffiffiffi
d CED
The solubility parameter is related to the molar
~ EX , and to the mixing
excess Gibbs free energy, G
where:
xi v~i
Fi ¼ (4)
x1 v~1 þ x2 v~2
And for the activity coefficient of species i:
 2
RTlngi ¼ v~i F2j di  dj (5)
The model is predictive for the solubility as far as
the d values of the two species are known and the
theory can depict correctly the physical behavior
of the mixture; indeed the equilibrium composi-
tion or solubility can be found applying the phase
equilibrium condition for the solute species.
Although the HS theory is not always appro-
priate, especially for solutions containing poly-
(1) mers, as it does not account for mixing volume
and excess entropy of mixing, and it uses the
geometric mean rule assumption for the binary
interactions between unlike molecules, the d
value is widely used to estimate a priori the
(2) mutual solubility of two species. Two species
with similar d values show little excess free
energy and are mutually soluble in the entire

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1264-1
2 Solubility Parameter

Solubility Parameter, Table 1 Solubility parameter values for some polymers

d (J1/2/cm3/2), experimental from d (J1/2/cm3/2), estimated with group contribution
Polymer mixing data methods
Polyethylene 15.8–17.1 16.0
Polypropilene 16.8–18.8 17.0
Polyisobutylene 16–16.6 16.4
Polystyrene 17.4–19 19.1
Poly(vinyl chloride) 19.2–22.1 19.7
Poly(vinyliden chloride) 20.3–25.0 20.6
Poly 12.7 11.7
(tetrafluoroethylene)
Poly 14.7–16.2 15.7
(chlorotrifluoroethylene)
Poly(vinyl alcohol) 25.8–29.1 –
Poly(vinyl acetate) 19.1–22.6 19.6
Poly(methyl acrylate) 19.9–21.3 19.9
Poly(ethyl acrylate) 18.8–19.2 19.2
Poly(methyl 18.6–26.2 19.0
methacrylate)
Polyacrylonitrile 25.6–31.5 25.7

composition range. Two components with dis-
similar solubility parameters have high values
of the excess free energy and can show a
miscibility gap.
In gas sorption in membrane systems the
values of solubility is higher if the gas and poly-
mer solubility parameters are similar, and lower
if they are dissimilar, at fixed condensability of
the gaseous penetrant.
In some cases, it is evident that the solubility
of different fluids in a membrane is strongly cor-
related to the solubility parameter difference.
Normally d values are tabulated at 25  C and
their value is almost constant with temperature.
For fluids, the values are easily retrievable. For
polymers, the vaporization quantities cannot be
measured, and the d values can be estimated from
experimental mixing data or with group contri-
bution methods like the ones by Hoftyzer and
Van Krevelen and by Hoy (Van Krevelen 1990).
In both methods the same assumption is made
that the cohesive energy is not only represented
by the dispersion interaction forces between mol-
ecules, as originally assumed by the HS theory,
but it accounts also for the polar groups interac-
tions and for the hydrogen bonds:
CED ¼ CEDD þ CEDP þ CEDH (6)
And correspondingly:
d2 ¼ d2D þ d2P þ d2H (7)
Some values of the solubility parameters for
polymers of interest in membrane separations,
as measured from mixture data and as estimated
by the group contribution method of Hoftyzer and
Van Krevelen are reported in Table 1 (Van
Krevelen 1990).
References
Sandler SI (2006) Chemical, biochemical and engineering
thermodynamics, 4th edn. Wiley, New York
van Krevelen DW (1990) Properties of polymers: their
correlation with chemical structure; their numerical
estimation and prediction from additive group contri-
butions, 3rd edn. Amsterdam, Elsevier
L
LTA Zeolite Membranes in
Pervaporation
Yanshuo Li
State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, CAS, Dalian,
China
LTA Zeolite Membrane in Pervaporation.
Pervaporation (PV) or vapor permeation (VP) is
a membrane-based separation process which
shows a high efficiency for the separation of
azeotropes and close-boiling mixtures (Huang
1991). In general, zeolites with low Si/Al ratio
can be adopted to produce hydrophilic
pervaporative membranes for dewatering of
organics, as exemplified by LTA, FAU, SOD,
and T-type zeolites (Bowen et al. 2004). Among
those, LTA zeolite membranes exhibit the
highest water to alcohol selectivity up to present,
owing to its lowest Si/Al ratio and proper pore
size (0.4 nm) that can block organic solvent mol-
ecules bulkier than water. LTA zeolite mem-
branes have been widely used for dewatering
various organics, including alcohols, aldehydes,
ketones, ethers, esters, amines, and amides. Typ-
ical performances of LTA membrane are listed in
Table 1.
LTA zeolite membrane is the first zeolite
membrane to be used in large-scale industries
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1275-2
for the dehydration of alcohols (Morigami
et al. 2001). Nowadays, commercial LTA zeolite
membranes (in NaA form) can be bought from
the Japanese company, the Nano-Research Insti-
tute Inc. (XNRI), a 100 % subsidiary of Mitsui &
Co., the European alliance between Smart
(UK) and Inocermic, and most recently the Chi-
nese company, HST Co. Ltd., located at Dalian.
Compared with azeotropic distillation and
pressure swing adsorption (PSA), LTA zeolite
membrane can remarkably reduce the energy
consumption for dewatering of organics. Taking
the production of anhydrous ethanol as an exam-
ple, LTA zeolite membrane-based VP process
can reduce the consumption of steam by 40 %
and cooling water by 30 % compared with PSA,
respectively.
References
Bowen TC, Noble RD, Falconer JL (2004) Fundamentals
and applications of pervaporation through zeolite
membranes. J Membr Sci 245:1–33
Huang RYM (1991) Pervaporation membrane separation
processes, Elsevier. ISBN 0444882278
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Tech 25:251–260
2 LTA Zeolite Membranes in Pervaporation

LTA Zeolite Membranes in Pervaporation, Table 1 Typical PV/VP performances of LTA zeolite membrane for
dewatering organics
Feed solution (10 wt.% of water) Temperature [ C] Water flux (kg/m2h) Separation factor
Water/methanol 65 (PV) 0.6 116
Water/ethanol 65 (PV) 1.0 10,000
Water/ethanol 120 (VP) 3.1 10,000
Water/n-propanol 110 (VP) 2.5 10,000
Water/i-propanol 65 (PV) 1.8 10,000
Water/ethyl acetate 65 (PV) 1.2 10,000
Water/acetone 50 (PV) 0.9 10,000
Water/i-propylamine 105 (VP) 3.2 10,000
L
LTA Zeolite Membranes
Yanshuo Li
State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, CAS, Dalian,
China
LTA zeolite membrane is one of the most well-
studied zeolite membranes for the separation of
light gases and dewatering of organics. LTA
(Linde type A) zeolite has a three-dimensional
pore structure, consisting of secondary building
units (SBUs) 4, 6, 8, and 4-4 (Meier et al.). An
example material is NaA zeolite (Linde type
A sodium form) with chemical formula of
Na12Al12Si12O48
27H2O. The unit cell of NaA
zeolite is cubic (a = 24.61 Å) with Fm-3c sym-
metry. The pore diameter of NaA zeolite is
defined by an eight-member oxygen ring with
size around 4.3 Å. Generally, LTA zeolite mem-
branes exist in the form of composite membranes,
for which porous ceramic supports, typically alu-
mina tubes, are usually used as substrates. The
effective LTA zeolite separating layer is usually
in the thickness of several microns (Fig. 1).
The most used strategies for the synthesis of
LTA zeolite membranes are in situ synthesis and
secondary (seeded) growth. Microwave
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1276-2
techniques combining with these strategies have
been applied for the synthesis of LTA zeolite
membranes (Li et al. 2008). As compared with
conventional hydrothermal synthesis, microwave
synthesis of zeolite membranes has the advan-
tages of shorter synthesis time, better membrane
performance, and easier to scale up.
LTA zeolite membrane has been extensively
studied for the separation of light gas mixtures,
e.g., H2/CH4, O2/N2, and n-C4H10/i-C4H10 gas
pairs. The observed separation factors beyond
the selectivities predicted from Knudsen diffu-
sion are attributed to the so-called molecular
sieving function. Another important application
of LTA (particularly NaA) zeolite membranes is
for removing water from various organics via
pervaporation (PV) or vapor permeation (VP),
thanks to its ultramicroporous channel structure
and its hydrophilic nature. Nowadays, VP
dewatering technology based on NaA zeolite
membranes has been widely used in the industries
of chemistry, bioenergy, electronics,
pharmaceutics, etc. Compared with azeotropic
distillation, pressure swing adsorption (PSA),
and polymeric membranes, zeolite membrane
can remarkably reduce the energy consumption
for dewatering of organics (Van hoof et al. 2004).
2 LTA Zeolite Membranes

LTA Zeolite Membranes, Fig. 1 (a) Framework structure of LTA zeolite, (b) typical SEM image of a NaA zeolite
single crystal, (c, d) typical SEM image of a LTA zeolite membrane

References Van Hoof V et al (2004) Economic comparison between

azeotropic distillation and different hybrid systems
Li YS (2008) Microwave synthesis of zeolite membranes: combining distillation with pervaporation for the dehy-
a review. J Membr Sci 316:3–17 dration of isopropanol. Sep Purif Technol 37:33–49
Meier WM, Olson DH, Baerlocher C, Atlas of zeolite
structure types, ISBN-13: 978-0444100153, Excerpta
Medica
M
Microwave Synthesis of Zeolite
Membranes
Yanshuo Li
State Key Laboratory of Catalysis, Dalian
Institute of Chemical Physics, CAS, Dalian,
China
Microwave synthesis of zeolite membranes
applies microwave irradiation to the synthesis of
zeolite membranes as heat source. Microwave
technique is regarded as a novel tool in chemical
synthesis which offers enhanced speed, reproduc-
ibility, and scalability compared to conventional
heating. The pioneer work on microwave synthe-
sis of zeolites can be traced back to 1988, and
work on zeolite films and membranes subse-
quently began in the late 1990s. Microwave
heating usually combines with two hydrothermal
synthesis strategies: in situ synthesis and second-
ary (seeded) growth. So far, LTA, MFI, AFI,
FAU, SOD, T, ETS-4, et al. types of zeolite
membranes have been successfully synthesized
with the assistant of microwave heating (Li and
Yang 2008). LTA zeolite membrane is most
extensively studied among them and achieves
scale-up to produce commercial zeolite mem-
branes (Xu et al. 2000; Li et al. 2006).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1277-2
Microwave synthesis of zeolite membranes
can have certain benefits over conventional syn-
thesis methods:
1. Shorter synthesis time with higher energy
efficiency
2. Uniform crystal size and facile morphology
control
3. Improved membrane compactness with higher
membrane selectivity
4. Easier for scaling up
It is generally accepted that microwave
heating mainly owes its superiority to being
instantaneous, volumetric, and selective, known
as “thermal effects.” Some researchers suggest
the existence of “nonthermal effects,” even in
liquids, which are supposed not to require the
transfer of microwave energy into thermal
energy. For microwave synthesis of zeolite mem-
branes, nonthermal effects are still part of an
ongoing debate. Some speculations of the non-
thermal effects are proposed for microwave syn-
thesis of LTA zeolite membranes (Li and Yang
2008). In their opinion, the acceleration effect of
microwave synthesis is mainly due to the thermal
effects, whereas the distinctive morphology of
LTA zeolite membranes synthesized by micro-
wave is due to the nonthermal effects.
2 Microwave Synthesis of Zeolite Membranes

References Li YS, Chen HL, Liu J, Yang WS (2006) Microwave

Li YS, Yang WS (2008) Microwave synthesis of zeolite
membranes: a review. J Membr Sci 316:3–17
synthesis of LTA zeolite membranes without seeding.
J Membr Sci 277:230–239
Xu XC, Yang WS, Liu J, Lin LW (2000) Synthesis of a
high-permeance NaA zeolite membrane by microwave
heating. Adv Mater 12:195–196
S
Stimuli Responsive
Jinming Peng1, Xueting Zhao2, Yanlei Su2, Hong
Wu2 and Zhongyi Jiang2
1
Key Laboratory for Green Chemical
Technology of Ministry of Education, School of
Chemical Engineering and Technology, Tianjin
University, Tianjin, People’s Republic of China
2
School of Chemical Engineering and
Technology, Tianjin University, Nankai, Tianjin,
People’s Republic of China
Stimuli responsive: Stimuli responsive is a phe-
nomenon in which materials are capable of
reversibly altering their properties depending on
the environmental conditions or external stimuli.
External stimuli typically encompass physical
(e.g., temperature, photo, redox signal, or mag-
netic field), chemical (e.g., pH, ionic strength, or
a specific molecule), or biological (e.g., viruses
or bacteria) stimuli. The stimuli-responsive
membrane often involves the conformational
variation of sensitive units covering on the mem-
brane surface or the pore surface, which causes
the changes in physicochemical properties, pore
size, and permeation flux. The stimuli-responsive
membranes are playing an increasingly important
part in a diverse range of applications, such
as drug delivery, diagnostics, tissue engineering,
biosensors, and chemical and biological
separations.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1278-5
Thermo-responsive membranes can adapt to
environmental temperature change due to the
thermo-responsive polymer, whose temperature-
dependant solubility can reversibly solubilize
upon changes in temperature and lead to confor-
mational changes: stimulated collapse by dehy-
dration and expansion by rehydration (Lee
et al. 2010). The polymers are soluble in aqueous
solution below lower critical solution tempera-
ture (LCST) through hydrogen bonding with
water molecules but become dehydrated and
insoluble when heated above the LCST. The typ-
ical thermo-responsive linear polymers such as
poly(N-isopropylacrylamide) (PNIPAAm)
exhibit sharp phase transitions around 32  C,
below which the mixture of polymer and solution
is miscible. The thermo-responsive membranes
prepared through grafting of PNIPAAm are often
utilized for drug delivery because the LCST of
PNIPAAm is close to body temperature. Usually,
a significant increase of permeation flux and a
reduction of rejection can be observed when the
temperature increases above the LCST.
The pH-responsive membranes are prepared by
ionizable polymers with a pKa between 3 and 10.
Weak acids and bases like carboxylic
acids, phosphoric acid, and amines exhibiting a
change in the ionization state upon variation of
the pH of aqueous solutions are the candidates for
preparing pH-sensitive membranes. Classical
monomers includes acrylic acid (AAc),
methacrylic acid (MAAc), maleic anhydride
(MA), and N,N-dimethylaminoethyl methacrylate
2 Stimuli Responsive
(DMAEMA). The unique properties of
pH-responsive polymers arise from the facile pH
adjustment which induces the ionic interaction and
hydrogen bonding, resulting in a reversible micro
phase separation or self-organization phenomenon
(Wischerhoff et al. 2010). Thus, pH-responsive
polymeric systems provide the possibility for the
preparation of smart functional materials which can
be used for potential therapeutic applications, e.g.,
controlled drug delivery based on pH-triggered
release. Usually, the membranes with negatively
charged surface possess a higher flux at the pH
lower than the pKa of monomer than that of at the
pH higher than the pKa.
Photo-responsive membranes usually possess
photo-responsive units such as azobenzene,
spiropyran, and diarylethenes in the polymer
side chains, which are capable of isomerization.
Structure changes in the photo-sensitive units on
membrane surface lead to changes in the macro-
scopic properties including wettability, charge,
and mass transport.
Salt-responsive membranes can adapt to envi-
ronmental salt concentration (ionic strength) and
are often prepared using zwitterionic polymers of
polyelectrolyte. The addition of salt was found
to screen the electrostatic interaction within
the polyelectrolyte, resulting in conformation
changes from stretched to collapsed form
(Wandera et al. 2011). Usually, the porous mem-
brane possesses higher permeation flux and low
rejection under high ionic strength due to the
collapse of polymer chains and the fully open
pores.
Multi-responsive membranes are responsive
to more than one stimulus. Membranes exhibit
responses to different stimuli such as tempera-
ture, pH, and photo that are prepared based on
temperature-responsive NIPAAm and pH- and
photo-responsive spirobenzopyran. Membranes
fabricated by using acrylic acid, NIPAAm, and
cinnamoyloxyethyl acrylate exhibit four kinds of
responses to pH, temperature, ionic strength, and
photo stimuli.
References
Lee H, Pietrasik J, Sheiko SS, Matyjaszewski K (2010)
Stimuli-responsive molecular brushes. Prog Polym Sci
35:24–44
Wandera D, Wickramasinghe SR, Husson SM (2010)
Stimuli-responsive membranes. J Membr Sci
357:6–35
Wischerhoff E, Badi N, Laschewsky A, Lutz J (2010)
Smart polymer surface: concepts and applications in
biosciences. Adv Polym Sci 240:1–33
A
Antifouling Membrane Surface
Zhongyi Jiang1, Jinming Peng2, Xueting Zhao1,
Yanlei Su1 and Hong Wu1
1
School of Chemical Engineering and
Technology, Tianjin University, Nankai, Tianjin,
People’s Republic of China
2
Key Laboratory for Green Chemical
Technology of Ministry of Education, School of
Chemical Engineering and Technology, Tianjin
University, Tianjin, People’s Republic of China
The term fouling generally refers to an undesir-
able process in which a surface becomes
encrusted due to the undesirable accumulation
of foulants, such as biomacromolecules, micro-
organisms, hydrocarbons, particles, and colloids
from the surrounding environment. Antifouling
surface, also referred to as a “stealth surface,” can
minimize the intermolecular forces of interac-
tions between the foulants and the synthetic sur-
face so that the foulants can be easily released
under low shear stresses. Antifouling surfaces lie
at the heart of several contemporary and
advanced technologies, ranging from coatings
for ship hulls, biomedical implants, biosensors,
drug delivery, and membrane separations. Anti-
fouling membrane surface is one kind of antifoul-
ing surfaces. The antifouling surface is often
relevant to membranes utilized in microfiltration,
ultrafiltration, nanofiltration, and reverse osmo-
sis. The major foulants are different for different
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1279-6
membrane processes. The main foulants are
microorganisms and emulsified oils for
microfiltration, biomacromolecules and colloids
for ultrafiltration, natural organic matters for
nanofiltration, inorganic salts and bioorganic/
organic substances for reverse osmosis.
All the strategies for construction of antifoul-
ing membrane surface are based on manipulating
the physicochemical and/or topography structure
of membrane surface to weaken the interactions
between foulants and membrane surface and thus
inhibiting foulants adsorption or settlement.
There are four major types of antifouling mem-
brane surfaces, including hydrophilic surface,
hydrophobic surface, amphiphilic surface, and
reactive surface. Whitesides (Ostuni et al. 2001)
first proposed that antifouling surface showing
resistance to protein should have the following
four attributes: hydrophilic, hydrogen-bond
acceptors but not hydrogen-bond donors, and
overall electrically neutral. Poly(ethylene glycol)
(PEG)-based polymers and zwitterionic polymers
are the most widely used materials to fabricate
antifouling membranes. The antifouling mecha-
nism of the PEG-based polymers can be mainly
ascribed to the large repulsive hydration forces of
tightly bound water layer around the polymer
chains via hydrogen bonds or electrostatic attrac-
tion. The objective of hydrophilic surface is to
prevent the foulants from attaching onto the
membrane surface, which is known as “fouling
resistance” (Callow and Callow 2011). The
hydrophilic membrane surface can resist the
2 Antifouling Membrane Surface
fouling caused by biomacromolecules and natu-
ral organic matter. The hydrophobic surface is
based on nonpolar, low surface energy hydropho-
bic polymers, such as poly(dimethylsiloxane)
(PDMS) elastomers and fluoropolymers. The
mechanism of this hydrophobic surface is that
polar molecules (including adhesive protein)
barely adhere to membrane surface because of
reduced opportunities for forming the hydrogen-
bonding and polar interactions. This hydrophobic
surface aims to weaken the interfacial bonds so
that the attached foulants are more readily
removed by hydraulic shear forces, not prevent
foulants from attaching, which is known as “foul-
ing release.” The hydrophobic membrane surface
is suitable for mitigating the microorganism and
hydrocarbon fouling. The amphiphilic surface
comprising hydrophilic domains and hydropho-
bic domains on membrane surface incorporates
some of the benefits of both hydrophobic and
hydrophilic surfaces. The general aim is to create
a dynamic and compositional surface complexity
that deters settlement of foulants and reduces the
interfacial bonding with membrane surface. The
general aim of amphiphilic surface is to combine
the nonpolar, low surface energy properties of
hydrophobic domains to reduce polar and
hydrogen-bonding interactions with foulants,
with the well-known protein repellency proper-
ties of the hydrophilic domains. The resulting
amphiphilic surface may lower the entropic and
enthalpic driving forces for the adsorption of the
protein and organism. The amphiphilic mem-
brane surface can defer the fouling caused by
microorganisms, biomacromolecules, natural
organic matter, and hydrocarbons. Therefore,
the amphiphilic membrane surface is the most
promising antifouling membrane surface for the
practical separation system containing a wide
range of foulants. The reactive surface immobi-
lizes the component which can degrade organic
composition of foulants on membrane surface.
The proteases and titania nanoparticles are often
immobilized on membrane surface, thus
preventing biomacromolecules and microorgan-
ism fouling via enzymatic or photocatalytic deg-
radation (Banerjee et al. 2011).
Several modification approaches are
employed to create antifouling membrane surface
including surface coating, surface grafting, and
surface segregation (Shannon et al. 2008; Rana
and Matsuura 2010; Wang et al. 2005). For sur-
face coating, membranes are immersed in a poly-
mer modifier solution or inorganic particles
suspension. The modifier is settled on membrane
surface to create antifouling coating through van
der Waals force or electrostatic interactions. For
surface grafting, the modifier is settled on mem-
brane surface via graft polymerization including
graft-to and graft-from approach. The termed
graft-to approaches consist of the grafting of the
pre-synthesized polymer chains with a reactive
terminal group. Alternatively, graft-from
approaches, in which a polymer is grown in situ
from the surface via a surface-adsorbed initiation
group, are generally capable of producing denser
polymer layers. The surface coating and surface
grafting belong to the post-modification
approach, whereas surface segregation belongs
to the in situ modification approach. The polymer
modifiers comprising hydrophobic backbones
and hydrophilic side chains are added to casting
solution, lining membrane surfaces, and internal
pore during the conventional phase inversion pro-
cess. The hydrophilic chains segregate to mem-
brane surface and endow membrane with surface
hydrophilicity and antifouling property, while
hydrophobic backbones anchor to membrane
matrix polymers to defer loss of modifier during
phase inversion process.
The fouling resistance property could be eval-
uated by flux recovery ratio (FRR), while the
fouling release property could be evaluated by
flux decline ratio (FDR). The flux recovery ratio
(FRR) is the ratio of the water flux after hydraulic
cleaning to initial water flux, while the flux
decline ratio is the ratio of flux decline (the initial
water flux minus the flux for real feed) to initial
water flux. The higher the value of FRR, the
better the fouling resistance property of the mem-
brane; the lower the FDR, the better the fouling
release property of the membranes.
Antifouling Membrane Surface
References
Banerjee I, Pangule RC, Kane RS (2011) Antifouling
coatings: recent developments in the design of surface
that prevent fouling by proteins, bacteria, and marine
organisms. Adv Mater 23:690–718
Callow JA, Callow ME (2011) Trends in the development
of environmentally friendly fouling-resistant marine
coatings. Nat Commun 2:244–253
Ostuni E, Chapman RG, Holmlin RE, Takayama S,
Whitesides GM (2001) A survey of structure-property
relationships of surfaces that resist the adsorption of
protein. Langmuir 17:5605–5620
3
Rana D, Matsuura T (2010) Surface modification for anti-
fouling membranes. Chem Rev 110:2448–2474
Shannon MA, Bohn PW, Elimelech M, Georgiadis JG,
Marinas BJ, Mayes AM (2008) Science and technol-
ogy for water purification in the coming decades. Sci-
ence 452:301–310
Wang YQ, Wang T, Su YL, Peng FB, Wu H, Jiang ZY
(2005) Remarkable reduction of irreversible fouling
and improvement of the permeation properties of
poly(ether sulfone) ultrafiltration membranes by
blending with Pluronic F127. Langmuir
21:1856–11862
B
Bioinspired Membranes
Zhongyi Jiang, Yifan Li and Hong Wu
School of Chemical Engineering and
Technology, Tianjin University, Nankai, Tianjin,
China
Bioinspired membrane can be thought of as a
comprehensive name for a big family of artificial
membranes of which the design originality arises
from biological phenomena and principles in
nature. Compared with biomimetic membrane,
bioinspired membrane is a much broader term
(Rawlings et al. 2012), because a bioinspired
membrane does not necessarily employ biologi-
cal membrane or biologically occurring thin film
as the archetype. On the one hand, the membrane
materials (organic, inorganic, or organic-
inorganic hybrid) can be synthesized by borrow-
ing the fundamental principles of the materials
processing in nature. On the other hand, the
advancement in any branch of biological mate-
rials science related to structure, function, and
structure-function relationships can be employed
and incorporated to rationally design the structure
or function of bioinspired membrane. As a result,
the membrane preparation is usually conducted
under very mild conditions (aqueous solution,
ambient temperature and pressure, neutral or
near neutral pH, etc.), the membrane materials
are often easily available and biodegradable, the
membrane structure can be finely tuned, and the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1280-5
membrane often displays multiple functions and
high application efficiency. To some extent, the
bioinspired membrane can be viewed as next-
generation membrane.
At present, several bioinspired platform tech-
niques based on fascinating biochemistry and
biology have been developed. For example,
inspired by formation process of biosilica, a plat-
form technique called “biomineralization” or
“biomimetic mineralization” was developed to
fabricate polymer-inorganic nanohybrid mem-
brane (Pan et al. 2010). By using biomolecules
as catalyst and/or template, silica nanoparticles
were in situ generated and well dispersed in a
polymer matrix, and the as-prepared hybrid
membrane synergistically combined the advan-
tages of two components. Another platform tech-
nique example is “bioadhesion” or “biomimetic
adhesion.” This technique originated from
mussel-inspired catecholic chemistry, which
was successfully utilized to construct ultrathin
and stable active layer of dense composite mem-
brane (Li et al. 2009). The other techniques are
mostly based on self-assembly, in particular
layer-by-layer (LBL) assembly. LBL assembly
technique provides a powerful platform to manip-
ulate multiple interactions, such as covalent
bond, hydrogen bonding, charge transfer, hydro-
phobic, host-guest, and coordination bond inter-
actions (Matsusaki et al. 2012), so as to prepare
membrane with precisely tailored nanostructures
(i.e., thickness, free volume, hydrophilicity, etc.).
Future effort on this type of bioinspired
2 Bioinspired Membranes
Bioinspired Membranes,
Fig. 1 Concept of
nanotube-based
hierarchically structured
membrane with durable
high permeability and
selectivity
membrane may turn to improving the fundamen-
tal mechanism and extending the application
fields. Of course, new bioinspired platform tech-
niques will be continuously explored.
Selective transport properties and the
corresponding membrane structures are another
major concern in bioinspired membrane realm. In
biology, the most effective membrane-mediated
separation/transport processes often involve
complex, nonplanar articulations of structure
that are highly optimized to support the multiple
functions. Inspired by the hierarchical structures
in biology, rational design and synthesis hierar-
chical structures within membranes may offer
immense opportunities for efficient molecular/
ion sieving processes. For example, nanotubes
have been utilized to mimic biological channels
for rapid and selective molecule transport. With
the aid of nanotubes, an ideal concept of verti-
cally aligned biomimetic channels within a mem-
brane matrix have been proposed and shown in
Fig. 1, where membrane permeability, selectiv-
ity, and durability are individually manipulated
by the highly permeable nanopores, the entrance
chemistry of the nanotube, and the robust
nonporous filling matrix. Here, the aligned
nanotubes are extremely like the channel proteins
inserted through cell membranes. This concept
has partially come true recently (Xu et al. 2011),
and it requires much more efforts to fulfill all the
potentials of this concept. Also, many block
copolymers have been designed to mimic the
hydrophilic-hydrophobic mosaic structure of
biomembrane for antifouling (Chen et al. 2011).
Moreover, many efforts have been dedicated to
mimicking the proton pump and ion channel so as
to accelerate proton transport (Wang et al. 2012;
Sharma et al. 2010). In addition to selective trans-
port properties, intelligent properties of
membranes show great promise in membrane
science and technology (Tokarev and Minko
2010). For instance, self-healing membrane,
self-cleaning membrane, and many sorts of
stimuli-responsive membranes have been
reported (Chen et al. 2011; Wang et al. 2011b;
Capadona et al. 2008; Tokarev and Minko 2010).
Such smart behaviors can endow the membrane
with ultra-high stability, switchable permeation
flux, alternative driving force, etc. Other proper-
ties, such as mechanical strength, interface adhe-
sion, water retention, etc., have been successfully
reinforced by learning from nature (Zeng
et al. 2010; Ma et al. 2010; Wang et al. 2011a).
Breakthroughs in understanding how a living
system works and exploring new inspiration
source will ensure the sustainable development
of bioinspired membrane.
References
Capadona JR, Shanmuganathan K, Tyler DJ, Rowan SJ,
Weder C (2008) Stimuli-responsive polymer
nanocomposites inspired by the sea cucumber dermis.
Science 319:1370–1374
Chen WJ, Su YL, Peng JM, Dong YA, Zhao XT, Jiang ZY
(2011) Engineering a robust, versatile amphiphilic
membrane surface through forced surface segregation
for ultralow flux-decline. Adv Funct Mater
21:191–198
Li B, Liu WP, Jiang ZY, Dong X, Wang BY, Zhong YR
(2009) Ultrathin and stable active layer of dense com-
posite membrane enabled by poly(dopamine). Lang-
muir 25:7368–7374
Ma J, Zhang MH, Jiang ZY, Nie MC, Liu GX (2010) Fac-
ile fabrication of structurally stable hyaluronic acid-
based composite membranes inspired by bioadhesion.
J Membr Sci 364:290–297
Matsusaki M, Ajiro H, Kida T, Serizaw T, Mitsuru
A (2012) Layer-by-layer assembly through weak inter-
actions and their biomedical applications. Adv Mater
24:454–474
Bioinspired Membranes
Pan FS, Cheng QL, Jia HP, Jiang ZY (2010) Facile
approach to polymer-inorganic nanocomposite mem-
brane through a biomineralization-inspired process.
J Membr Sci 357:171–177
Rawlings AE, Bramble JP, Staniland SS (2012) Innovation
through imitation: biomimetic, bioinspired and
biokleptic research. Soft Matter 8:2675–2679
Sharma M, Yi MG, Dong H, Qin HJ, Peterson E, Busath
DD, Zhou HX, Cross TA (2010) Insight into the mech-
anism of the influenza aproton channel from a structure
in a lipid bilayer. Science 330:509–512
Tokarev I, Minko S (2010) Stimuli-responsive porous
hydrogels at interfaces for molecular filtration, sepa-
ration, controlled release, and gating in capsules and
membranes. Adv Mater 22:3446–3462
Wang JT, Zhang H, Yang XL, Jiang SA, Lv WJ, Jiang ZY,
Qiao SZ (2011a) Enhanced water retention by using
polymeric microcapsules to confer high proton con-
ductivity on membranes at low humidity. Adv Funct
Mater 21:971–978
3
Wang M, Janout V, Regen SL (2011b) Hyper-thin organic
membranes with exceptional H2/CO2 permeation
selectivity: importance of ionic crosslinking and self-
healing. Chem Commun 47:2387–2389
Wang JT, Yue XJ, Zhang ZZ, Yang Z, Li YF, Zhang H,
Yang XL, Wu H, Jiang ZY (2012) Enhancement of
proton conduction at low humidity by incorporating
imidazole microcapsules into polymer electrolyte
membranes. Adv Funct Mater. doi:10.1002/
adfm.201201436
Xu T, Zhao N, Ren F, Hourani R, Lee MT, Shu JY, Mao S,
Helms BA (2011) Subnanometer porous thin films by
the co-assembly of nanotube subunits and block copol-
ymers. ACS Nano 5:1376–1384
Zeng H, Hwang DS, Israelachvili JN, Waite JH
(2010) Strong reversible Fe3+-mediated bridging
between dopa-containing protein films in water. Proc
Natl Acad Sci 107:12850–12853
B
Biomimetic Membranes
Zhongyi Jiang, Jing Zhao, Shaofei Wang,
Dong Yang and Hong Wu
School of Chemical Engineering and
Technology, Tianjin University, Nankai, Tianjin,
China
Biomimetic membrane is designed and fabricated
by imitating the composition, structure, forma-
tion process, as well as functions of biological
membrane. As we know, biological membrane is
the vital structural basis in organism, on which
the essential life activities in cell take place. The
asymmetric and hierarchical bilayer structure
formed by the in situ self-assembly of amphi-
philic phospholipid and functional proteins
(Nielsen 2009) ensures the biological membrane
take important roles in keeping the environmen-
tal stability of cell, participating in the multiple
interactions of different cells, and efficiently
achieving the conversion of energies, the signal
transduction between cells, as well as the conver-
sion and transmembrane transport of some sub-
stances (Zhu et al. 2011). Biological membrane
has a very sophisticated structure consisting of
abundant species of lipids and proteins, which is
difficult to imitate completely due to the con-
straints of current science and technologies
(Eeman and Deleu 2010). As a simplification
and transition, biomimetic membranes
containing part of (not all) the key components
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1281-6
or characteristics of biological membrane are
being actively developed in the last few decades.
Biomimetic membranes can be divided into
two categories in terms of structural morphology:
freestanding membrane and supported mem-
brane. The freestanding membrane is often
utilized for theoretical investigation purpose, in
other words, as a simplified model for studying
the structure and function of biological mem-
branes. This type of biomimetic membranes
mainly includes the lipid monolayer membrane
and the bilayer lipid membrane or named black
lipid membrane (BLM) (Eeman and Deleu 2010;
Kim et al. 2012). The BLM is suitable for inves-
tigating membrane phase behavior and mem-
brane processes such as membrane fusion and
molecular recognition for its closer structure
with biological membrane, while the lipid mono-
layer is suitable for mimicking and evaluating the
insertion of amphipathic compounds (Eeman and
Deleu 2010). The biomimetic membrane has pro-
vided an effective platform for exploring the
complex structure and function of biological
membrane, even though further endeavors both
in biological science and fabrication technology
are still needed.
The supported membrane often contains a
bilayer residing onto a solid substrate, which
delicately ameliorates the weak stability and
short lifetime of BLM (Li et al. 2012). Further-
more, the self-assembly of block copolymer
(black polymer membrane, BPM) as another
approach to form the bilayer can be an alternative
2 Biomimetic Membranes
of BLM for its higher stability, controllability,
and ability to prevent the direct contact of embed-
ded proteins to solid substrate, which otherwise
will inactivate the proteins (Duong et al. 2012;
Nielsen 2009). The supported BLM or BPM can
be prepared by several methods, of which vesicle
collapse technique is commonly used (Eeman
and Deleu 2010). In addition to act as model of
biological membrane for investigating protein-
lipid interaction, this type of biomimetic mem-
brane performs well as functional membrane in
various fields by incorporating different func-
tional proteins: (1) energy conversion (energy
converter, energy-production devices), (2) signal
transduction (biosensor and bioanalysis), and
(3) substance transport and conversion (drug
delivery, immobilized enzyme catalysis, and
membrane-based separation). To further exploit
the application efficiency and area of biomimetic
membrane, more efforts may be devoted to the
following two aspects: (1) utilize channel pro-
teins directly for the preparation of biomimetic
membrane while acquiring the good control over
the channel density and the protein activity and
(2) deepen the insight into the structure-function
relationship of membrane proteins.
References
Duong PHH, Chung TS, Jeyaseelan K, Armugam A,
Chen Z, Yang J, Hong M (2012) Planar biomimetic
aquaporin-incorporated triblock copolymer mem-
branes on porous alumina supports for nanofiltration.
J Membr Sci 409–410:34–43
Eeman M, Deleu M (2010) From biological membranes to
biomimetic model membranes. Biotechnol Agron Soc
14:19–736
Kim YR, Jung S, Ryu H, Yoo YE, Kim SM, Jeon TJ
(2012) Synthetic biomimetic membranes and their
sensor applications. Sensors 12:9530–9550
Li X, Wang R, Tang C, Vararattanavech A, Zhao Y,
Torres J, Fane T (2012) Preparation of supported
lipid membranes for aquaporin Z incorporation. Col-
loids Surf B 94:333–340
Nielsen CH (2009) Biomimetic membranes for sensor and
separation applications. Anal Bioanal Chem
395:697–718
Zhu B, Li J, Xu D (2011) Porous biomimetic membranes:
fabrication, properties and future applications. Phys
Chem Chem Phys 13:10584–10592
F
Fouling Release
Zhongyi Jiang1, Xueting Zhao1, Jinming Peng2,
Yanlei Su1 and Hong Wu1
1
School of Chemical Engineering and
Technology, Tianjin University, Nankai, Tianjin,
China
2
Key Laboratory for Green Chemical
Technology of Ministry of Education, School of
Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, China
Fouling release is one of the general strategies to
achieve desired non-fouling surfaces. Any sur-
face immersed in a specific aqueous system
(wastewater, seawater, tap water, etc.) is
subjected to the undesirable settlement and
nonspecific adsorption of biomolecules (e.g., pro-
tein and polysaccharide), natural organic matter,
hydrocarbon, and microorganism (e.g., bacteria,
algae, and mollusks), known as fouling.
Non-fouling surfaces to resist different foultants
are vital in a wide range of applications including
chemical separation and purification, drug deliv-
ery systems, biomaterials, biosensors, and marine
coatings. The concept of fouling release initially
comes from marine non-biocidal coating. Foul-
ing release refers to the feature that the attached
and adhering foulants are more easily removed
from the depositing surfaces at low hydrody-
namic shear forces due to the weakened interfa-
cial bond between the synthetic surface and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1282-5
different foultants, promoting adhesive failure.
The release ability of foulants is proportional to
the surface energy and modulus (gE)1/2 (Brady
and Singer 2000). The lower the surface energy
and modulus, the stronger reduction of the
enthalpy of adsorption and the higher fouling
release potential of the surface. Surface with
compositional heterogeneous hydrophobic/
hydrophilic domains can also reduce interactions
with the bioadhesives. In the design of surfaces to
eliminate the adhesion of various foulants,
polysiloxane- and fluorinated polymer-based sur-
faces are usually hydrophobic and most effective
in reducing adhesion. The major advantage of
polysiloxane-based surfaces is the synergy
between low surface energy (to minimize the
work of adhesion) and low elastic modulus. The
major advantage of fluorinated polymer-based
surfaces lies in hydrophobicity and oleophobicity
with low surface energy.
Marine non-fouling coatings provide a source
of inspiration for fouling release membrane.
Membranes with fouling release property are
essential for preventing fouling growth on the
surfaces whose antifouling performance relies
on the low adhesion strength and easy release of
foulants on such a membrane. In recent years,
surface modification of membranes using low
surface energy materials to enhance fouling
release ability is under active studying
microfiltration, ultrafiltration, nanofiltration,
reverse osmosis, etc. The surface energy and het-
erogeneities are introduced in the elucidation of
2 Fouling Release
membrane fouling release mechanism during
membrane filtration. The lower surface energy
and larger chemical heterogeneity correspond to
a lower driving force for the adsorption of the
foulants, thereby resulting in effective fouling
release ability. Surfaces which fulfill these
requirements are often derived from
polysiloxane- and fluorine-based polymers. In
situ forced surface segregation of amphiphilic
copolymers and grafting low surface energy mol-
ecules or monomers to already formed mem-
branes are popular methods to fabricated fouling
release membrane. Membranes with low surface
energy chains (such as PDMS, poly(ethylene
glycol)-fluoropolymers, perfluoroalkyl polymers,
perfluoropolyether polymers, and fluorine-
containing block)showed a high release rate.
The release rates of PDMS and perfluoroalkane
polymer-functionalized membranes are about
five times higher than those of hydrophilic sur-
face as a result of the low interaction between the
low surface energy surfaces and protein (Thérien-
Aubin et al. 2011). There is a growing body of
evidence that amphiphilic or chemically hetero-
geneity membrane surfaces can present both low
surface energy and high hydration energy
microdomains and show promising performance
against a wide range of foulants. Membrane pre-
pared from amphiphilic copolymers with hydro-
philic segments and fluorine-containing
segments via nonsolvent-induced phase
separation (NIPS) process through forced surface
segregation showed enhanced oil, protein, and
bacteria release ability (Chen et al. 2011). The
low surface energy microdomains on the mem-
brane surface minimize the intermolecular forces
of interactions (polar or and hydrogen-bonding
interactions) between the foulants and the mem-
brane surface, remarkably reducing the flux
decline and reducing energy consumption during
the dynamic filtration process.
In the application of antifouling membranes
for water treatment and biomedical application,
fouling release membranes offer an interesting
alternative to environmentally friendly strategies
to facilitate foulants removal, such as hydrocar-
bon substances, biomolecules, and
microorganisms.
References
Brady RF, Singer IL (2000) Mechanical factors favoring
release from fouling release coatings. Biofouling
15:73–81
Chen WJ, Su YL, Peng JM, Dong Y, Zhao XT, Jiang ZY
(2011) Engineering a robust, versatile amphiphilic
membrane surface through forced surface segregation
for ultralow flux-decline. Adv Funct Mater
21:191–198
Thérien-Aubin H, Chen L, Ober CK (2011) Fouling-
resistant polymer brush coatings. Polymer
52:5419–5425
F
Fouling Release Membranes
Zhongyi Jiang1, Xueting Zhao1, Jinming Peng2,
Yanlei Su1 and Hong Wu1
1
School of Chemical Engineering and
Technology, Tianjin University, Tianjin,
People’s Republic of China
2
Key Laboratory for Green Chemical
Technology of Ministry of Education, School of
Chemical Engineering and Technology, Tianjin
University, Tianjin, People’s Republic of China
Fouling release membrane is a novel kind of
membrane that has the chemical structure and
main feature of nonpolar low surface energy
microdomains and hydrophilic domains,
inhibiting the nonspecific adsorption of a variety
of foulants. The low surface energy
microdomains on the membrane surface, which
can be constructed with silicone- and fluorine-
based polymers, are used to minimize the
intermolecular forces of interactions (polar
and/or hydrogen-bonding interactions) between
the foulants and the membrane surface. The
hydrophilic domains are used to bind water mol-
ecules and generate hydration layer similar with
widely popular hydrophilic modification
methods. Considering that foulants tend to adsorb
on traditional hydrophobic membrane surfaces
driving by the decrease of the Gibbs free energy
of the system, the surface energy of membranes is
regarded as one of the most relevant
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1283-5
physicochemical parameters influencing free
energy of the adsorption process. The reduction
of the surface energy causes a strong reduction of
the enthalpy of adsorption which describes the
strength of interaction between the protein and
the surface and thus strongly decreases the driv-
ing force for the foulants to adsorb to the surface
(Worz et al. 2012). Due to the presence of non-
polar low surface energy microdomains on the
membrane surface, foulants in the feed solution
can easily release from the membrane surface and
diffuse back to the bulk feed solution during the
dynamic membrane filtration process. Inspired by
marine fouling release materials, this kind of
membrane is initially designed to detach the
foulants from the surface at low hydrodynamic
shear force, and now it is applied to achieve low
permeation flux decline and high permeation flux
recovery simultaneously during the membrane
filtration process.
To construct fouling release membrane sur-
face, majority of the existing researches have
been carried out to reduce the surface free energy
through fluorine-based polymers. In situ forced
surface segregation and post-surface grafting are
the two general surface modification methods
being explored to introduce low surface energy
microdomains onto the membrane surface. In the
process of the forced surface segregation, amphi-
philic copolymers with hydrophilic segments and
fluorine-containing segments are used as addi-
tives or polymer membrane materials as that usu-
ally applied in surface segregation approach.
2 Fouling Release Membranes
HFBM segments surface coverage
F HFBM =0
agitating
a b
agitating
agitating
feed solution oil
Fouling Release Membranes, Fig. 1 Tentative illustration of the flux decline resistant mechanism of membranes
(Chen et al. 2011b)
Considering that fluorine-containing segments
are not able to spontaneously segregate onto the
polymer-water interface due to the unfavorable
thermodynamics, the forced surface segregation
coupled with nonsolvent-induced phase separa-
tion process is proposed for achieving membrane
surfaces with fluorine-containing microdomains.
In the immersion-precipitation step, hydrophilic
segments of the copolymers segregate to the
polymer-water interface freely and drag the
fluorine-containing hydrophobic segments to
enrich on membrane surfaces. Both the composi-
tion of hydrophilic and hydrophobic segments
and the volatility of casting solvent can affect
the surface segregation behavior and the fouling
release ability of membrane surfaces (Chen
et al. 2011a, b). The membrane materials used
in the post-surface grafting method must be rich
of reactive groups. Surface grafting by chemical
reaction is a facile method for introducing low
surface energy microdomains onto hydrophilic
F HFBM =15.4%
agitating agitating
c
agitating agitating
agitating agitating
PHFBM microdomain membrane
membrane surfaces. Low surface energy
perfluoroalkyl or even polysiloxyl molecules
with active groups are used as modifiers to
improve the fouling release ability of membrane
(Thérien-Aubin et al. 2011; Zhao et al. 2012).
Although hydrophilic surface modification
can significantly enhance the antifouling property
of the membrane, it, unfortunately, often results
in a drastic flux decline during the separation and
purification process. Fouling release membrane is
an alternative to traditional hydrophilic mem-
brane which leads to lower permeation flux
decline. Figure 1 reports a tentative flux decline
resistant mechanism of fouling release mem-
brane. The random presence of nonpolar low
surface energy (typically fluorinated)
microdomains on the hydrophilic membrane sur-
face creates a surface with chemical heterogene-
ity that is vital to constructing a truly fouling
release membrane surface. At moderate shear
rate along membrane surface, nonpolar low
Fouling Release Membranes
surface energy microdomains prevent the coales-
cence, migration, and spreading of the hydropho-
bic oil droplets or limit the accumulation/
coalescence of polar biofoulants, thus endowing
the membrane surface with outstanding fouling
release potential without inducing a flux decline.
References
Chen WJ, Su YL, Peng JM, Dong YN, Zhao XT, Jiang ZY
(2011a) Engineering a robust, versatile amphiphilic
membrane surface through forced surface segregation
for ultralow flux-decline. Adv Funct Mater
21:191–198
3
Chen WJ, Su YL, Peng JM, Zhao XT, Jiang ZY, Dong YN,
Zhang Y, Liang YP, Liu JZ (2011b) Efficient waste-
water treatment by membranes through constructing
tunable antifouling membrane surfaces. Environ Sci
Technol 45:6545–6552
Thérien-Aubin H, Chen L, Ober C (2011) Fouling-
resistant polymer brush coatings. Polymer
52:5419–5425
Worz A, Berchtold B, Moosmann K, Prucker O, Ruhe
J (2012) Protein-resistant polymer surfaces. J Mater
Chem 22:19547–19561
Zhao XT, Su YL, Chen WJ, Peng JM, Jiang ZY
(2012) Grafting perfluoroalkyl groups onto polyacry-
lonitrile membrane surface for improved fouling
release property. J Membr Sci 415–416:824–834
M
Microcapsule Membranes
Zhongyi Jiang1, Xiaoli Wang1, Hong Wu1 and
Jiafu Shi2
1
School of Chemical Engineering and
Technology, Tianjin University, Tianjin, China
2
School of Environment Science and
Engineering, Tianjin University, Tianjin, China
Definition
Microcapsule is defined as a hollow microsphere
comprising large interior void and semiperme-
able shells. The interior void serves as storage
space or reaction chamber, while the shell pro-
tects the bioactive materials/nanoparticles in the
interior void from the attack of surrounding envi-
ronment or controls the transfer of substance
in/out the microcapsule. Till now, microcapsule
with single shell, double shells, and multiple
shells as well as yolk-in-shell structure has been
designed and prepared. Since the shell of the
microcapsule often possesses nanometer/
micrometer thickness and distinct semipermeable
property, it fits the typical features of membrane.
Therefore, microcapsule shell can be also called
microcapsule membrane, which was first intro-
duced by Chang in 1960s (Chang 1964).
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1284-9
Characteristics
Microcapsule membrane can be categorized into
inorganic, organic, and inorganic–organic hybrid
membranes based on the material composition.
Inorganic microcapsule membrane usually pos-
sesses porous structure and high mechanical sta-
bility, which is often synthesized under relatively
harsh conditions (e.g., hydrothermal treatment,
calcinations, or organic solvent treatment). In
comparison, the synthesis of organic microcap-
sule membrane (mainly self-assembly of amphi-
pathic polymer, layer-by-layer self-assembly, or
surface polymerization) is often conducted under
rather mild conditions; however, the mechanical
stability of organic microcapsule membrane is
usually much lower than that of inorganic micro-
capsule membrane as a result of lack of stiff
blocks. Recently, incorporating inorganic com-
ponents/moieties into organic microcapsule
membrane has been demonstrated as a facile,
generic to enhance the mechanical stability.
Moreover, considering the advantage that hybrid-
ization could offer new opportunities to create
multifunctional materials with unique properties
by combining the merits of inorganic and organic
building blocks, hybrid microcapsule membrane
may win more promising applications in the
future.
Microcapsule membrane has single-, double-,
or multiple-layered structure. Single-layered
microcapsule membrane is usually composed of
homogeneous polymers or inorganics, while
2 Microcapsule Membranes
double-layered microcapsule membrane is often
composed of two separate layers with different
kinds of materials. Multiple-layered microcap-
sule membrane mainly refers to the microcapsule
membrane which is composed of multilayers
through the alternative deposition/self-assembly
of two kinds of oppositely charged polymers,
polymer/inorganic hybrids.
Microcapsule has been applied in diverse
areas, including biocatalysis, drug delivery, pol-
lutants removal, biosensing, etc., where micro-
capsule membrane plays the crucial role in
governing the overall performance of the micro-
capsule. For instance, Jiang et al. prepared
protamine–titania hybrid microcapsule mem-
brane and encapsulated the biocatalyst enzyme
in the capsule lumen. The enhanced recycling
stability of enzyme was due to the high mechan-
ical stability of microcapsule membrane (Jiang
et al. 2009). Caruso et al. developed a redox-
responsive microcapsule membrane and encap-
sulated hydrophobic cargo in the capsule lumen.
The cargo could be released in simulated intra-
cellular conditions, which were ascribed to
reversible disulfide linkages of membrane mate-
rials (Yan et al. 2011). Kreft et al. designed a
light-responsive microcapsule membrane and
encapsulated dextran in the capsules. The dextran
is released when near-infrared laser light illumi-
nated the capsules, which was ascribed to the
incorporation of light-absorbing gold
nanoparticles into the microcapsule membrane
(Kreft et al. 2007). Li et al. reported that the
porous MnO2 microcapsules showed good ability
to remove an organic pollutant (azo dye Congo
red) in wastewater, which was ascribed to the
excellent dye adsorption capability of porous
microcapsule membrane (Fei et al. 2008). Yu
et al. prepared polymeric microcapsule mem-
brane and encapsulated rhodamine 6G. The cap-
sules rapidly released rhodamine 6G in ethanol
but cannot release in aqueous solution. This was
because the charge density of microcapsule mem-
brane in ethanol was markedly decreased due to
its low dielectric constant as compared to that in
aqueous solution (Yu et al. 2009).
References
Chang TMS (1964) Semipermeable microcapsules. Sci-
ence 146:524–525
Fei JB, Cui Y, Yan XH, Qi W, Yang Y, Wang KW, He Q,
Li JB (2008) Controlled preparation of MnO2 hierar-
chical hollow nanostructures and their application in
water treatment. Adv Mater 20:452–456
Jiang YJ, Yang D, Zhang L, Sun QY, Sun XH, Li J, Jiang
ZY (2009) Preparation of protamine-titania microcap-
sules through synergy between layer-by-layer assem-
bly and biomimetic mineralization. Adv Funct Mater
19:150–156
Kreft O, Skirtach AG, Sukhorukov GB, Möhwald
H (2007) Remote control of bioreactions in multicom-
partment capsules. Adv Mater 19:3142–3145
Yan Y, Wang YJ, Heath JK, Nice EC, Caruso F (2011)
Cellular association and cargo release of redox-
responsive polymer capsules mediated by exofacial
thiols. Adv Mater 23:3916–3921
Yu B, Wang D, Ye Q, Zhou F, Liu W (2009) Robust
polydopamine nano/microcapsules and their loading
and release behavior. Chem Commun 6789–6791
B
Breakthrough Pressure
Renzo Di Felice
University of Genoa, Genoa, Italy
The pressure required for a liquid to enter the
membrane pore is called breakthrough pressure.
This parameter is of practical relevance as the
membrane will not work properly if liquid enters
the pores reducing in this way the contact effi-
ciency. Breakthrough pressure can be estimated
by using the Young-Laplace equation
2s cos y
P¼
r
where s is the liquid surface tension, y the contact
angle, and r the radius of membrane pore. It can
be seen that high breakthrough pressure can be
obtained by using liquids with high surface
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1287-3
tension, by reducing the pore size, and by increas-
ing the contact angle. However, there are practi-
cal limitations. For example, most of the physical
solvents used for bulk CO2 removal have low
surface tensions, and the reduction in the mem-
brane pore size beyond certain limit results into
reduced transport of the gas through the mem-
brane due to diffusion limitations. The higher
contact angle for a given solvent is favored by
the membrane material having low surface
energies.
In order to give an idea, a hydrophobic poly-
propylene membrane with a pore size of 0.05 mm
has a breakthrough pressure larger than 1 MPa
(Wiesler 1996).
References
Wiesler F (1996) Ultrapure water. UP130427
D
Diffusivity
Renzo Di Felice
University of Genova, Genova, Italy
Synonyms
Diffusive transport; Molecular diffusivity
For a species in a homogeneous phase, gas,
liquid, or solid, diffusivity can be defined as any
material transport driven by concentration differ-
ence. Its physical origin lies in the random molec-
ular motion that leads to an overall phenomenon
of smoothing concentration gradients: any batch
systems originally showing concentration differ-
ence for one or more species will eventually be
completely mixed if enough time is elapsed. Dif-
fusivity is easily quantified by the diffusivity flux,
i.e., by how much a species diffuses per unit area
per unit time.
There are various practical situations which
for different reasons, both theoretical and practi-
cal, have received particular attention and have
been investigated in depth. A brief summary is
given here (Cussler 1997).
• Molecular diffusivity. In this case, the fluid
where the phenomenon is taking is considered
unbounded so that there is no physical
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1289-5
interaction between the diffusing species and
the system boundaries. Moreover, the species
are considered to be diluted so that any inter-
action between the diffusing molecules can
also be neglected. This is probably the most
studied cases, and many systems can be con-
sidered to fall in these categories.
• Diffusivity of strong electrolytes. As before
here we considered the system to be
unbounded. However, there is an interaction
between the diffusing molecules which affects
the transport rate and must be taken into
account.
• Diffusivity of associating solutes. The solute
associates to form aggregates (weak electro-
lytes or micelle), and again this affects the
transport rate.
• Solvation. Solute-solvent interactions cannot
be ignored in this case.
• Solute-boundary interactions are important:
here we can have diffusion in porous media
or composite, diffusion in cylindrical pore
(Knudsen or surface or capillary or molecular
sieving).
References
Cussler EL (1997) Diffusion. 2nd edition, Cambridge
University Press, Cambridge (UK)
E

Effective Diffusivity wild values, as high as ten, which are difficult to

justify with geometrical arguments alone.
Renzo Di Felice The concept of effective diffusivity is also
University of Genova, Genova, Italy applied for the case of species diffusing in het-
erogeneous media, such a polymer filled with a
second, less permeable, material. Maxwell
Effective diffusivity is a convenient parameter (1873) has obtained an exact expression, in the
which is introduced when diffusion takes place case of composite media filled with spheres, for
in non-homogenous media. Consider, for exam- the effective diffusivity given as
ple, the case where a species is diffusing through
 
porous particles, such as reactant diffusing inside 2 1 1 1
þ  2f 
a catalytic solid. In this case, the molecules have DS D D D
Deff ¼D  S 
to travel for a longer distance given that the pores 2 1 1 1
of the catalytic particles are not straight, and þ þf 
DS D DS D
moreover diffusion takes place over a smaller
area due to the solid being wall impermeable. where D is the diffusion coefficient in the primary
These effects are taken into account by defining media, Ds the diffusion coefficient through the
an effective diffusivity as spheres, and f the sphere volume fraction. For
e the limiting case of the spheres being completely
Deff ¼ D impermeable, Maxwell expression simplify to
t
1f
where e is the particle void fraction and thereby Deff ¼ D
f
takes into account the reduced flow area available 1þ
and t is the tortuosity which considers the longer 2
distance traveled by the molecules. It should be
Various empirical expressions have been
stressed, however, that more often than not, the
reported in literature in order to take into account
parameter inside the parenthesis is utilized as a
the deviation from sphericity of the foreign mate-
fitting factor derived from experimental data
rial. Particularly simple and efficient is the
rather than predicting factor from the solid phys-
expression proposed by Nielsen (1967):
ical characteristics. These result in the reported
tortuosity factor, for example, to assume rather

# Springer-Verlag Berlin Heidelberg 2014

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1290-3
2 Effective Diffusivity

1f References
Deff ¼ D
af
1þ Di Felice R, Cazzola D, Cobror S, Oriani L (2008) Oxygen
2
permeation in PET bottles with passive and active
walls. Packag Technol Sci 21:405–415
where a is the dispersed material aspect ratio. Maxwell JC (1873) A treatise on electricity and magne-
Nielsen relationship has been shown to do a sat- tism, vol 1. Clarendon Press, Oxford
isfactory job against experimental evidence Nielsen LE (1967) Models for the permeability of filled
(Di Felice et al. 2008). polymer systems. J Macromol Sci A1(5):929–942
E
Effectiveness Factor
Renzo Di Felice
University of Genova, Genova, Italy
The concept of effectiveness factor is utilized
when the effect of diffusion on the overall rate
of a reacting process wants to be taken into
account. Let’s consider a catalytic solid particle
where a reaction takes place. For a species to
react, it must, at the same time, diffuse inside
the catalytic particle and react. It is intuitive that
the diffusion step slows the overall process rate,
and an effectiveness factor is defined as
¼
actual rate of process
rate of process if diffusion were infinitively fast
This definition is equivalent to consider reactant
concentration on any point in the catalytic parti-
cle equal to that at the external surface.
A rather straightforward mass balance allows
the determination of the effectiveness factor for a
single cylindrical pore where a first-order reac-
tion is taking place on the wall:
tanhf
¼
f
where f is the Thiele module defined as
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1291-3
sffiffiffiffiffiffiffiffi
f¼L
k
Deff
with L the pore length, k the chemical reaction
kinetic factor, and Deff the reacting species effec-
tive diffusivity.
As expected the effectiveness factor
approaches 1 when Thieles module is very
small, i.e., for very short pores or very slow
reaction or very high diffusion coefficients. On
the other hand, for very high value of Thiele
modules, effectiveness factor approaches the
inverse of the Thiele module.
The above result can be easily generalized for
the case of flat plate by putting L equal to half the
plate width, for the case of long cylindrical pellets
by putting L equal to half the pellet radius, and to
the case of spherical pellets by putting L equal to
one third the sphere radius. Extension to kinetic
different from the first order has been presented in
literature, and a summary can be found, for exam-
ple, in Satterfield (1991).
References
Satterfield CN (1991) Heterogeneous catalysis in indus-
trial practice. McGraw-Hill, New York
I
Intrinsic Activation Energy
Renzo Di Felice
University of Genova, Genova, Italy
Transport phenomena and chemical reaction
rates are influenced by temperature. This effect
is reflected on the numerical value of the coeffi-
cient rate, which therefore depends on the vari-
able temperature. Both for mass transfer
coefficient and chemical reaction coefficient, var-
ious theoretical approaches have been suggested
in order to predict and quantify their dependency
on the temperature. However, these approaches
have had limited success, and the effect of the
temperature is generally obtained through exper-
imental evidence. A generally accepted relation-
ship linking kinetic coefficient and temperature is
the Arrhenius’ law, which is written as
 
E value of the ratio (E/R) and consequently that
k ¼ k0 exp 
RT
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1292-3
where k is the generic kinetic coefficient, E is the
activation energy, R is the universal gas constant,
and T is the absolute pressure.
Arrhenius’ law is basically an empirical rela-
tionship which however has been found to repro-
duce with the satisfactory accuracy of
experimental data and the effect of temperature.
A small value of the activation energy
E corresponds to a weak influence of the temper-
ature on the kinetic constant, whereas a large
value of the activation energy E is representative
of kinetic constant strongly influenced by tem-
perature. Just as a reference, for gas phase chem-
ical reaction, the activation energy is normally
high, in the range of 50–250 kJ/mol, while that
for diffusion coefficient is less than 10 kJ/mol).
The classic way to estimate the activation
coefficient from experimental data is to utilize a
plot having 1/T on the x-axis and ln(k) on the
y-axis. The slope of the best fitting curve passing
through the experimental points will yield the
of E.
K
Knudsen Diffusion
Renzo Di Felice
University of Genova, Genova, Italy
Synonyms
Knudsen transport modeling
Whenever a species is diffusing inside a confined
space, such as cylindrical pore, an interaction
between the diffusive molecules and the pore
wall is to be expected. One possibility is given
by the pore wall physically interacting with the
diffusive molecules and hindering, as a conse-
quence, their movement. The phenomenon,
called Knudsen diffusion, is relevant whenever
the distance between molecular collisions is
greater than the pore diameter. This interaction
can be the governing factor of the diffusion rates.
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1293-3
Liquid have a relatively small mean-free path,
few angstroms, so that Knudsen diffusion in not
important in practical cases, but on the other
hand, for gas this parameter can assume values
larger than 1,000 Å and therefore be significant.
The diffusion coefficient, DKn, in the Knudsen
regime can be estimated from gas kinetic theory,
and it is given by
rffiffiffiffiffi
T
DKn ¼ 4850d
M
where d is the pore diameter in cm, T the absolute
temperature, and M the molecular weight of the
diffusive species. Unlike diffusion in unbounded
systems, Knudsen diffusion coefficient is inde-
pendent of pressure and of the molecular weight
of the second species.
L
Liquid Entry Pressure (LEP or LEPW)
Renzo Di Felice
University of Genova, Genova, Italy
In membrane distillation it is of paramount
importance that liquid does not fill the membrane
pores, in order to keep membrane efficiency to
the highest possible value. To this end hydropho-
bic membranes are normally used. The hydro-
phobicity can be quantified through the
so-called liquid entry pressure (LEP) parameter,
defined as the pressure difference at which liquid
penetrates into the membranes pores.
The pressure required to force water through
the structure is inversely proportional to the open-
ing size and dependent on the polymeric proper-
ties of the membrane. A theoretical expression,
based on Young-Laplace equation, enables the
estimation of LEP (see, e.g., El Bourawi
et al. 2006):
2gcosy
DP ¼
r Kim B-S, Harriot P (1987) Critical entry pressure for
where g is the liquid surface tension, y the contact
angle between liquid and membrane, and r is the
pore radius.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1295-1
Given the practical difficulty of obtaining the
exact value of the above physical parameters, it is
not uncommon to estimate LEP experimentally,
and Smolders and Franken (1989) described a
detailed procedure which should be followed in
this case. Basically pressure difference is gradu-
ally applied on both side of the membrane until
the first drop of the liquid appears on the perme-
ate side (more specific description is given in the
suggested reference). Typical values of LEP
range from tenth to tens of bars (0.1–20 bar): for
example, with liquid water at ambient condition,
a PTFE membrane with 95 % porosity, 25 mm
thickness, and 3 mm nominal pore size has an LEP
of 0.13 bar, whereas a PTFE supported mem-
brane with 75 % porosity, 120 mm thickness,
and 0.2 nominal pore size has an LEP of 4.0 bar
(Kim and Harriot 1987).
References
El Bourawi S, Ding Z, Ma R, Khayet M (2006)
A framework for better understanding membrane dis-
tillation separation processes. J Membr Sci 285:4–29
liquids in hydrophobic membranes. J Colloid Interface
Sci 115:1–8
Smolders K, Franken ACM (1989) Terminology for mem-
brane distillation. Desalination 72:249–262
M
Mass Transport Equations
Renzo Di Felice
University of Genova, Genoa, Italy
Synonyms
Mass transfer resistance
Mass transfer is a phenomenon, generated by a
concentration difference, by which a component
is transferred from a point to another. The intro-
duction of a mass transfer coefficient is a simple
way to quantify this phenomenon. Mass transfer
coefficient is defined as the ratio between the
component flux and the driving force generating
the flux (Cussler 1997),
rate of component flux
k¼
driving force
The unit of the mass transfer coefficient depends
on the units used to quantify flux and driving
force. For example, if we express fluxes in
kmol/m2s and driving force is a concentration
difference (kmol/m3) then k will have the unit
of m/s. However, reader should be aware that
different units are sometime used, depending on
the circumstances: fluxes can be expressed in
mass rather than moles, and driving force can be
a partial pressure or a molar fraction difference.
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1298-1
The definition of a mass transfer coefficient
could not be simpler but nothing can be said a
priori about its numerical value. For the way is
has been defined, mass transfer coefficient is a
function of the two points considered for the mass
transfer, although in the vast majority of cases
one point is the fluid phase (gas or liquid) bulk
and the other is a system boundary, such as a tube
wall or an interface. The coefficient numerical
value depends on the specific system considered
(flow in pipes, fixed bed of particles, falling liquid
film) and on the physical parameters (such as
diffusivity, density, viscosity, etc.). As it is most
useful for situations where an analytical approach
is not practical or too complex, its quantification
relies on experimental measurements. Much
effort has been devoted to generalizes as much
as possible data collected from experimental
measurements, and this has been done by corre-
lating the data through dimensional parameter,
(1)
generally involving a suitable defined Sherwood
number, containing the mass transfer coefficient,
Reynolds number, and Shmidt number, in anal-
ogy with observation on heat transfer which cor-
relate Nusselt number with Reynolds and Prandtl
numbers. Practical relevant examples are the case
of mass transfer taking place for the flow inside a
pipe between the phase bulk and the tube wall
Nu ¼ 0:026 Re0:8 Sc0:33
2 Mass Transport Equations

or the flow outside and perpendicular to a capil- driving force, a parameter which is given by the
lary bed “homogenized” difference between pA and CA
obtained by substituting the concentration in
Nu ¼ 0:80 Re0:47 Sc0:33 one phase with the corresponding equilibrium
value in the other phase. In other word
The concept of mass transfer coefficient can also
be utilized when transfer between different pA
Driving force ¼ pA  HCA ¼  CA
phases is considered, such as mass transfer H
between a gas and a liquid phase or mass transfer
where H is the parameter expressing the partition
between fluids separated by a dense membrane.
equilibrium of the component A between the gas
The definition given in Eq. 1 is still applicable
and the liquid phase (which assumes a constant
although care must be taken when the driving
value if a Henry law type equilibrium applies).
force is to be quantified. As a descriptive exam-
ple, let’s consider the case of mass transfer of a
component A taking place between the bulk of
gas phase, with pA the component partial pressure References
and the bulk of a liquid phase, with CA the com-
ponent concentration. The overall mass transfer Cussler EL (1997) Diffusion. Mass transfer in fluid sys-
tems, vol 2. University Press, Cambridge
coefficient can be defined in this case as the ratio
between component A mass flux and overall
B

Block Copolymer Membrane Am
X þ Y
Bn ! Bn þ XY
Am

If the species are bifunctional, multiblock

Mario Malinconico
copolymers can be obtained. Despite the general
Research Director, Institute for Polymers,
indications just described, the interest for the
Composites and Biomaterials (IPCB-CNR),
production of block copolymers is focused on
Pozzuoli, Naples, Italy
anionic initiators and polymerization processes
having living character. This way, derived from
the original studies of M. Szwarc (1956), pro-
Block Copolymers
vides copolymer sequences well defined, with
desired molecular weights, structures, and com-
Block copolymers are polymeric materials in
positions. All this is achieved with diene mono-
which macromolecules of two or more different
mers, vinyl (nonpolar), esters, ethers, or cyclic
homopolymers (blocks) are chemically bonded
sulfides.
together to form complex macromolecules with
The key technologies for producing block
linear (di-, tri-, multiblock copolymers) or
copolymers with anionic initiators can be indi-
nonlinear (mixed arm star, block, or graft copol-
cated schematically in the following way:
ymers) architecture (Fig. 1).
The routes of synthesis of block copolymers
– Sequential polymerization of the monomers
are two:
(especially in the case of di-blocks)
– Polymerization of the second monomer with
1. Creating centers or active sites (radical,
the functionalized prepolymers of the first
anionic, cationic) of a polymer chain that can
monomer
subsequently trigger the polymerization of a
– Use of reactions of coupling between reactive
second monomer. If the location of the termi-
terminals and a compound reagent that
nal active center is not specified, this defini-
becomes the junction site:
tion also includes graft copolymers.
2. Condensation between functional groups
2Am
Bn ! Am
Bn
X
Bn
Am
located at the end of the polymer or
prepolymer:
– Use of bifunctional initiators

The synthesis of multiblock copolymers can

be obtained by an alternately sequential addition

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1306-1
2 Block Copolymer Membrane

ABC triblock Mixed arm

AB diblock
star block
AB

ABA triblock

(AB)n star (AB)n multiblock

Block Copolymer Membrane, Fig. 1 Linear and nonlinear architecture of block copolymers

of different comonomers into a living copolymer- the precursors because most of the reactive end
ization system or, alternatively, by the coupling groups are segregated inside the polymer chains
of difunctional homopolymeric precursors. coiled in good solvent. Moreover, for long poly-
In the first case, anionic polymerization or, mer chains, the concentration of the reactive end
more recently, living radical polymerization groups is too low to have an effective coupling or
methods can be in principle used. In real cases linking reaction because the overall polymer con-
(Ekizoglou and Hadjichristidis 2002; Buzdugan centration cannot be too high. Therefore, the
et al. 2000; Reuter et al. 1991), each addition of a essential problem is how to expose and concen-
new monomer will inevitably make some living trate the reactive end groups of long polymer
chains dead because of impurities, leading to the chains, while the overall polymer concentration
resultant block copolymer with lower block num- will not be increased.
bers and broad molecular weight distribution.
Therefore, the sequential addition method can
only be used to make copolymers with a few
Block Copolymers in Membranes
blocks, such as triblock copolymers. Another
limitation of the sequential addition of different
Copolymers, and in particular block copolymers
comonomers is their reaction compatibility: each
(BCPs), in recent years have aroused great inter-
added monomer must be sufficiently reactive so
est in the field of specialty polymer applications,
that the chain can propagate. Often, a living
including nanotechnologies (Park et al. 2003;
A block can initiate comonomer B, but a living
Krausch and Magerle 2002; Hamley 2003;
B block cannot initiate comonomer A.
Lazzari and Lopez-Quintela 2003; Lu and Sastry
In the second approach, multiblock copoly-
2007; Hawker and Russell 2005; Li et al. 2005;
mers could be in principle prepared by coupling
Segalman 2005; Cheng et al. 2006; Stoykovich
(Yagci and Tasdelen 2006) different polymer
and Nealey 2006; Krishnamoorthy et al. 2006; Li
chain di-ends terminated with suitable reactive
and Ober 2006; Fasolka and Mayes 2001; Darling
groups or by linking (Yagci and Tasdelen 2006;
2007; Kim and Hinsberg 2008; Bates and
Rahman et al. 2007) di-end-functionalized poly-
Fredrickson 1999; Abetz and Simon 2005; van
mer chains using so-called difunctional linking
Zoelen and ten Brinke 2009), given their ability
agents in solution. However, both coupling and
to self-organize into structures with periodicity
linking reactions are extremely ineffective when
down to the nanometer scale.
long polymer chains (Mw >5  103) are used as
Block Copolymer Membrane
Block Copolymer
Membrane,
Fig. 2 Schematic of “self- A
assembly” in BCPs due to
phase separation
block copolymer
If the different polymer blocks are chemically
incompatible, phase separation occurs with spon-
taneous segregation of different macromolecules
in different microdomains (Fig. 2).
Microdomains formed are not arranged in a ran-
dom but show a regular arrangement which
involves the formation of periodic structures.
This phenomenon, called “self-assembly,”
determines the spontaneous formation of
nanostructures. It is associated with the competi-
tion between the tendency to separation of phase,
due to the incompatibility of the blocks, and
chemical connectivity that prevents it; periodic
structures are formed in which the contact area
between the incompatible microdomains is min-
imized. The minimization of the interfacial area
between the domains involves a reduction in
interfacial energy for which even if from an
entropic point of view the individual polymer
chains prefer a conformation random coil, in the
case of block copolymers, macromolecules tend
to assume more extended conformations at the
interface between the two blocks so as to allow
similar blocks to organize into microstructures
that minimize the ratio (surface exposed/
volume).
The frequency and size of these domains
depend on the lengths of the regular blocks and,
therefore, from the molecular masses.
Block copolymers find many interesting appli-
cations in membrane technology.
Block copolymers have found application in a
class of rubbery membranes, having the unique
ability to separate CO2 from gas streams, with a
consequent increase in performance compared to
3
phase-separated
block copolymer
that of the analogous homopolymers (Guan and
De Simone 1994).
The polyethylene oxide [PEO] is, for example,
one of the most interesting materials for the sep-
aration of CO2, especially when cross-linked with
other polymers or incorporated into block copol-
ymers (Lin et al. 2006; Pethe et al. 2008).
Because of its amorphous character and of its
flexibility, it suitably directs the permselectivity
of CO2 through the polymer matrices, especially
when the length of the segment, the weight, and
the molecular ratio with the other blocks of the
copolymer complexes are changed.
Bondar et al. (2000) observed that the perme-
ability of CO2 increases with the amount of
polyether [PEO or PTMEO] when segmented
block copolymers are incorporated into the
polyether-b-polyamide, where they form the seg-
regated phase of nylon-6 [PA6] or nylon-12
[PA12]. In particular, they have observed that
the copolymers 57PEO/PA6 and 55PEO/PA12
exhibit a better selectivity to pure gas CO2/N2
56 (PCO2 66 barrer) and CO2/H2 9.8 (PCO2
20 barrer), respectively, compared to more con-
ventional polymers rubbery and glassy.
Higher performance was observed when more
than one unit polar (PEO and PA6) were included
in the polymer chain, suggesting the critical role
of interesting polar intermolecular interactions
between the polymer chain and the penetrating
molecules. Membranes PEO/PBT have been ad
hoc designed in order to obtain block copolymers
with high performance for the separation of CO2
(Zhao et al. 2008). Separation factors for the pairs
of gases, such as CO2/H2, CO2/N2, and CO2/CH4,
4 Block Copolymer Membrane
were obtained in different ratios of the polymer
chain. When mixed with the polyether glycol
[PEG], a significant improvement of the perme-
ability and selectivity for various block copoly-
mers was observed.
References
Abetz V, Simon PF (2005) Phase Behaviour and Morphol-
ogies of Block Copolymers. Adv Polym Sci 189:125
Bates FS, Fredrickson GH (1999) Block Copolymers-
Designer Soft Materials. Phys Today 52:32
Bondar VI, Freeman BD, Pinnau I (2000) Gas transport
properties of poly(ether-b-amide) segmented block
copolymers. J Polym Sci Part B Polym Phys
38:2051–2062
Buzdugan E, Ghioca P, Stribeck N (2000) Synthesis and
properties of styrene-isoprene multiblock copolymers.
Mater Plast 37(3):138–144
Cheng JY, Ross CA, Smith HI, Thomas EL (2006)
Templated self-assembly of block copolymers: top-
down helps bottom-up. Adv Mater 18:2505
Darling SB (2007) Directing the self-assembly of block
copolymers. Prog Polym Sci 32:1152
Ekizoglou N, Hadjichristidis NJ (2002) Synthesis of
model linear tetrablock quaterpolymers and
pentablock quintopolymers of ethylene oxide. Polym
Sci Part A Polym Chem 40(13):2166–2170
Fasolka MJ, Mayes AM (2001) Block copolymer thin
films: physics and applications. Annu Rev Mater Res
31:323
Guan Z, De Simone JM (1994) Fluorocarbon-based
Heterophase Polymeric Materials: Block Copolymer
Surfactants for Carbon Dioxide Applications. Macro-
molecules 27:5527–5532
Hamley IW (2003) Nanotechnology with soft materials.
Angew Chem Int Ed 42:1692
Hawker CJ, Russell TP (2005) BCP lithography: merging
“bottom-up” with “top-down” processes. MRS Bull
30:952
Kim HC, Hinsberg WDJ (2008) Surface patterns from
block copolymer self-assembly. J Vac Sci Technol
A 26:1369
Krausch G, Magerle R (2002) Nanostructured thin films
by self-assembly of block copolymers. Adv Mater
14:1579
Krishnamoorthy S, Hinderling C, Hcinzelmann H (2006)
Nanoscale patterning with block copolymers. Mater
Today 9:40
Lazzari M, Lopez-Quintela MA (2003) Block copolymers
as a tool for nanomaterial fabrication. Adv Mater
15:1583
Li MQ, Ober CK (2006) Block copolymer patterns and
templates. Mater Today 9:30
Li MQ, Coenjarts CA, Ober CK (2005) Patternable Block
Copolymers. Adv Polym Sci 190:183
Lin H, Van Wagner E, Swinnea JS, Freeman BD, Pas SJ,
Hill AJ, Kalakkunnath S, Kalika DS (2006) Transport
and Structural Characteristics of Crosslinked Poly(eth-
ylene oxide) Rubbers. J Membr Sci 276:145–161
Lu W, Sastry AM (2007) Self-assembly for semiconduc-
tor industry. IEEE Trans Semicond Manuf 20:421
Park C, Yoon J, Thomas EL (2003) Enabling Nanotech-
nology with Self Assembled Block Copolymer Pat-
terns. Polymer 44:6725
Pethe VV, Wang HP, Hiltner A, Baer E, Freeman BD
(2008) Oxygen and carbon dioxide permeability of
EAA/PEO blends and microlayers. J Appl Polym Sci
110:1411–1419
Rahman MS, Sama LS, Lee JS (2007) Quantitative In
Situ Coupling of Living Diblock Copolymers for the
Preparation of Amphiphilic Coil-Rod-Coil Triblock
Copolymer Poly(2-vinylpyridine)-b-poly(n-hexyl iso-
cyanate)-b-poly(2-vinylpyridine). Macromolecules
40(26):9279–9283
Reuter H, Berlinova IV, Horing S, Ulbricht J (1991) The
anionic block copolymerization of ethylene oxide with
tert-butyl methacrylate. Diblock and multiblock
copolymers. Eur Polym J 27(7):673–680
Segalman RA (2005) Patterning with block copolymer
thin films. Mater Sci Eng R Rep 48:191
Stoykovich MP, Nealey PF (2006) Block copolymers and
conventional lithography. Mater Today 9:20
Szwarc M (1956) ‘Living’ Polymers. Nature 178:1168
van Zoelen W, ten Brinke G (2009) Thin films of
complexed block copolymers. Soft Matter 5:1568
Yagci Y, Tasdelen MA (2006) Mechanistic transforma-
tions involving living and controlled/living polymeri-
zation methods. Prog Polym Sci 31(12):1113–1170
Zhao Y, Cao Y M, Ding X L, Zhou MQ, Liu J H and Yuan
Q (2008) Poly(ethylene oxide) induced cross-linking
modification of Matrimid membranes for selective
separation of CO2. J Membrane Sci 320, 179–184
P
Proton-Exchange Membranes
for Fuel Cells
He Bai1 and W.S. Winston Ho2
1
Momentive Performance Materials Inc, Friendly,
WV, USA
2
Department of Chemical and Biomolecular
Engineering, The Ohio State University, Columbus,
OH, USA
A fuel cell is an electrochemical device that can
directly convert the chemical energy of a fuel into
electricity. It is regarded as a promising energy
conversion approach in the twenty-first century
and has received increasing attention worldwide.
Among all types of fuel cells, the proton-
exchange membrane fuel cell (PEMFC) is con-
sidered as the most promising candidate for small
stationary power generators and automotives due
to its high power density, relatively low operating
temperature, and fast startup. Compared to inner
combustion engines, PEMFCs can reduce pollu-
tion (with only water in emission when using
hydrogen as fuel), increase energy efficiency
(40–50 % for PEMFC vs. 20–35 % for inner
combustion), and decrease the nation’s depen-
dence on foreign oil (Song 2002).
The proton-exchange membrane is a very
important component inside a PEMFC, and its
main functions include (a) separation of oxygen
from the fuel, (b) conduction of protons, and
(c) barrier of electrons. As summarized by
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1309-3
Hickner et al., there are six common criteria
critical to all high performance PEMs, including
(1) high proton conductivity and low electron
conductivity, (2) desirable thermal, chemical,
oxidative, and hydrolytic stability, (3) desirable
mechanical properties in both dry and hydrated
states, (4) low permeability to both fuel and the
oxidant, (5) low cost, and (6) capability of being
fabricated into membrane electrode assemblies
(MEAs). Majority of PEM materials rely on
absorbed water and its interaction with acid
groups for producing proton conductivity. Thus,
in most cases, proton conductivities of PEMs
increase with the increase of relative humidity
(RH) (Hickner et al. 2004).
Dupont’s Nafion ® and other perfluorinated
sulfonic acid membranes (e.g., Aciplex ® from
Asahi Kasei, Femion ® from Asahi Glass,
PRIMEA ® Series of MEAs from W.L. Gore &
Associates, etc.) are currently popular to use for
low temperature (<100  C) PEMFCs due to their
high proton conductivity, desirable mechanical
strength, and good chemical stability. However,
some disadvantages, such as high cost and high
dependence of proton conduction on the water
content, seriously limit the industrial application
of these membranes. It is desirable for a PEMFC
to operate at high temperatures and low RHs
since high-temperature operations can accelerate
the reaction rates at the anode/cathode and
increase the anode’s tolerable level of CO in the
fuel, and low humidity operations can facilitate
the water management of the fuel cell system.
2 Proton-Exchange Membranes for Fuel Cells
The US Department of Energy has established a
goal of 0.1 S/cm for the proton conductivity of the
PEM, with target operating conditions at 120  C
and 50 % RH (Hickner et al. 2004).
Cost-effective and thermally stable alternative
membranes, including sulfonated polyimide
(SPI), sulfonated poly(arylene ether sulfone)
(SPAES), sulfonated poly(aryl ether ketone)
(SPAEK), and polybenzimidazole (PBI)-based
membranes, etc., have drawn interests in the
past decade. SPI, SPAES, and SPAEK copoly-
mers are synthesized by copolymerization of
sulfonated monomers (Hickner et al. 2004).
These sulfonated copolymer-based membranes
are still highly dependent on water content, and
a hydrophilic component has been incorporated
into the membrane for water retention (Bai and
Ho 2011). But, the oxidative and hydrolytic sta-
bility of these copolymers needs to be further
improved prior to long-term operations. On the
other hand, H3PO4-doping has been identified as
a successful approach for the application of PBI
as high-temperature and low humidity PEMs
(Li et al. 2009; Bai and Ho 2011). In this case,
fuel humidification is not necessary in fuel cell
operations due to the unique proton conduction
mechanism by self-ionization and self-
dehydration of H3PO4. In addition, the PBI
polymer showed very desirable stability under
fuel cell operations, even at high-temperature
(>150  C) conditions. However, acid leakage
through such membranes during long-term fuel
cell operations remains to be a concern. Signifi-
cant research efforts are continuing in both aca-
demia and industry for the further improvement/
development of perfluorinated, alternative hydro-
carbon polymer-based and polymer/inorganic
hybrid PEMs.
References
Bai H, Ho WSW (2011) Recent developments on fuel
processing and proton-exchange membranes for fuel
cells. Polym Int 60:26–41
Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath
JE (2004) Alternative polymer systems for proton
exchange membranes (PEMs). Chem Rev
104:4587–4612
Li Q, Jensen JO, Savinell RF, Bjerrum NJ (2009) High
temperature proton exchange membranes based on
polybenzimidazoles for fuel cells. Prog Polym Sci
34:449–477
Song C (2002) Fuel processing for low-temperature and
high-temperature fuel cells: challenges and opportuni-
ties for sustainable development in the 21st century.
Catal Today 77:17–49
B
Butanol-Water Mixtures: Separation
by Pervaporation
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Because of the shortage of crude oil and the
environmental requirement, the utilization of
renewable resources for energy production, such
as using the potential acetone-butanol-ethanol
(ABE) fermentation process to produce butanol
as a biofuel, has been receiving increased atten-
tion in recent years. However, the fermentation
process suffers from severe inhibition due to the
high toxicity of butanol to microorganisms even
at low concentrations (4–6 g
L 1). In order to
eliminate the inhibition, in situ product recovery
systems have been developed (Vane 2005).
Pervaporation (PV) is considered to be a particu-
larly promising recovery technique, because of
its general advantages in energy saving and envi-
ronmental issue, particularly no medium ingredi-
ents removed from the fermentation broth and no
harmful effects on microorganisms.
The hydrophobic pervaporation membranes
used for butanol recovery and concentrate
include: polydimethylsiloxane (PDMS) and its
modified copolymer and mixed matrix
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1316-1
membranes, liquid membrane, poly[-1-
(trimethylsilyl)-1-propyne] (PTMSP) membrane,
poly(ether block amide) (PEBA) membrane,
polypropylene (PP) membrane, polytetrafluor-
oethylene (PTFE) membrane, etc. (Vane 2005;
Liu et al. 2011). PDMS, as the most typical
hydrophobic polymeric membrane, is widely
investigated and proved to be stable and prospec-
tive for industrial applications. The operating
parameters of PV, including feed temperature
(T), feed concentration (C), feed flow rate and
permeate pressure (P), etc., have significant
impacts on membrane performance. Take the
PDMS/ceramic membrane, for example, flux
increased as temperature increased, while the
separation factor decreased slightly. As the buta-
nol concentration increased, the total flux
increased while the separation factor changed
slightly. The total flux increased with the flow
rate, but the separation factor changed little (Liu
et al. 2011).
Pervaporation using hydrophobic membranes
might not be enough for concentrating butanol for
direct reuse. Hydrophobic membranes were pre-
ferred for concentrating butanol when the con-
centration of butanol is low. As an alternative,
when the butanol concentration is high and the
water content is low, the hydrophilic membranes
should be used for the water removal, so that the
pervaporation process is economic for butanol
production.
2 Butanol-Water Mixtures: Separation by Pervaporation
The hydrophilic pervaporation polymeric
membranes used for dehydration of butanol-
water mixtures include: poly (vinyl alcohol)
(PVA) membrane, polyimide membrane,
chitosan membrane, sodium alginate membrane,
polyelectrolyte, etc. (Chapman et al. 2008). PVA
is the most commonly used hydrophilic poly-
meric membrane, but it often shows a lack of
chemical, mechanical, and thermal stability. In
recent years, the PI membrane began to be used
for dehydration because of its excellent mechan-
ical and thermal stability. The main inorganic
membranes used for butanol dehydration are sil-
ica membrane (Verkerk et al. 2001) and A-type
zeolite (NaA) membrane (Morigami et al. 2001).
References
Chapman PD, Oliveira T, Livingston AG, Li K (2008)
Membranes for the dehydration of solvents by
pervaporation. J Membr Sci 318:5–37
Liu GP, Hou D, Wei W (2011) Pervaporation separation
of butanol-water mixtures using PDMS/ceramic com-
posite membrane. Chin J Chem Eng 19:1–5
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Technol 25:251–260
Vane LM (2005) A review of pervaporation for product
recovery from biomass fermentation processes.
J Chem Technol Biotechnol 80:603–629
Verkerk AW, van Male P, Vorstman MAG, Keurentjes
JTF (2001) Description of dehydration performance of
amorphous silica pervaporation membranes. J Membr
Sci 193:227–238
B
Biobutanol Recovery from Biomass
Fermentation Broth
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Biobutanol recovery from biomass acetone-
butanol-ethanol (ABE) fermentation broth by
pervaporation is a process that couples ABE fer-
mentation with in situ pervaporation recovery
acetone, butanol, and ethanol from fermentation
broth.
During the past decade, there has been an
increasing interest for the production of biofuels
from renewable resources because of growing
concerns about global warming and increasing
consumption of crude oil. Butanol, as compared
to ethanol, is less volatile and explosive, contains
more energy, and can easily mix with gasoline in
any proportion. In addition, butanol can be used
directly or blended with gasoline or diesel with-
out any vehicle retrofit, since the air to fuel ratio
and the energy content of butanol are close to
gasoline (Qureshi and Ezeji 2008). Biobutanol
is produced from renewable resources (biomass)
by acetone butanol ethanol (ABE) fermentation
process. However, usually the maximum concen-
tration of total solvents (ABE) do not exceed
20 g/L due to the end-product inhibition on
microbes, resulting in high energy cost to recover
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1317-1
ABE from the dilute fermentation broth by dis-
tillation. Therefore, several in situ product-
removal technologies, such as adsorption, gas
stripping, liquid-liquid extraction, perstraction,
pervaporation, and reverse osmosis, have been
developed. These technologies could be coupled
with ABE fermentation process to reduce the
effect of product inhibition and improve the
sugar utilization and solvent productivity
(Garcı́a et al. 2011).
Pervaporation (PV) is a membrane process for
liquid separation, in which a polymeric or inor-
ganic membrane usually serves the separating
barrier. The application of PV for butanol recov-
ery from fermentation broth is based on the selec-
tive permeation of organic compounds through
the membrane when the nature of the membrane
is hydrophobic. PV is especially effective for the
system in which the concentration of the targeted
species is low; for instance, the butanol content in
the fermentation broth is very low. Furthermore,
the pervaporation process is energy efficient and
it is harmless to the fermentation broth.
PV membranes can be made from either poly-
meric or inorganic materials, even both of them
(Qureshi and Blaschek 1999). The polymeric
pervaporation membranes for extracting butanol
from fermentation broth include polydimethyl-
siloxane (PDMS) membranes, poly
[1-(trimethylsilyl)-1-propyne] (PTMSP) mem-
branes, poly(ether block amide) (PEBA) mem-
branes, liquid membranes, other modified
polymer membranes, as well as porous
2 Biobutanol Recovery from Biomass Fermentation Broth
Biobutanol Recovery from Biomass Fermentation Broth, Fig. 1 ABE fermentation-pervaporation-coupled
process
polypropylene (PP) membranes and polytetra-
fluoroethylene (PTFE) membranes. Among
them, the commonly used PDMS membranes
with good selectivity and stability are regarded
as the most potential PV membranes for butanol
recovery application. The typical inorganic mem-
brane for PV is hydrophobic zeolite membrane,
such as ZSM-5 and silicalite-1 membrane. The
process of biobutanol recovery from biomass
ABE fermentation broth by pervaporation is
also called ABE fermentation-pervaporation-
coupled process; its conventional flow chart is
shown in Fig. 1 (Liu et al. 2011). A pervaporation
membrane module is connected to the fermentor,
and the ABE solvent can be selectively and con-
tinuously removed from the fermentation broth
and then concentrated in the membrane down-
stream side. As result, the ABE concentration in
the broth is kept at low level to facilitate the
continuous fermentation process as well as
enhance the solvent productivity. In addition, a
microfiltration/ultrafiltration unit can be
alternatively installed before the pervaporation
module, in order to retain microbes and avoid
the biofouling of pervaporation membranes.
References
Garcı́a V, Päkkilä J, Ojamo H, Muurinen E, Keiski
R (2011) Challenges in biobutanol production: how
to improve the efficiency. Renew Sustain Energy Rev
15:964–980
Liu G, Wei W, Wu H, Dong X, Jiang M, Jin W (2011)
Pervaporation performance of PDMS/ceramic com-
posite membrane in acetone butanol ethanol (ABE)
fermentation-PV coupled process. J Membr Sci
373:121–129
Qureshi N, Blaschek H (1999) Butanol recovery from
model solution/fermentation broth by pervaporation:
evaluation of membrane performance. Biomass
Bioenergy 17:175–184
Qureshi N, Ezeji T (2008) Butanol “a superior biofuel”
production from agricultural residues (renewable bio-
mass): recent progress in technology. Biofuels
Bioprod Biorefin 2:319–330
C
Ceramic Membrane
for Pervaporation
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Ceramic membrane for pervaporation, which is
also called inorganic pervaporation membrane,
belongs to inorganic microporous membranes
made from silica, alumina, or zeolite, which has
a narrow pore size distribution typically with pore
diameter smaller than 1 nm. Inorganic
pervaporation membranes have better structural
stability without the problems of swelling or
compaction relative to organic membranes.
They usually can withstand harsh chemical envi-
ronments and high temperatures (Wee
et al. 2008). Most of the inorganic pervaporation
membranes are asymmetrical, with several
macroporous support layers providing the
mechanical strength and a microporous selective
top layer providing the selectivity. According to
the membrane materials, inorganic pervaporation
membranes generally have two kinds: zeolite
membranes and silica membranes.
Zeolites are microporous aluminosilicate min-
erals with crystalline structures that have uniform
and molecular-sized pores, which have been used
extensively as catalysts and adsorbents. Zeolite
membranes are synthetized by the deposition of
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1318-1
continuous polycrystalline zeolite layers on porous
supports, first reported by Suzuki in 1987 (Suzuki
1987). Zeolite structures are made up of TO2,
where T represents tetrahedral framework atoms,
such as Si, Al, B, Ge, Fe, and P. Most zeolites
contain Si with other metals substituted into the
framework (Bowen et al. 2004). The zeolite pores
are made from rings in the framework and are
designated by the number of oxygen atoms making
up the ring. Small-pore zeolites include those struc-
tures made up of eight-member oxygen rings,
medium-pore zeolites have 10-member rings, and
large-pore zeolites have 12-member rings. Exam-
ples of each of these are shown in the ball-and-stick
representations of zeolite frameworks in Fig. 1
(Bowen et al. 2004). Several zeolite structures
such as MFI, LTA, MOR, and FAU are widely
reported as zeolite membranes used for
pervaporation, due to their unique characteristic
such as pore structure, adsorption properties, and
their mechanical and chemical stability, as
described in Table 1 (Baerlocher et al. 2002). Zeo-
lite membranes are most often prepared by hydro-
thermal synthesis, including in situ synthesis,
secondary growth method, continuous flow synthe-
sis method, microwave synthesis, etc. (Wee
et al. 2008). By utilizing the properties of molecu-
lar sieving and preferential adsorption, the current
pervaporation applications of zeolite membranes
mainly include alcohol (e.g., ethanol,
iosopropanol, butanol) dehydration, organic/
organic separations (e.g., xylene isomers, metha-
nol/methyl-tert-butyl ether mixtures, methanol/
2 Ceramic Membrane for Pervaporation

Ceramic Membrane
for Pervaporation,
Fig. 1 Atomic stick
representations for the
frameworks of CHA (a),
MFI (b), and MOR (c)
zeolite structures. The
nodes represent tetrahedral
framework atoms and the
sticks represent oxygen
bridges (Reproduced from
Bowen et al. 2004)

Ceramic Membrane for Pervaporation, Table 1 Characteristics of the zeolite applied in membrane and an example
of its application in pervaporation (Reproduced from Baerlocher et al. 2002)
Zeolite
A Y ZSM-5 Mordenite
Structure type LTA FAU MFI MOR
Si/Al ratio 1 2.3 8
1 4
Cations Na Na, Ca Na Na
Pore size 0.41 nm  0.74 nm  0.74 nm 0.51 nm  0.55 nm 0.65 nm  0.70 nm
0.41 nm 0.53 nm  0.56 nm 0.34 nm  0.48 nm
0.26 nm  0.57 nm
Channel network Three Three dimensional Three dimensional One dimensional
dimensional
Application Dehydration of Separation of Separation of Separation of benzene/
organic mixture methanol/MTBE xylene isomers p-xylene mixture
mixture

benzene mixtures), and acid separations (e.g.,
acetic acid/water mixtures). In 2000, the first
industrial-scale separation plant, based on NaA
zeolite membrane for pervaporation dehydration
of organic-water mixtures, was developed by
Mitsui Engineering and Shipbuilding Co. Ltd. in
Japan (Morigami et al. 2001). Until Now, NaA
zeolite membranes have been commercialized by
the Busan Nano-Research Institute Inc. (BNRI, a
subsidiary of Mitsui), SMART Chemical company
(UK), Inocermic GmbH (Germany), and Nanjing
Jiusi Hi-Tech Co. (China) (Gascon et al. 2012).
Unfortunately, NaA zeolite membranes are very
sensitive to even the slightest acidity.
Ceramic Membrane for Pervaporation
Another kind of ceramic membrane for
pervaporation is silica membranes, which now
are commercially available and developed by
The Netherlands Energy Research Corporation
(ECN) (Verkerk et al. 2001). The microporous
silica membranes consist of four support layers of
a- and g-alumina, and the selective top layer at
the outer wall of the tube is made of amorphous
silica. Silica membranes are mechanically and
chemically robust. Not only are the silica mem-
branes stable in a normal industrial environment,
they can even be used to remove water from
condensation reactions like esterifications,
where strongly acidic conditions predominate.
However, silica membranes are not stable against
water, and thus the addition of oxides such as
ZrO2 and TiO2 is often employed to improve
the membrane stability toward water and alkali
(Wee et al. 2008).
3
References
Baerlocher C, Meier WM, Olson DH (2002) Atlas of
zeolite framework types, 5th edn. Elsevier,
Amsterdam
Bowen TC, Noble RD, Falcone JL (2004) Fundamentals
and applications of pervaporation through zeolite
membranes. J Membr Sci 245:1–33
Gascon J, Kapteijn F, Zornoza B, Sebastián V, Casado C,
Coronas J (2012) Practical approach to zeolitic mem-
branes and coatings: state of the art, opportunities,
barriers, and future perspectives. Chem Mater
24:2829–2844
Morigami Y, Kondo M, Abe J, Kita H, Okamoto K (2001)
The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif
Technol 25:251–260
Suzuki H (1987) Composite membrane having a surface
layer of an ultrathin film of cage-shaped zeolite and
processes for production thereof. US Patent 4,699,892
Verkerk AW, van Male P, Vorstman MAG, Keurentjes
JTF (2001) Description of dehydration performance of
amorphous silica pervaporation membranes. J Membr
Sci 193:227–238
Wee S-L, Tye C-T, Bhatia S (2008) Membrane separation
process-pervaporation through zeolite membrane. Sep
Purif Technol 63:500–516
T
Thermopervaporation (Thermo-PV)
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Pervaporation is a membrane separation process
which is based on difference of vapor pressure as
driving force. It is a well-established tool for
component recovery from the aqueous phase.
Nowadays, pervaporation is usually performed
industrially with vacuum as driving force. Vac-
uum pumps are switched periodically to remove
non-condensable gases. For some actual produc-
tion process, it is unfavorable (Volkov and
Bortisov 2012). In vacuum operation only a
small pressure loss can be allowed at the perme-
ate side, because an increase in partial down-
stream pressure influences flux and selectivity
negatively. Since large apparatus volumes are
necessary, leakage problems may occur, oxygen
might diffuse into the apparatus, which would
lead to oxidation (Franken et al. 1990).
Thermopervaporation is also called thermo-
pervaporation or thermo-PV. It overcomes the
drawbacks of vacuum pervaporation. A reduced
partial pressure at the permeate side can also be
gained by a temperature difference between feed
side and permeate side of the membrane. Based
on this technology, it is possible to integrate the
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1319-4
condensation energy for direct heating of the feed
during pervaporation in one single module.
Thermopervaporation is a new concept for
pervaporation that benefits from small distances
in a membrane module to recover internal heat to
the most.
The thermopervaporation process (shown in
Fig. 1) aims at making effective use of the con-
densation energy of pervaporation vapors. The
energy comes from heating the feed. Shortening
the vapor transport distances can make the most
use of the energy. The initial feed stream
(F) enters the module in the condenser at temper-
ature Tl1 (heat resistance in the condenser has
been neglected). The feed is heated up to Tl2
using enthalpy of condensation of the permeate
(P). Then the feed temperature is further
increased to T02 by means of an external heat
source. There are resulting vapor pressure differ-
ences between feed and permeate side of the
membrane, so a fraction of the feed permeates
the membrane as a vapor and condenses on the
condenser plate (Eva et al. 2010). There are many
differences between thermopervaporation and
pervaporation, which are shown in Table 1.
With the thermopervaporation concept, it is
possible to recover heat during pervaporation
process in an efficient manner. The process has
been established using ethanol separation.
Thermo-PV can be operated using low-cost heat
(80–100  C), which is effective in actual produc-
tion. Besides, the experiments were carried out in
2 Thermopervaporation (Thermo-PV)

Thermopervaporation
(Thermo-PV), F T11 x20 R T10 x10
Fig. 1 Concept of
thermopervaporation (Eva
et al. 2010) T11 x11 T10 x10

membrane

Saturated vapor

Liquid feed
Liquid permeate

Saturated vapor
Condensing
sheet

T21 x21 T20 x20

P T21 x21
Thermopervaporation (Thermo-PV), Table 1 Features of thermopervaporation in contrast with pervaporation (Nitta et al. 1986)
Thermopervaporation Pervaporation
Principle Model
Th > Tc
Thermopervaporation (Thermo-PV)

Evacuation

Feed
Cooling
Feed Water
Permeate

Permeate
Mechanism Evaporation to permeation Permeation to evaporation
Driving force Temperature (steam pressure) difference Pressure difference
Membrane Material Hydrophobic Hydrophilic
Structure Porous Nonporous
Operation pressure Normal pressure Evacuation
Operation temperature Less than boiling point Room temperature
3
4 Thermopervaporation (Thermo-PV)
a small and suboptimally configured module;
results showed that this concept has great poten-
tial for commercial applications (Eva et al. 2010).
References
Eva SF, Peter G, Earl L, Goetheer V (2010) Thermo
pervap: the next step in energy efficient pervaporation.
Desalination 250:1053–1055
Franken ACM, Mulder MHV, Smolders CA
(1990) Pervaporation process using a thermal gradient
as the driving force. J Membr Sci 53:127–141
Nitta K, Ashida A, Mitani K, Ebara K, Yamada A (1986)
Water recycling system using thermopervaporation
method, In: International Symposium on Space
Technology and Science, 15 th, Tokyo, Japan, 1986,
pp. 1355–1359
Volkov VV, Bortisov IL (2012) Thermopervaporation
membrane bioreactor as a new concept for the
low-cost production of biobutanol. In: Euromembrane
conference, London, 23–27 Sept 2012
S
Sulfur Odorous Compounds
Removal by Pervaporation
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing University of
Technology, Nanjing, China
Sulfur oxide emissions generated by vehicle
engines may cause some serious problems, for
instance, inducing the formation of acid rain,
decreasing the efficiency of catalytic converters,
and promoting corrosion of engine parts. As a
result, removal of sulfur from gasoline has
received increasing attention with growing envi-
ronmental awareness. Much attention has been
paid to pervaporation (PV) which is a promising
and feasible technology for desulfurization of
gasoline since Grace Davison Company offered
the PV membrane-based S-Brane process in
2002. Mercaptans, sulfides, disulfides, thiophene,
and its derivatives are the typical sulfur compo-
nents of fluid catalytic cracking (FCC) gasoline in
which thiophenic sulfur represented a large frac-
tion (80 % and over) after alkali cleaning process
(Lin et al. 2009). For this reason, the main aim for
FCC gasoline desulphurization is to remove
thiophenic sulfur compounds, at present.
Unwisely, it is more difficult to remove
thiophenic sulfur impurities than to other sulfur
compounds in FCC gasoline.
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1320-1
Quite a lot of PV membranes for sulfur
removal have been reported by Grace Davison
Company (White et al. 2004). PUU membrane
showed higher sulfur enrichment than polyimide
(PI) and other commercial membranes they
reported. However, its practical application is
not satisfying due to the low flux (less than
0.1 kg/(m2.h)). Exxon Mobil Research and Engi-
neering Company presented two types of mem-
brane for desulphurization which are nonionic
and ionic membranes. Reported nonionic mem-
branes included polyvinylpyrrolidone (PVP) and
cellulose triacetate (CTA), while the preferred
ionic membranes (Saxton et al. 2004) included
Nafion RTM-type acidic membranes, e.g., Nafion
RTM117, that had been optionally treated by
ion-exchange reaction or with bases. The good
news is that certain investigations have been
made on some commercial membranes. Mara-
thon Oil Company also studied the process for
removing sulfur from hydrocarbon, while Trans
Ionics Corporation has developed a PV process,
TranSep-S, for sulfur removal from gasoline boil-
ing range feeds.
Besides, some polymer materials with sound
sulfur removal performance, for instance, cross-
linked polyethylene glycol/polyethersulfone
(PEG/PES) composite membranes, were also
used for FCC gasoline desulphurization (Lin
et al. 2006). The performance of polydimethyl-
siloxane (PDMS) and polyimide PI membrane
composite membranes was studied for sulfur
removal from model gasoline (Qi et al. 2006). It
2 Sulfur Odorous Compounds Removal by Pervaporation
has been showed that the membrane modification
methods lead to achieve high selectivity or high
flux (Lin et al. 2009). For example, cross-linking
modification for PEG increased sulfur enrich-
ment factor from 3.31 to 7.31 for model com-
pounds feed and from 1 to 3.05 for FCC gasoline.
AgY zeolite incorporation in PDMS membranes
led to a significant increase in total flux. At the
same time, higher sulfur enrichment factor and
permeation flux were obtained from
PEG/polyurethane (PU) blend membranes for
gasoline desulphurization. It should not be
ignored that the performance for various mem-
branes mainly depends on the properties of the
membrane materials while the types of mem-
brane structure also have a significant influence
on the membrane performance. Ceramic-
supported PDMS membrane exhibits a higher
permeation flux and an acceptable sulfur enrich-
ment factor in comparison with those composite
membranes using polymeric supports
(Xu et al. 2010). The operating parameters of
PV, including feed temperature, feed concentra-
tion, feed flow rate, permeate pressure, etc., have
significant impacts on membrane performance.
Take ceramic-supported PDMS membrane as an
example; the increase of sulfur content in feed
leads to a higher total flux but a lower sulfur
enrichment factor. By increasing the feed tem-
perature, the total flux increased while sulfur
enrichment factor decreased. It was appropriate
that low permeate pressure and high feed flow
rate were beneficial to improve total flux and
sulfur enrichment factor (Xu et al. 2010).
References
Lin L, Kong Y, Wang G (2006) Selection and crosslinking
modification of membrane material for FCC gasoline
desulphurization. J Membr Sci 285:144–151
Lin L, Zhang YZ, Kong Y (2009) Recent advances in
sulfur removal from gasoline by pervaporation. Fuel
88:1799–1809
Saxton RJ, Minhas BS (2004) Ionic membranes for
organic sulfur separation from liquid hydrocarbon
solutions. US Patent 6,702,945
Qi R, Wang Y, Li J (2006) Pervaporation separation of
alkane/thiophene mixtures with PDMS membrane.
J Membr Sci 280:545–552
White LS, Wormsbecher RF, Lesemann M (2004) Mem-
brane separation for sulfur reduction. Patent US
0211706 A1
Xu R, Liu GP, Dong XL, Jin WQ (2010) Pervaporation
separation of n-octane/thiophene mixtures using
polydimethylsiloxane/ceramic composite membranes.
Desalination 258:106–111
A
Analytical Pervaporation
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
The relatively new developed pervaporation in
analytical chemistry is in principle a separation
technique for the removal of volatile analytes or
their volatile derivatives from the sample matrix.
Also, it can be used for sample pretreatment, e.g.,
for solid samples where leaching and derivatiza-
tion of the analytes are done simultaneously.
Analytical pervaporation can be defined as the
integration of evaporation and gas diffusion in a
single module. Through a porous membrane, the
volatile substances present in a heated donor
phase evaporate. And on the other side of the
membrane, the vapor condenses on the surface
of a cool acceptor stream. The driving force for
the separation is due to the temperature differ-
ence, which leads to a vapor pressure difference
across the membrane. For analytical
pervaporation, an important feature is that the
existence of a constant-volume air gap between
the sample in the donor chamber and the mem-
brane, which hinders any contact between them.
As a result, the clogging and/or deterioration of
the membrane can be avoided (Luque de
Castro 1998).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1321-2
The conventional version of the analytical
pervaporation module is shown in Fig. 1 and
consists of the following parts: (i) a lower donor
chamber (DC) in which the sample containing the
analyte is introduced, either by injection or by
continuous aspiration for liquid samples and by
direct weighing for solid samples, (ii) an upper
acceptor chamber (AC) in which an appropriate
fluid is circulated for receiving the pervaporated
analytes, (iii) a membrane support
(MS) approximately 1 mm thick, and
(iv) spacers of varying thickness (between 2 and
10 mm) which can be placed above or below the
membrane support in order to increase the vol-
ume of the corresponding chamber. The different
parts of the module are aligned by inserting
metallic rods into four orifices and a closer con-
tact is achieved by screwing them between two
aluminum supports (AS). The whole module is
normally made of methacrylate, which permits
continuous monitoring of the sample level in the
lower chamber during the experiments Luque de
Castro and Papaefstathiou (1998).
Constantly being hydrophobic, the mem-
branes for analytical pervaporation are usually
employed in ultrafiltration and gas-diffusion pro-
cesses. Practically, polytetrafluoroethylene
(PTFE) is the most frequently used membrane
material, followed by hydrophobic
polyvinylidene fluoride (PVDF) Luque de Castro
and Gdmiz-Gracia (2000). In combination with
the large surface area of both the donor and
acceptor chambers, the ultrafiltration
2 Analytical Pervaporation
Analytical Pervaporation, Fig. 1 Conventional
pervaporation module. DC donor chamber, AC acceptor
chamber, MS membrane support, m membrane, AG air
gap, AS aluminum supports, DI, DO inlet/outlet of donor
stream, respectively, AL, AO inlet/outlet of acceptor
stream, respectively
membranes, which are very thin, lead to their
easy bending. In result, the flux of the permeating
component changes through an altered mem-
brane area, and therefore, it leads to a change in
the efficiency of the process in addition to repro-
ducibility problems; consequently, the mem-
branes must be changed quite often. Due to their
thickness, gas-diffusion membranes are not so
easily bent, so the same membrane can be used
over longer periods. The efficiency of the process
is influenced by the pore size of the membrane
(or its directly proportional thickness) and hence
the sensitivity of the method; it affords applica-
tion to samples with variable analyte concentra-
tions, as a result.
Analytical pervaporation can be used for the
determination of a single analyte or a number of
analytes, being of inorganic, organic, or organo-
metallic nature. Application of analytical
pervaporation in the environmental field has
been reported especially for food analysis
Amador and Luque de Castro (2000). which is
the analytical field in which pervaporation has
been most widely applied. Other fields of appli-
cation of pervaporation have been pharmaceuti-
cal and clinical analyses.
References
Amador HJ, Luque de Castro MD (2000) Pervaporation: a
useful tool in food analysis. Food Chem 68:387–394
Luque de Castro MD, Gdmiz-Gracia L (2000) Analytical
pervaporation: an advantageous alternative to head-
space and purge-and-trap techniques.
Chromatographia 52:265–272
Luque de Castro MD, Papaefstathiou I (1998) Analytical
pervaporation: a new separation technique. Trends
Anal Chem 17:41–49
E
Ethanol Production by Continuous
Fermentation-Pervaporation
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Ethanol production by continuous fermentation-
pervaporation is a process that couples ethanol
fermentation with in situ pervaporation
(PV) recovery of ethanol from fermentation
broth.
With the fast increasing of fossil fuel con-
sumption and the deterioration of environment,
it is commonly accepted that the fossil fuel for
human energy use has to be replaced generally by
renewable resources. Compared with traditional
resources, bioethanol produced by fermentation
process can be sustainably developed without
extra yield of greenhouse gas (Peng et al. 2011).
Bioethanol is produced from renewable resources
(biomass) by ethanol fermentation process. How-
ever, usually, the maximum concentration of sol-
vents (ethanol) does not exceed 8 wt% owing to
the end-product inhibition on microorganism,
resulting in high energy cost to separate ethanol
from the dilute fermentation broth by distillation.
Therefore, several in situ product-removal tech-
nologies, such as adsorption, gas stripping,
liquid-liquid extraction, perstraction,
pervaporation, and reverse osmosis, have been
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1322-2
developed. These technologies could be coupled
with ethanol fermentation process to decrease the
effect of product inhibition and improve the sugar
utilization and solvent productivity (Vane 2005).
Pervaporation coupled with fermentation,
which is also called fermentation-pervaporation
coupled process, has been regarded as the most
promising separation method because this pro-
cess can in situ extract organic components
which is harmless for microorganisms in mild
condition. Figure 1 shows its typical flow chart
(Vane 2005). A pervaporation membrane module
is connected to the fermentor to form a circula-
tion of fermentation broth. Preheated fermenta-
tion solution is continuously circulated from
fermentor through the membrane upstream side
with another side being vacuumed using vacuum
pump. Therefore, ethanol solvent can be selec-
tively and continuously removed from the fer-
mentation broth and then concentrated in the
membrane downstream side. As a result, ethanol
concentration in the broth is kept at low level to
facilitate the continuous fermentation process as
well as enhance the solvent productivity. In addi-
tion, a microfiltration/ultrafiltration unit can be
alternatively installed before the pervaporation
module, in order to filter microbes and avoid the
biofouling of pervaporation membranes.
PV membranes can be made from either poly-
meric or inorganic materials, even both of them
(Peng et al. 2011). The polymeric pervaporation
membranes for extracting ethanol from fermen-
tation broth include polydimethylsiloxane
2 Ethanol Production by Continuous Fermentation-Pervaporation
Ethanol Production by Continuous Fermentation-Pervaporation, Fig. 1 Ethanol fermentation-pervaporation
coupled process
(PDMS) membranes, poly[1-(trimethylsilyl)-1-
propyne] (PTMSP) membranes, poly(ether
block amide) (PEBA) membranes, liquid mem-
branes, other modified polymer membranes, as
well as porous polypropylene (PP) membranes
and polytetrafluoroethylene (PTFE) membranes.
Among them, the commonly used PDMS mem-
branes with good selectivity and stability are
regarded as the most potential PV membranes
for ethanol recovery application (Xiangli
et al. 2008). The typical inorganic membrane
for PV is hydrophobic zeolite membrane, such
as ZSM-5 and Silicalite-1 membrane.
References
Peng P, Shi B, Lan Y (2011) A review of membrane
materials for ethanol recovery by pervaporation. Sep
Sci Technol 46:234–246
Vane LM (2005) A review of pervaporation for product
recovery from biomass fermentation processes.
J Chem Technol Biotechnol 80:603–629
Xiangli FJ, Wei W, Chen YW, Jin WQ, Xu NP
(2008) Optimization of preparation conditions for
polydimethylsiloxane (PDMS)/ceramic composite
pervaporation membranes using response surface
methodology. J Membr Sci 311:23–33
E
Enzymatic Ultrafiltration
Membranes: Immobilization
of Urease and Trypsin
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Fuel is any material that stores potential energy in
a form that can be practicably released and used
as heat energy. The conventional fuels refer to
chemical fuels including fossil fuels and biofuels.
Fossil fuels are hydrocarbons, primarily coal and
petroleum (liquid petroleum or natural gas),
formed from the fossilized remains. Biofuel can
be broadly defined as solid, liquid, or gas fuel
consisting of or derived from biomass.
Since the heightened concerns for cleaner air
and more stringent environmental quality
requirements for sulfur concentration in oil prod-
ucts, ultra-deep desulfurization from fuels, par-
ticularly from gasoline, has become a very
important subject in petroleum refining industry.
It is well known that sulfur removal from FCC
gasoline can be achieved by catalytic hydrodesul-
furization. However, this hydrotreating process
results in a significant reduction of octane number
due to the saturation of olefins (Lin et al. 2009).
Pervaporation has been given much more atten-
tion as a promising and feasible technology for
desulfurization of gasoline since Grace Davison
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1323-2
Company reported the pervaporation membrane-
based S-brane process in 2002 (White
et al. 2005). The sulfur components can be pref-
erentially removed from the gasoline feed due to
its higher affinity with and/or quicker diffusivity
in the membrane. Pervaporation desulfurization
demonstrates distinct advantages over conven-
tional technologies such as low energy consump-
tion, simple operation, and little reduction of
octane number. The pervaporation membrane
materials involved in desulfurization are mainly
hydrophobic polymers including polyurethane
(PU), polyurea/urethane (PUU), polyimide (PI),
natural rubber and poly(styrene-co-butadiene)
rubber, and polydimethylsiloxane (PDMS), as
well as some hydrophilic polymers such as
polyvinylpyrrolidone (PVP), cellulose triacetate
(CTA), and polyethylene glycol (PEG) (Lin
et al. 2009).
Among the variety of possible biofuels from
the biorefinery, liquid transportation fuels in the
form of bioethanol currently account for the vast
majority of biofuels produced all over the world.
A typical corn-to-ethanol production process
consists of pretreatment of the starch to sugars
with enzymes, fermentation of the sugars to eth-
anol with yeast, followed by distillation and
dehydration processes of ethanol. Downstream
from the fermentor is usually a dilute aqueous
solution containing about 5–12 wt.% ethanol.
Separation technologies such as pervaporation
are applied for the subsequent ethanol/water sep-
aration. On the one hand, hydrophobic
2 Enzymatic Ultrafiltration Membranes: Immobilization of Urease and Trypsin
pervaporation membranes such as PDMS
(Xiangli et al. 2008) and silicalite-1 zeolite mem-
branes could be used for selective recovery of
ethanol from fermentation broth. In addition, the
fermentation process can be coupled with hydro-
phobic pervaporation membranes for in situ
removal of the inhibitors (e.g., ethanol product
and phenols) from the fermentation broth to real-
ize the continuous fermentation. On the other
hand, hydrophilic pervaporation membranes
including PVA (Zhu et al. 2010) and NaA zeolite
membranes (Yang et al. 2012) could be used for
dehydration of concentrated ethanol aqueous
solution (usually containing 90–95 wt.% etha-
nol), obtaining the final bioethanol product.
References
Lin LG, Zhang YZ, Kong Y (2009) Recent advances in
sulfur removal from gasoline by pervaporation. Fuel
88:1799–1809
White LS, Wormsbecher RF, Lesemann M (2005) Mem-
brane separation for sulphur reduction. US Patent:
6,896,796
Xiangli FJ, Wei W, Chen YW, Jin WQ, Xu NP
(2008) Optimization of preparation conditions for
polydimethylsiloxane (PDMS)/ceramic composite
pervaporation membranes using response surface
methodology. J Membr Sci 311:23–33
Yang ZZ, Liu YM, Yu CL, Gu XH, Xu NP (2012) Ball-
milled NaA zeolite seeds with submicron size for
growth of NaA zeolite membranes. J Membr Sci
392–393:18–28
Zhu YX, Xia SS, Liu GP, Jin WQ (2010) Preparation of
ceramic-supported poly(vinyl alcohol)-chitosan com-
posite membranes and their applications in
pervaporation dehydration of organic/water mixtures.
J Membr Sci 349:341–348
C

Continuous Electrodeionization Continuous electrodeionization is an alternative

Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology, Technicka 5, Prague
6, Czech Republic
term for electrodeionization; however, it empha-
sizes the fact that, in contrast to classical deioni-
zation by ionic exchange, this process is
continuous.

# Springer-Verlag Berlin Heidelberg 2015

E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1324-1
M
Membrane Emulsification and Food
Applications
Emma Piacentini
Institute on Membrane Technology (ITM-CNR),
University of Calabria, Rende, CS, Italy
Emulsion production for encapsulation and deliv-
ery of functional compounds such as vitamins or
probiotics or bioactive lipids is one of the emerg-
ing fields of membrane emulsification applied to
food industry. Benefits of membrane emulsifica-
tion for food applications include the low shear
properties and the uniform size distribution that
give high encapsulation efficiency and better con-
trol of the release properties. Vitamin B12 was
encapsulated in multiple solid-in-oil-in-water
emulsion by premix membrane (Kukizaki 2009)
and in solid lipid microcapsules by two-step
membrane emulsification technique (Kukizaki
and Goto 2007). Astaxanthin-loaded o/w emul-
sions were prepared by repeated premix mem-
brane emulsification (Ribeiro et al. 2005).
Lactobacillus casei cells have been encapsulated
in uniform emulsions and microcapsules using
the membrane emulsification technique (Song
et al. 2003). The aim is to increase the activity
and viability of the microorganism to the stressful
conditions of the stomach and the upper intestine
by encapsulation. Fish oil microcapsules were
produced from oil-in-water emulsions by premix
membrane emulsification (Ramakrishnan
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1331-3
et al. 2013). The combination of a low-energy
emulsification technique (premix membrane
emulsification) with spray drying allowed the
production of fish oil microcapsules with an oil
encapsulation efficiency of more than 50 %. Fish
oil-in-water emulsions containing multilayered
membranes produced by premix membrane
emulsification demonstrated low in vitro digest-
ibility (Gudipati et al. 2010). Results indicated
that these emulsion systems could be used to
modify the release of bioactive lipids in the gas-
trointestinal tract.
Milk components are often used in the prepa-
ration of food emulsions. The molecular or ultra-
structural status of the milk components at the fat
surface plays an important role in determining the
functional properties of the food products. The
advantage of membrane emulsification was
pointed out to be the low shear forces on the
physicochemical and molecular properties of the
proteins. Oil-in-water emulsions with vegetal oil
as dispersed phase and a milk proteins solution as
continuous phase have been prepared using SPG
(Scherze et al. 1999) and ceramic membranes
(Joscelyne and Trägårdh 1999). Na-caseinate
and b-lactoglobulin were used also in combina-
tion with the nonionic surfactant, Tween 20, in
oil-in-water emulsions preparation by membrane
emulsification (Christov et al. 2002).
Membrane emulsification has been tested also
in the preparation of specific emulsion-based
food product such as foamed food products like
chocolate mousse, ice cream, or fresh cheese and
2 Membrane Emulsification and Food Applications
low-fat product such as double emulsions and
spread. Foamed food product where air is present
as a component of several food products present
(dispersed phase of bubbles or pores) was pro-
duced by membrane foaming. The method is
based on pressing the dispersed phase as a form
of gas through the membrane pores into the con-
tinuous phase while the continuous phase,
containing whey proteins as surface-active sub-
stances, flowed along the membrane surface
(Bals and Kulozik 2003a, b). Rotating membrane
emulsification was also used in the preparation of
gas dispersion to improve the foam microstruc-
ture in terms of size and size distributions
(M€uller-Fischeret al. 2007). The Morinaga Milk
Industry (Japan) developed and commercialized
a low-fat spread using membrane technology
(Okonogi et al. 1992). The volume fraction of
dispersion water-phase reaches up to 75 % and
the product is reported to be very stable, with
suitable texture, and tasty. The potential for the
easy scale-up is another attractive quality of
membrane emulsification technology. Microen-
capsulation of vegetable oil droplets using cold
water fish gelatine/gum arabic complex coacer-
vation has been obtained at batch and large scale
production using the stirred and the pulsed flow
membrane emulsification (Piacentini et al. 2013).
References
Bals A, Kulozik U (2003a) The influence of pore size, the
foaming temperature and the viscosity of the continu-
ous phase on the properties of foams produced by
membrane foaming. J Membr Sci 220:5–11
Bals A, Kulozik U (2003b) Effect of pre-heating on the
foaming properties of whey protein isolate using a
membrane foaming apparatus. Int Dairy J 13:903–908
Christov NC, Ganchev DN, Vassileva ND, Denkov ND,
Danov KD, Kralchevsky PA (2002) Capillary mecha-
nisms in membrane emulsification: oil-in-water emul-
sions stabilized by Tween 20 and milk proteins.
Colloids Surf A 209:83–104
Gudipati V, Sandra S, McClements DJ, Decker EA
(2010) Oxidative stability and in vitro digestibility of
fish oil-in-water emulsions containing multilayered
membranes. J Agric Food Chem 58:8093–8099
Joscelyne SM, Trägårdh G (1999) Food emulsions using
membrane emulsification: conditions for producing
small droplets. J Food Eng 39:59–64
Kukizaki M (2009) Preparation of solid lipid microcap-
sules via solid-in-oil-in-water dispersions by premix
membrane emulsification. Chem Eng J 151:387–396
Kukizaki M, Goto M (2007) Preparation and evaluation of
uniformly sized solid lipid microcapsules using mem-
brane emulsification. Colloids Surf A 293:87–94
M€uller-Fischer N, Bleuler H, Windhab EJ (2007) Dynam-
ically enhanced membrane foaming. Chem Eng Sci
62:4409–4419
Okonogi S, Kumazawa R, Toyama K, Kato M, Asano Y,
Takahashi IK, Fujimoto M (1992) Production of dou-
ble emulsified spread and its production. JP4258251
Piacentini E, Giorno L, Dragosavac MM, Vladisavljević
GT, Holdich RG (2013) Microencapsulation of oil
droplets using cold water fish gelatine/gum Arabic
complex coacervation by membrane emulsification.
Food Res Int 53:362–372
Ramakrishnan S, Ferrando M, Aceña-Muñoz LS, Lamo-
Castellví D, G€ uell C (2013) Fish oil microcapsules
from O/W emulsions produced by premix membrane
emulsification. Food Bioprocess Technol
6:3088–3101
Ribeiro HS, Rico LG, Badolato GG, Schubert H (2005)
Production of o/w emulsions containing astaxanthin
by repeated premix membrane emulsification. J Food
Sci 70:117–123
Scherze I, Marzilger K, Muschiolik G (1999) Emulsifica-
tion using micro porous glass (MPG): surface behav-
iour of milk proteins. Colloids Surf B 12:213–221
Song SH, Cho YH, Park J (2003) Microencapsulation of
Lactobacillus casei YIT 9018 using a microporous
glass membrane emulsification system. J Food Sci
68:195–200
H
Hollow Fiber Carbon Molecular Sieve application as reported by He et al. (He and
Membranes Hägg 2011a). Different techniques such as scan-
Xuezhong He
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Sør-Trøndelag,
Norway
Carbon molecular sieve (CMS) membranes have
been studied in more than twenty years as prom-
ising and energy-efficient membranes for gas
separation. Due to their high permeability, selec-
tivity, and also thermal and chemical stability
under adverse and harsh conditions, the CMS
membranes are becoming increasingly important
for separating gas mixtures with quite similar
molecular kinetic diameter. Carbon molecular
sieve membranes can be prepared by controlling
the carbonization procedure during carbonization
of different polymeric materials such as
polyimide, polyacrylonitrile (PAN), phenolic
resin, poly(phthalazinone ether sulfone ketone),
poly(phenylene oxide), cellophane paper, cellu-
lose, and deacetylated cellulose acetate. The car-
bonization parameters (e.g., purge gas, purge gas
flow rate, final temperature, heating rate, and final
soak time) will affect the resulting carbon mem-
brane performance, and the optimal condition
was obtained on the basis of experimental design
and statistical analysis to prepare the high-
performance carbon membranes for a specific
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1332-9
ning electron microscopy (SEM), Fourier trans-
form infrared spectroscopy (FTIR), and X-ray
diffraction (XRD) have been used to characterize
the membrane’s structure and morphology.
Figure 1 shows the cross section and inside sur-
face of the precursors and HFCMs, respectively
(He et al. 2011). The outer diameter and wall
thickness of the HFCMs were approximately
250 mm and 30 mm, respectively, indicating a
significant radical shrinkage comparing to the
precursor membranes with 400 mm and 50 mm.
The pore size and pore-size distribution (PSD)
can be estimated by gas gravimetric adsorption
measurements equipped with a Rubotherm mag-
netic suspension balance (MSB) (Belmabkhout
et al. 2009). The structural parameters of a
cellulosic-based carbon membrane have been
estimated from CO2 sorption measurements, and
a narrow pore-size distribution was found by He
et al. (He and Hägg 2012), and the results were
shown in Table 1, which will be helpful to under-
stand the transport mechanism through carbon
membranes.
The operating parameters such as feed pres-
sure, temperature, and flow rate of retentate will
greatly affect the CMS membrane separation per-
formances and need to be optimized for a specific
application as reported by He et al. (He and Hägg
2011b). Considering the aging problem for most
carbon membranes, different regeneration tech-
niques can be used to recover the performances
2 Hollow Fiber Carbon Molecular Sieve Membranes

Hollow Fiber Carbon Molecular Sieve Membranes, Fig. 1 SEM images of cross section of precursor and HFCM-2.
(a, c) are the cross section of the precursor; (b, d) are the cross section of the prepared carbon membrane (He et al. 2011)

Hollow Fiber Carbon Molecular Sieve Membranes, Table 1 Structural parameters of the cellulosic-based carbon
membranes (He and Hägg 2012)
W0 Average
Carbon True density, rs Bulk density, rb (cm3 E0 micropore width
membranes (g cm 3)a (g cm 3) g 1) (kJ mol 1) (Å) Reference
HFCM-1 1.53 1.24 0.15 32.2 5.2 This work
HFCM-2 1.38 1.12 0.17 30.8 5.6 This work
CMSM1 1.6 1.1 0.28 31.6 5.5 (Lagorsse
et al. 2004)
CM-V823 0.16 22.75 (Lua and Su
2006)
a
Density of carbons is 1.3–1.8 g/cm3 as compared to 2.2 g/cm3 for graphite (Koresh and Soffer 1983)

online or off-line (Lie 2005; Hagg and He 2011). constructed. Figure 2 shows a schematic and
In order to ensure the efficiency of the carbon lab-scale hollow fiber carbon membrane module
membrane separation process, a hollow fiber (He and Hägg 2011b), while Fig. 3 shows a small
membrane module should be designed and pilot-scale module (designed by one of
Hollow Fiber Carbon Molecular Sieve Membranes 3

Retentate Feed
Hollow fibre
carbon membranes
Epoxy Epoxy

Effective length Permeate

Feed
Retentate

Permeate

Hollow Fiber Carbon Molecular Sieve Membranes, Fig. 2 A schematic and lab-scale carbon membrane module
(He and Hägg 2011b)

Hollow Fiber Carbon

Molecular Sieve
Membranes, Fig. 3 A
small pilot-scale carbon
membrane module
(Designed by HyGear)
(He 2011)

NanoGloWa project partner, HyGear B.V.)
(He 2011). Single-gas permeability tests at dif-
ferent temperatures and pressures were mostly
conducted by using the lab-scale module, while
the small pilot-scale module was employed to test
the gas mixture at a higher permeate flux in order
to determine the gas composition more precisely.
Based on the experimental investigations and
process simulations, the carbon membranes show
high potential for selected industrial applications
such as CO2-CH4 separation for biogas upgrading
(Hägg and Lie 2006), H2-CH4 separation wher-
ever relevant (Grainger and Hägg 2008), and CO2
capture from flue gases (He and Hägg 2011b; He
et al. 2009). Moreover, carbon molecular sieve
membranes also show a great potential in air
separation, petrochemical, and high-temperature
membrane reactor applications.
4 Hollow Fiber Carbon Molecular Sieve Membranes
References
Belmabkhout Y, Serna-Guerrero R, Sayari A (2009)
Adsorption of CO2 from dry gases on MCM-41 silica
at ambient temperature and high pressure. 1: pure CO2
adsorption. Chem Eng Sci 64(17):3721–3728
Grainger D, Hägg MB (2008) The recovery by carbon
molecular sieve membranes of hydrogen transmitted
in natural gas networks. Int J Hydrog Energy
33(9):2379–2388
Hagg M-B, He X (2011) Carbon molecular sieve mem-
branes for gas separation. In: Drioli E, Barbieri G (eds)
Membrane engineering for the treatment of gases:
Gas-separation Problems Combined with Membrane
Reactors, The Royal Society of Chemistry,
Cambridge, Vol. 2, pp 162–191
Hägg M-B, Lie JA (2006) Upgrading of biogas by mem-
branes for vehicle fuel or injection into the European
Gas Network. ECI Conferences, Tomar
He X (2011) Development of Hollow Fiber Carbon Mem-
branes for CO2 Separation [PhD]. Norwegian Univer-
sity of Science and Technology, Trondheim, p 42
He X, Hägg M-B (2011a) Optimization of carbonization
process for preparation of high performance hollow
fiber carbon membranes. Ind Eng Chem Res
50(13):8065–8072
He X, Hägg M-B (2011b) Hollow fiber carbon mem-
branes: investigations for CO2 capture. J Membr Sci
378(1-2):1–9
He X, Hägg M-B (2012) Structural, kinetic and perfor-
mance characterization of hollow fiber carbon mem-
branes. J Membr Sci 390–391:23–31
He X, Lie JA, Sheridan E, Hagg M-B (2009) CO2 capture
by hollow fibre carbon membranes: experiments and
process simulations. Energy Procedia 1(1):261–268
He X, Lie JA, Sheridan E, Hägg M-B (2011) Preparation
and characterization of hollow fiber carbon mem-
branes from cellulose acetate precursors. Ind Eng
Chem Res 50(4):2080–2087
Koresh JE, Soffer A (1983) Molecular sieve carbon mem-
brane part I: presentation of a new device for gas
mixture separation. Sep Sci Technol 18:723–734
Lagorsse S, Magalhães FD, Mendes A (2004) Carbon
molecular sieve membranes: sorption, kinetic and
structural characterization. J Membr Sci
241(2):275–287
Lie JA (2005) Synthesis, performance and regeneration of
carbon membranes for biogas upgrading-a future
energy carrier [PhD]. Norwegian University of Sci-
ence and technology, Trondheim
Lua AC, Su J (2006) Effects of carbonisation on pore
evolution and gas permeation properties of carbon
membranes from Kapton?polyimide. Carbon
44(14):2964–2972
M
Membranes for CO2 Capture from
Flue Gas
Xuezhong He
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Sør-Trøndelag,
Norway
The control of anthropogenic emissions of green-
house gases (GHG) is one of the most challenging
environmental issues owing to the implications of
GHG for global climate change. Among these
GHG, CO2 is the largest contributor in regard of
its amount present in the atmosphere contributing
to 60 % of global warming effects, although
methane and chlorofluorocarbons have much
higher greenhouse effect as per mass of gases
(Yamasaki 2003). A lot of efforts have been put
on the reduction of CO2 emission from large CO2
point sources such as fossil fuel power plants and
other industries (e.g., cement, steel and iron pro-
duction, natural gas sweetening, and biogas
upgrading processes). Such plants emit large
quantities of CO2; for example, the fossil fuel
power plants are responsible for roughly 40 %
of total CO2 emissions and coal-fired plants being
the main contributor. Clearly, coal-fired plants
need to be addressed first, especially by
retrofitting existing plants.
Different techniques such as chemical absorp-
tion (e.g., MEA, MDEA), physical absorption
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1333-12
(e.g., Selexol, Rectisol), physical adsorption
(e.g., molecular sieves, metal-organic frame-
works), cryogenics, and membrane separation
could be used for CO2 capture. Chemical absorp-
tion has been widely used in natural gas for over
60 years and separates out relatively high purity
CO2 stream. However, conventional amine
absorption technologies are energy intensive
and costly, which would result in large incremen-
tal costs. National Energy Technology Labora-
tory (NETL) estimates that amine unit will
increase the cost of electricity production by
70 % (Elwell and Grant). Membranes are already
an alternative and competitive technology for the
selected gas separation processes such as air sep-
aration, natural gas sweetening, biogas
upgrading, and hydrogen production during the
last two or three decades. Membrane technology
will become steadily more attractive due to its
high energy efficiency and low economical costs.
Although polymeric membranes are still domi-
nating, the current industrial uses for gas separa-
tion, the trade-off of permeability/selectivity, and
the limitation of operating temperature and
adverse conditions such as the presence of acid
gases SO2 and NOx could probably direct the
development of polymer membranes into the
other types of membranes such as microporous
organic polymers (MOPs), fixed-site-carrier
(FSC) membranes, mixed matrix membranes,
carbon molecular sieve membranes, as well as
inorganic (ceramic, metallic, zeolites)
membranes.
2 Membranes for CO2 Capture from Flue Gas

CO2,
ADJ-2 retentate1 vent
3.3%
E19 E17
mix1 K-108
E-100 feed1 E11 CO2,
retentate2
MIX-100 sweep1 RCY-1 0 92%
Carbon E15 E-105
membrane E14 to
module E-107 feed2 pipeline
E-106
cooling 3 sweep permeate2
membrane
cooling
permeate1 cooling1
8
CO2, Mix2 cooling 2
15%
Flue
gas
E1 E13 E16 E12
K-100 K-106 K-107 ADJ-1 K-105

Membranes for CO2 Capture from Flue Gas, Fig. 1 A schematic flow sheet of two-stage membrane units for CO2
capture from flue gases (He and Hägg 2013)

Gas separation membrane system offers a results showed that membrane process using a
potentially lower cost, more energy-efficient high-performance FSC membrane was feasible
CO2 capture option. However, there are some for CO2 capture, even with a low CO2 concentra-
challenges related to the limited application of tion (~10 %) in flue gas, compared to amine
membrane system for CO2 capture from flue gas absorption in terms of energy requirement, and
in post-combustion process; examples are as fol- it was possible to achieve >90 % CO2 recovery
lows: large quantities of gas need to be treated and a purity above 95 % CO2 in permeate stream.
due to a low CO2 concentration, high compres- Recently, this type of membrane performance has
sion energy consumption required to achieve a been significantly improved as reported by Kim
high driving force for membrane operation, and et al. (2013). Thus, this environmentally friendly
challenges of acid gases such as SO2 and NOx and technique could promote membrane gas separa-
high content of water. According to these chal- tion system as a promising candidate for CO2
lenges, highly CO2-permeable and CO2-selective capture from flue gas in post-combustion process
membranes with a low cost are required for mem- if the abovementioned challenges can be well
brane system to compete with traditional chemi- addressed.
cal absorption method for CO2 capture. He
et al. investigated the application of hollow fiber
carbon membranes for CO2 capture from flue
References
gases (He and Hägg 2013). They reported that a
capital cost of 100 $/tonne CO2 avoided for a Elwell LC, Grant WS (nd) Technology options for
two-stage carbon membrane system (illustrated capturing CO2. [Cited 25 Sept 2010]; Available from:
in Fig. 1), which is still higher than a traditional http://www.powermag.com/coal/Technology-options-
chemical method of MEA (59 $/tonne CO2 for-capturing-CO2_582.html
Grainger D (2007) Development of carbon membranes for
avoided reported by Rao and Rubin (Stoeckli hydrogen recovery. Norwegian University of Science
et al. 2002)), but the referred carbon membranes and technology. PhD thesis
had a clear potential of further optimization. He X, Hägg M-B (2013) Hollow fiber carbon membranes:
Hussain et al. conducted a feasibility analysis by from material to application. Chem Eng
J 215–216:440–448
HYSYS integrated with an in-house membrane Hussain A, Hägg M-B (2010) A feasibility study of CO2
program (ChemBrane, developed by Grainger capture from flue gas by a facilitated transport mem-
(2007)) to investigate the influence of process brane. J Membr Sci 359(1–2):140–148
parameters on energy demand and flue gas Kim T-J, Vrålstad H, Sandru M, Hägg M-B (2013) Sepa-
ration performance of PVAm composite membrane for
processing cost using a novel CO2-selective CO2 capture at various pH levels. J Membr Sci
FSC membrane (Hussain and Hägg 2010). The 428(0):218–224
Membranes for CO2 Capture from Flue Gas 3

Stoeckli F, Slasli A, Hugi-Cleary D, Guillot A (2002) The Yamasaki A (2003) An overview of CO2 mitigation
characterization of microporosity in carbons with options for global warming – emphasizing CO2
molecular sieve effects. Microporous Mesoporous sequestration options. J Chem Eng Jpn 36(4):361–375
Mater 51(3):197–202
M
Membranes for Natural Gas
Sweetening
Xuezhong He
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Sør-Trøndelag, Trondheim,
Norway
Natural gas sweetening (CO2 removal from nat-
ural gas) is mandatory to meet the specifications
of natural gas grid. Decision on which technology
to use for CO2 removal from natural gas is mainly
dependent on process conditions and the crude
natural gas composition. Conventional chemical
absorption is well known and has been commer-
cially used for CO2 removal in various processes
and considered as a state-of-the-art technology.
However, membrane system shows a great poten-
tial for natural gas sweetening since it possesses
many advantages such as small footprint, low
capital and operating costs, and environmental
friendly and exhibits process flexibility even
though it has only 5 % of the market today.
Membrane unit cost and CH4 loss are two crucial
parameters used for evaluation of membrane pro-
cess efficiency, which are mainly dependent on
the membrane performance and process design.
Some representative suppliers of membrane sys-
tems using different materials for CO2 separation
from natural gas are shown in Table 1. Although
common polymer membranes for natural gas
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1334-6
sweetening are still using cellulose acetate/triac-
etate and polyimide, the novel, high-performance
fixed-site-carrier (FSC) membranes showed a
great interest for CO2/CH4 separation (Deng
et al. 2009a).
High-pressure operation is the main challenge
for natural gas processing with membrane sys-
tem. Membrane plasticization is found to be a
well-known phenomenon in most polymer mem-
branes which absorb a high content of CO2 at
high pressure (Donohue et al. 1989; Wind
et al. 2004), resulting to a significant decrease of
CO2 permeance as well as selectivity of CO2/
CH4. The possible strategies to overcome mem-
brane plasticization are cross-linking of mem-
brane material (Wind et al. 2002) and
fabrication of mechanical strength-enhanced
membranes, e.g., mixed matrix membrane, by
adding inorganic fillers into polymer matrix.
Adams et al. prepared a 50 % (vol.) zeolite
4A/poly(vinyl acetate) (PVAc) MMM for CO2
separation from natural gas (Adams et al. 2011).
They found that the prepared MMMs can
approach Robeson CO2/CH4 upper bound, and
CO2 permeability remained effectively
unchanged with a 63 % increase in selectivity
compared to pure PVAc. Their membranes
showed a promising application in high-pressure
natural gas sweetening. Deng et al. reported that
carbon nanotubes (CNTs) reinforced PVAm/
PVA blend FSC membrane and presented a
good CO2/CH4 separation performance (Deng
et al. 2009b; He et al. 2014). It shows a much
2 Membranes for Natural Gas Sweetening
Membranes for Natural Gas Sweetening, Table 1 Representative commercial membrane systems for CO2 removal
from natural gas
Membrane Material
SeparexTM Cellulose acetate
Cynara ® Cellulose acetate
Prism ® Polysulfone
Cytop Perfluoropolymers
Medal Polyimide
strong mechanical strength which could have
possibility to maintain a good separation perfor-
mance even at high pressure.
Process design for CO2 removal by membrane
system from natural gas depends on the mem-
brane permeability and selectivity, CO2 concen-
tration in feed stream, specific separation
requirement, as well as the location of the plant.
Peters et al. conducted process design, simula-
tion, and optimization for CO2 removal from
natural gas using HYSYS integrated with an
in-house membrane program (ChemBrane)
(Peters et al. 2011). They reported that a
two-stage membrane system with a CO2
permeance 0.3 m3 (STP)/(m2 h bar) and a CO2/
CH4 selectivity 40 is comparable to that of amine
process. Although the purity of sweet gas is a
little low, it can still achieve the sales gas stan-
dards (<2 % CO2 in natural gas). A combination
of hybrid processes comprising a membrane sys-
tem for bulk removal of CO2 from crude natural
gas feed with an amine unit for final purification
to reach the pipeline specification (<2 % CO2)
could be the optimal process for natural gas
sweetening. Future direction of natural gas
sweetening using membrane systems will focus
on the development of high-performance mem-
branes with an active layer on the order of 0.1 mm
to compete with the other separation methods. In
addition, membranes should also have to be resis-
tant to warm and high-pressure operating condi-
tions and mechanically strong. Membrane
plasticization and long-term compaction at high
pressure should be further investigated.
Company Module
UOP Spiral wound
NATCO Hollow fiber
Air Products Hollow fiber
MTR –
Air Liquide Hollow fiber
Moreover, how to predict the long-term perfor-
mance in commercial application based on the
short-term lab-scale tests could be a continuing
challenge of membrane system for high-pressure
natural gas sweetening.
References
Adams RT et al (2011) CO2–CH4 permeation in high
zeolite 4A loading mixed matrix membranes.
J Membr Sci 367(1–2):197–203
Deng L et al (2009a) PVA/PVAm blend FSC membrane
for natural gas sweetening. In: Hassan EA
(ed) Proceedings of the 1st annual gas processing
symposium. Elsevier, Amsterdam, pp 247–255
Deng L, Zhao T, Hägg M-B (2009b) CNTs reinforced
nanocomposite FSC membrane for CO2 separation.
In: The 8th China international nanoscience and tech-
nology symposium, Xiangtan
Donohue MD, Minhas BS, Lee SY (1989) Permeation
behavior of carbon dioxide-methane mixtures in cel-
lulose acetate membranes. J Membr Sci
42(3):197–214
He X, Kim T-J, Hägg M-B (2014) Hybrid fixed-site-
carrier membranes for CO2 removal from high pres-
sure natural gas: Membrane optimization and process
condition investigation. J Membr Sci 470:266–274
Peters L et al (2011) CO2 removal from natural gas by
employing amine absorption and membrane
technology – a technical and economical analysis.
Chem Eng J 172(2–3):952–960
Wind JD et al (2002) The effects of crosslinking chemistry
on CO2 plasticization of polyimide gas separation
membranes. Ind Eng Chem Res 41(24):6139–6148
Wind JD, Paul DR, Koros WJ (2004) Natural gas perme-
ation in polyimide membranes. J Membr Sci
228(2):227–236
B
Biogas Upgrading
Xuezhong He
Department of Chemical Engineering,
Norwegian University of Science and
Technology, Trondheim, Sør-Trøndelag,
Norway
Biogas is produced in anaerobic digesters from
biodegradable wastes such as sewage sludge,
manure, organic fraction of household, and
industrial waste. The composition of biogas
varies from the origin of the anaerobic digestion
process, and the main components are methane
(CH4) and carbon dioxide (CO2) as shown in
Table 1 (Rasi et al. 2007). Biogas has a very
high-energy potential due to the presence of
methane (CH4) and thus is a great source for
renewable energy production, which can be
used for heating, combined heat and power
(CHP) generation, vehicle fuel, fuel cell, and
substitute natural gas. Depending on the different
end uses, the specific biogas treatment should be
executed. For the applications as vehicle fuels
and natural gas grid injection, CO2 should be
removed from the raw biogas, i.e., biogas
upgrading, to reduce the corrosion caused by the
acid gases and increase the Wobbe index which is
directly proportion to the methane concentration.
However, biogas upgrading process will add
extra costs into the biogas production. Thus, an
optimized upgrading technology in terms of low
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1335-9
energy consumption and high efficiency should
be developed to reduce the biogas production
cost. Moreover, the minimum emission of CH4
should also be addressed since methane has a
greenhouse effect of around 23 times higher
than that of CO2.
Different techniques such as pressure swing
adsorption (PSA), physical absorption (e.g.,
water scrubbing), chemical absorption (e.g.,
amines), and membrane system have been inves-
tigated for biogas upgrading. The choice of a
suitable technology is mainly dependent on the
specific condition at a plant, such as availability
of low price for heating, electricity, and water, as
well as the amount of gas to be handled. Today,
most of biogas upgrading plants in Sweden are
still using PSA even though the methane content
in the upgraded gas is low (96 %) and methane
loss is quite high (3–10 %), while some plants
using water scrubbing technique will additionally
produce a lot of wastewater, and electricity con-
sumption is also quite high. Membrane system
could be favorable for biogas upgrading due to a
series of advantages including the safety and
simplicity of the operation and easy maintenance
without any hazardous chemicals (Makaruk
et al. 2010). Figure 1 shows a schematic diagram
of membrane system for biogas upgrading.
As illustrated in the above flow sheet, H2S and
water vapor must be removed before feeding into
the membrane system. Compression of gas may
vary depending on whether it goes to natural gas
grid (<80 bar) or will be used for vehicle fuel
2 Biogas Upgrading

Biogas Upgrading, Table 1 Typical gas composition from different sources (Rasi et al. 2007)
Composition (vol, %)
Process CO2 CH4 N2 O2 H2O H2S/SO2 (ppm)
Farm biogas plant 37–38 55–58 <2 <1 4–7 32–169
Sewage digester 38.6 57.8 3.7 0 4–7 62.9
Landfill 37–41 47–57 <1 <1 4–7 36–115

CH4 65%
CO2 35%
H2S 200-300ppm
FeCl2 Water saturated

Drier
Filter
Raw biogas
Compressor Cooler

Biomass
Bioreactor Filter

10-30 bar
Propane/ odour

Compressor
Waste solids

Upgraded biogas,
CH4>96% Cooler 2nd membrane 1st membrane

CO2-rich permeate

Biogas Upgrading, Fig. 1 A schematic diagram for biogas upgrading process by membrane systems

(~200 bar). The main challenge of a membrane
system is the pretreatment of biogas to protect the
membrane materials, especially for the biogas
produced from the sewage treatment plants and
landfill sites where it usually have a lot of mali-
cious gas components. Polyvinyl amine (PVAm)/
polyvinyl alcohol (PVA) blend fixed-site-carrier
(FSC) membranes for biogas upgrading have
been investigated by Deng et al. (Deng and
Hägg 2010). Their results indicated that a mem-
brane process with a CH4 recovery of 99 % at a
low operation cost could be designed to achieve
the specification of natural gas network distribu-
tion, which makes this environmentally friendly
technology more competitive compared to the
other conventional technologies currently used.
Makaruk et al. pointed out that membrane system
provides enough flexibility for heat integration
within biogas plants (Makaruk et al. 2010), and
the expected energy requirement for a single-
produced cubic meter of natural gas substitute is
estimated to be around 0.3 kWh, which is close to
the values reported in an industrial scale demon-
strator for membrane biogas upgrading plant at
Bruck an der Leitha in Austria (Miltner
et al. 2008). Moreover, a new carbon membrane
company MemfoACT (http://www.memforact.
no) was launched in 2008 in Norway, which
mainly focuses on the biogas upgrading using
their patented hollow fiber carbon molecular
sieve membranes. Their contributions could
Biogas Upgrading
promote to bring this technology into the com-
mercial application in the near future.
References
Deng L, Hägg M-B (2010) Techno-economic evaluation
of biogas upgrading process using CO2 facilitated
transport membrane. IJGGC 4:638–646
3
Makaruk A, Miltner M, Harasek M (2010) Membrane
biogas upgrading processes for the production of nat-
ural gas substitute. Sep Purif Technol 74:83–92
Miltner M, Makaruk A, Harasek M (2008) Application of
gas permeation for biogas upgrade – operational expe-
riences of feeding biomethane into the Austrian gas
grid. 16th European Biomass Conference & Exhibition
from Research to Industry and Markets, Valencia
Rasi S, Veijanen A, Rintala J (2007) Trace compounds of
biogas from different biogas production plants. Energy
32:1375–1380
C
Cell Encapsulation
Cecile Legallais
UMR CNRS 7338 Biomechanics and
Bioengineering, Université de Technologie de
Compiegne (UTC), Compiegne, France
Encapsulation can be generally defined as a pro-
cess that allows the entrapment of substances in a
spherical-shaped porous material Chang (1964).
When sieving is ensured by an ultrathin mem-
brane formed around a liquid core, the term of
“capsule” is appropriate. When sieving is ensured
by the whole core of the sphere, the term of
“bead” is preferred and the porosity is homoge-
nous across the structure.
In case of cell encapsulation for 3D tissue
engineering, the goal is to host cells of a specific
organ type into a porous scaffold in order to
maintain their original functions and recreate a
tridimensional organization mimicking the tissue
to be replaced. Although many applications (such
as pancreas, liver) have been developed in the last
30 years, there is still no clear consensus on the
best choice for biomaterials and cells, whatever
the organ type.
The materials hosting the cells should offer
biocompatibility, adapted surface properties,
and adequate porosity to allow the transfer of
nutrients, oxygen, metabolites, and low molecu-
lar weight proteins such as albumin, but also
immune protection and mechanical stability.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1337-4
They can be native or benefit from chemical and
biological modifications to better mimic the
cells’ niche and create microenvironments to
control their response. Alginate is up to now the
materials of reference. Alginate beads or capsules
hosting cells are easy to produce by extrusion
techniques, using coaxial air flow, electrostatic
force, or vibrating noozle to adjust the bead diam-
eter. Encapsulation can be performed at room or
body temperature, at physiological pH, and in
isotonic solutions. The alginate bead or capsule
might be coated in some approaches with a poly-
L-lysine layer (PLL) to improve mechanical sta-
bility and reduce external porosity Orive
et al. (2006). Other materials such as collagen,
chitosan, gelatin, and agarose can also be
employed, alone or in combination with alginate.
The spherical shape of beads or capsules pro-
vides them with interesting characteristics that
can be considered advantageous to other porous
scaffolds with plate or cylindrical (hollow fiber,
for instance) geometries. This spherical shape is
considered as the most efficient one for the pro-
motion of mass transfer. Indeed, the sphere brings
the best surface-to-volume ratio, leading to
proper solutes’ bidirectional diffusion, provided
that the sieving properties of the material are
tuned. The size of the beads or capsules related
can be adjusted by the manufacturing process.
Usually, their diameter does not exceed
500–1000 mm to avoid cell necrosis in the center.
In addition, beads or capsules of this size can be
easily frozen. Microencapsulation decreases cell
2 Cell Encapsulation

a b
cells plasma/blood
nutrients

IgG

oxygen

metabolites

barrier cells

Cell Encapsulation, Fig. 1 Principle of biohybrid constructs. (a) Description of the mass transfer expected between
cell compartment and host. (b) Application to microencapsulation

damage during cryopreservation and allows thus
an easy storage before use, leading to readily
available encapsulated cells when needed.
The choice of cells depends on the targeted
application as organ supply. For clinical applica-
tion of tissue engineering, only primary cells
(from animal or human origin) and cell lines
have been employed. To reconstitute the func-
tions of a failing organ or tissue, multiple
pre-differentiated stem cell populations could be
used and/or combined in biomaterials to form
biohybrid constructs (Fig. 1).
References
Chang TM (1964) Semipermeable microcapsules. Science
146(3643):524–525
Orive G et al (2006) Biocompatibility of alginate-poly-
L-lysine microcapsules for cell therapy. Biomaterials
27(20):3691–3700
B
Biocatalytic Membrane Reactors
with Chemically Bound Enzyme
Lidietta Giorno, Giuseppe Vitola, Giuseppe
Ranieri and Francesca Militano
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, National
Research Council of Italy, Rende (CS), Calabria,
Italy
Synonyms
Biocatalytic membrane reactors with covalent
bound enzyme
Attachments of biocatalysts to membrane can
result from ionic binding, cross-linking, and
covalent linking. Since 1954, when protease
was covalently bound to diazotized polystyrene,
enzyme immobilization via covalent bonds has
been an established immobilization technique,
usually carried out by means of
bi/multifunctional reagents, such as glutaralde-
hyde, (3-aminopropyl)triethoxysilane (APTES),
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
hydrochloride (EDC), etc.
The crucial aspect is the use of mild reaction
conditions that do not denature the enzyme dur-
ing the covalent bond formation.
When the extent of initial denaturation is
acceptable in the economics of the process,
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1338-1
enzymes bound to membranes can be used in
continuous flow reactors.
Table 1 shows the protein functional groups
involved in covalent bond with functional groups
present or grafted on the membrane, in mild
conditions.
Table 2 summarizes most commonly used
cross-linking agents to bridge enzyme to
functionalized membranes.
Hydrophilic, hydrophobic polymeric mem-
branes as well as inorganic membranes can be
used as support for covalent bound of enzymes.
Polymeric membranes based on natural mate-
rials, such as cellulose and its derivatives
(regenerated cellulose, cellulose acetate, etc.)
have been extensively used as support for the
covalent immobilization of enzymes. Cellulose
membranes can be activated by a variety of
agents to produce reactive centers for the cova-
lent binding of enzymes. Its chemical structure is
mainly composed of hydroxyl groups, and then
the most common activation methods are based
on the conversion of the hydroxyl groups into
more reactive functional groups. In particular,
carbonyl groups are very suitable for enzyme
immobilization since they can react with primary
amines from enzymes (e-amino group of lysine
residues) to form imine. The most used method of
forming carbonyl groups onto the cellulose skel-
eton is periodate oxidation. The hydroxyl groups
(secondary alcohol groups) of the glucose units
are oxidized into the corresponding aldehydes by
means of sodium periodate (NaIO4). The
2 Biocatalytic Membrane Reactors with Chemically Bound Enzyme

Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Table 1 Protein functional groups involved in
covalent bond with membranes in mild conditions
Protein chemical group Structure
Epsilon amino groups of lysine
O
H2N
OH

NH2
Epsilon amino groups of arginine
NH O

H2N N OH
H NH2
Beta and gamma carboxyl groups of aspartic and glutamic acids
O

HO OH

O NH2

Phenol ring of tyrosine

O

OH

NH2
HO

Thiol group of cysteine

O

HS OH

NH2
Hydroxyl groups of serine and threonine
O OH O

OH OH
HO
NH2 NH2
Imidazole group of histidine
O
H
N OH

N NH2

Indole group of tryptophan

O

OH

N NH2
H
Biocatalytic Membrane Reactors with Chemically Bound Enzyme 3

Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Table 2 Bi/multifunctional reagents com-
monly used in enzymatic covalent immobilization
Reactive chemical
Cross-linker Structure group
Glutaraldehyde (GA) Aldehydic groups
O O
(3-aminopropyl) triethoxysilane (APTES) Ethoxyl and amino
O groups
Si NH2
O O

Dimethylaminopropane (DAMP) Amino groups

H2N NH2

O, O0 - Bis(2-aminopropyl)-polyethylene glycol Amino groups

500 (bNH2PEG) PEG
H2N NH2
1,3,5-benzene tricarbonyl chloride (or trimesoyl Carbonyl chloride
chloride TMC) O Cl groups

O O

Cl Cl
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide Carbodiimide group
hydrochloride (EDC) + Cl–
Spacer Arm 0.0 Å N NH
C
N
Dicyclohexylcarbodiimide (DCC) Carbodiimide group
Spacer Arm 0.0 Å
N
C
N

covalent binding of the enzyme can be achieved
by direct reaction with the aldehyde-active
groups on the membrane surface (Xiao-Jun
et al. 2011) or via different spacers. The introduc-
tion of an appropriate spacer between the enzyme
and the membrane often improves the perfor-
mance of immobilized enzyme, such as enzyme
stability and retained activity. Spacers of differ-
ent lengths are generally introduced by using
bifunctional agents such as diamines (esp.
ethylenediamine, pentaethylenehexamine, etc.)
that are coupled or activated with glutaraldehyde
before enzyme immobilization (Peng-Cheng
et al. 2011). The reaction mechanism involves
the amino groups of the enzyme and the aldehyde
groups of glutaraldehyde on the membrane sur-
face. The schematic representation of an enzyme
covalently attached onto cellulose-activated
membrane is reported in Fig. 1.
Poly(vinylidene fluoride) (PVDF) membrane
has been used either for scientific research or
industrial application in particular micro- and
ultrafiltration process. The great interest to
PVDF membrane is due to its extraordinary ther-
mal, mechanical, and chemical resistance in addi-
tion to membrane-forming properties. Its
structure consisting of repeated – (CH2-
CF2)n – units confers to PVDF these good prop-
erties, but makes impossible enzyme immobili-
zation on native PVDF in a covalent manner. This
disadvantage can be overcome performing PVDF
functionalization, in order to introduce on the
polymeric membrane structure, reactive groups
that can covalently couple with enzyme func-
tional groups. Surface modification of existing
PVDF membrane can be performed by coating
or grafting. Coating modification is preferred when
only an improved hydrophilicity of the membrane
4 Biocatalytic Membrane Reactors with Chemically Bound Enzyme

H OH H OH H OH
H O periodate H O
O H2N-(CH2)n-NH2 H O
HO oxidation O O
H O O O
OH H O diamine spacer OH
H H H
H H N H
Cellulose H (CH2)n NH2
dialdehyde

H OH H OH
OHC (CH2)3 CHO H O H2N
H O
O
O OH O
glutaraldehyde enzyme coupling O OH
activation H H
N H
H (CH2)n (CH2)3 O N H
N H (CH2)n N
C (CH2)3 N
H C C
H C
H H

Biocatalytic Membrane Reactors with Chemically activated with periodate oxidation and a generic diamine
Bound Enzyme, Fig. 1 Schematic representation of an spacer, n represent the number of CH2 groups
enzyme covalently immobilized onto cellulose membrane

–
–H2O – –F
[n
—[ CF2– CH– CF2– CH2 — [n
—[ CF2– CH– CF – CH2 — [n
—[ CF2– CH= CF – CH2 —
H F
–
OH

H F
–
–

[n
—[ CF2– CH= CF – CH2 — –HF
[n
—[ CF2– C – C – CH2 — [n
—[ CF2– CH= C – CH2 —
– +
+
¨ H2N HN
H2N
NH2 NH2
NH2

Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 2 Possible mechanism of alkaline-
induced DAMP grafting on PVDF

H O O
Na2CO3
+ H2N NH2 NH2 + O H N H N N
pH11 50°C Enzyme
DAMP GA

PVDF PVDF-DAMP PVDF-DAMP-GA PVDF-DAMP-GA-Enzyme

Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 3 Illustration of various steps for PVDF
functionalization with amino groups and subsequent enzyme attachment via cross-linking with glutaraldehyde

surface is required, but it is not useful as anchor acting on degree of grafting and type of func-
point for enzyme immobilization because of the tional chain introduced, it is possible to affect or
instability of the coated layer which interacts with not affect membrane bulk properties as, for
the membrane merely by physical adsorption. example, hydrophobicity.
More interesting for enzyme immobilization is Surface grafting can be performed by high-
grafting modification which can introduce on energy radiation techniques like plasma treat-
the PVDF backbone functional chains that can ment, ozonation, and UV or by wet chemistry in
be used for enzyme immobilization; in addition harsh basic environment. For example, grafting
 Biocatalytic Membrane Reactors with Chemically Bound Enzyme

Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 4 Schematic representation of stages involved in an example of enzymatic covalent immobili-
zation onto inorganic membranes
5
6 Biocatalytic Membrane Reactors with Chemically Bound Enzyme
of amino groups on PVDF membrane surface can
be achieved by treatment at high pH and high
temperature with diamine reagent. The high pH
promotes fluorine elimination from the PVDF
chains and the grafting of diamino reagent
(Vitola et al. 2015) (Fig. 2).
Subsequently the pendant amino groups can
be activated for enzyme immobilization in mild
conditions using condensing reagent like glutar-
aldehyde (Fig. 3).
Polymeric membrane based on
polyethersulfone (PES) is widely used mem-
branes in ultrafiltration processes due to their
high performance and low-cost profile. PES
membranes have been used also in more sophis-
ticated application such as carrier for immobili-
zation of bioactive molecules in membrane
bioreactors. For this aim effort has been done to
introduce reactive groups for biomolecule immo-
bilization without affecting the overall bulk prop-
erties. Photochemical surface modification of
existing PES membrane is the most popular tech-
nique for introduction of reactive groups on PES
membrane. In fact PES has an intrinsic
photoreactivity making possible to perform the
modification in mild reaction condition. Mono-
mer like acrylic acid has been grafted in this way
on PES membrane and then activated for enzyme
immobilization using 1-ethyl-3-(3-dimethylami-
nopropyl) carbodiimide hydrochloride (EDC).
Inorganic membranes, such alumina, titania,
silica, etc., can be also used for enzymatic immo-
bilization via covalent binding if functionalized
in a suitable way. Hydroxyl groups present onto
inorganic membrane surface are not able to
directly coupling enzymes. Activation of
hydroxyl groups can be performed by silanization
reagents, such as (3-aminopropyl)triethoxysilane
(APTES). APTES exhibits terminal amino
groups available for the attachment of cross-
linking reagents such as glutaraldehyde. Termi-
nal aldehydic group of glutaraldehyde reacts with
the exposed amino groups of the organosilane by
forming a Schiff base. Final covalent binding
occurs through formation of a new Schiff base
between aldehydic terminal group of glutaralde-
hyde and amino groups exposed from the enzy-
matic amino acid residues of lysine (S. Tanvir
et al. 2009). Schematic reaction of an example of
enzymatic covalent immobilization onto inor-
ganic supports is illustrated in Fig. 4.
Applications of covalently immobilized mem-
brane systems are membrane electrodes for ana-
lytical purposes, reactions of substrates whose
molecular weight is low as compared to mem-
brane molecular weight cut-off, and enzymatic
conversion of macromolecules to lower molecu-
lar weight species able to permeate the
supporting membrane.
References
Chen P-C, Huang X-J, Huang F, Ou Y, Chen M-R, Xu Z-K
(2011) Immobilization of lipase onto cellulose
ultrafine fiber membrane for oil hydrolysis in high
performance bioreactor. Cellulose 18:1563–1571
Huang X-J, Chen P-C, Huang F, Ou Y, Chen M-R, Xu Z-K
(2011) Immobilization of Candida rugosa lipase on
electrospun cellulose nanofiber membrane. J Mol
Catal B Enzym 70:95–100
Tanvir S, Pantigny J, Boulnois P, Pulvin S (2009) Cova-
lent immobilization of recombinant human cyto-
chrome CYP2E1 and glucose-6-phosphate
dehydrogenase in alumina membrane for drug screen-
ing applications. J Membr Sci 329:85–90
Vitola G, Mazzei R, Fontananova E, Giorno L (2015)
PVDF membrane biofunctionalization by chemical
grafting. J Membr Sci 476:483–489
S
Solubility of Gases in Membranes
Maria Grazia De Angelis
Dipartimento di Ingegneria Civile, Chimica,
Ambientale e dei Materiali, Università di
Bologna, Bologna, Italy
The solubility of gases in membranes directly
affects the gas separation performance in pro-
cesses governed by the solution-diffusion mech-
anism. Gaseous solutes (penetrants) are absorbed
onto the upstream membrane side, diffuse
through the membrane, and desorb from the
membrane in the downstream side toward the
permeate gas phase. According to Fick’s law, in
steady state, the flux of penetrant i through the
membrane is associated with the diffusivity and
concentration gradient DCi/l as follows:
DCi
J i ¼ Di ðsteady stateÞ
l including the solubility, can vary with time,
Amorphous Rubbery Membranes
In polymer membranes above their glass transi-
tion point (rubbery), the solubility has a unique
value once the temperature and penetrant fugac-
ities are fixed. The solubility isotherms of gases
in rubbers are linear, for light gases, or concave
up for non-light gases and vapors (Fig. 1i). High-
pressure gases (e.g., supercritical CO2) are shown
to exhibit a decrease of slope of the solubility
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1347-1
isotherms at pressures above the critical one; in
such range the fluid behavior resembles the liquid
one, in which the properties vary slightly with the
pressure (Fig. 1ii).
If the rubbery polymer is cross-linked, the
swelling of the rubbery matrix and the solubility
are lower than those measured in the uncross-
linked rubber; indeed cross-linking can prevent
plasticization of the membrane by highly soluble
vapors. The solubility of gases in rubbery mem-
branes can be estimated with the Flory-Huggins
and related activity coefficient models or with
equation of state models (lattice fluid, SAFT,
PHSC, etc.) (De Angelis and Sarti 2011).
Amorphous Glassy Membranes
Membranes below their glass transition point
(glassy) are not at equilibrium due to the hindered
mobility of polymeric chains, and the properties,
(1)
either because of aging or as a consequence of
thermal, mechanical, and chemical treatments.
The state of the glassy membrane has to be
defined with a proper parameter, such as the
glassy membrane density, or equivalently the
fractional free volume, in addition to the other
state variables.
The solubility isotherms of gases in glassy
membranes are linear for light gases or concave
down for other gases and vapors (Fig. 1i). Some
vapors (e.g., alcohols) in certain glassy polymers
2 Solubility of Gases in Membranes
(i)
Solubility
a
b
c
Pressure, fugacity or activity
(iii)
Solubility
Pressure, fugacity or activity
Solubility of Gases in Membranes, Fig. 1 Different
shapes of solubility isotherms in polymeric membranes.
(i) (a) Sorption of gases and vapors in glassy membranes,
(b) sorption of light gases in glassy and rubbery mem-
branes, and (c) sorption of gases and vapors in rubbery
membranes. (ii) Supercritical sorption in rubbery
can show a sigmoidal shape of the solubility
isotherm (Fig. 1iii).
If the glassy membrane is close to its glass
transition temperature and/or if the penetrant
has high solubility in the membrane and is able
to significantly swell and plasticize the mem-
brane, a glass transition can be observed at con-
stant temperature by increasing the gas pressure
(ii)
Solubility
Supercritical
behavior
Pressure, fugacity or activity
Solubility (iV)
Supercritical
behavior
Sorption-induced glass transition
Pressure, fugacity or activity
membranes (e.g., CO2 in PDMS), (iii) sigmoidal sorption
of polar vapors in hydrocarbon glassy membranes (e.g.,
alcohols in PTMSP) (Nakanishi et al. 1987), and (iv) CO2
sorption in an initially glassy membrane (e.g., PMMA)
(Carlà et al. 2005)
(sorption-induced glass transition), which occurs
as a change of concavity of the solubility iso-
therm (Fig. 1iv). The solubility in glassy mem-
branes can be modeled by the dual mode
empirical model (Barrer et al. 1958) or the
nonequilibrium approaches proposed by
Doghieri and coworkers (Doghieri and Sarti
1996, De Angelis and Sarti 2011).
Solubility of Gases in Membranes
Semicrystalline Membranes
The crystalline phase is considered impermeable
and insoluble, and the solubility of the matrix is
given by
Ci ¼ ð1  fCR ÞCi, AM (2)
where fCR is the fraction of crystalline phase and
Ci,AM is the solubility in the amorphous phase. In
some cases, however, the presence of the crystal-
line phase may vary the amorphous phase prop-
erties with respect to the pure state ones. In
particular, it can reduce the specific volume or
reduce the ability of the matrix to swell, with a
consequent lower solubility of the amorphous
phase with respect to the pure phase: such phe-
nomenon has been modeled invoking an addi-
tional pressure term, using both molecular and
equation of state methods (Memari et al. 2010,
Minelli and Angelis 2014).
Composite (Mixed Matrix) Membranes
In mixed matrix membranes, the solubility Ci of a
fluid in a mixed matrix membrane (MMM) can be
estimated with an additive rule based on the poly-
mer (P) and filler (F) fractions in the MMM, and
the solubility values in the corresponding pure
phases, Ci,P and Ci,F:
Ci ¼ fP Ci, P þ ð1  fP ÞCi, F (3)
However, in many cases, a deviation from this
rule is observed. The filler phase, if porous, can
3
be obstructed by contact with the polymer and its
sorption capacity lowered. The imperfect adhe-
sion between polymer and filler phase can modify
the morphology and properties of the polymeric
phase and its sorption capacity, as in the case of
mixed matrices formed by glassy polymers and
nanometric silica. In such systems the solubility
increases, due to an increased free volume of the
polymer (De Angelis and Sarti 2012).
References
Barrer RM, Barrie JA, Slater J (1958) Sorption and diffu-
sion in ethyl cellulose. Part III. Comparison between
ethyl cellulose and rubber. J Polym Sci 27:177–197
Carlà V, Wang K, Hussain Y, Efimenko K, Genzer J,
Grant C, Sarti GC, Carbonell RG, Doghieri F (2005)
Nonequilibrium model for sorption and swelling of
bulk glassy polymer films with supercritical carbon
dioxide. Macromolecules 38:10299–10313
De Angelis MG, Sarti GC (2011) Solubility of gases and
liquids in glassy polymers. Annu Rev Chem Biomolec
Eng 2:97–120
De Angelis MG, Sarti GC (2012) Gas sorption and per-
meation in mixed matrix membranes based on glassy
polymers and silica nanoparticles. Curr Opin Chem
Eng 1:148–155
Doghieri F, Sarti GC (1996) Nonequilibrium lattice fluids:
a predictive model for the solubility in glassy poly-
mers. Macromolecules 29:7885–7896
Memari P, Lachet V, Rousseau B (2010) Molecular sim-
ulations of the solubility of gases in polyethylene
below its melting temperature. Polymer 51:4978–4984
Minelli M, De Angelis MG (2014) An equation of state
(EoS) based model for the fluid solubility in semicrys-
talline polymer. Fluid Phase Equilibr 367:173–181
Nakanishi K, Odani H, Kurata M, Masuda T, Higashimura
T (1987) Sorption of alcohol vapors in a disubstituted
polyacetylene. Polym J 19:293–296
L
Leather Industry, Soaking
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
In this operation, raw skins are exposed to water
and chemicals (small quantities of imbibing sub-
stances) in order to hydrate proteins and fibers, to
solubilize the denatured proteins, and to elimi-
nate salt compounds with dirt (blood, excrement,
earth) which are attached to the skins.
The soaking-exhausted effluent-containing
excrements, salts, and chemical additives are nor-
mally discharged into a water-treatment plant
(Sharphouse 1983).
UF membranes can be used to concentrate
organic components in the feed tank of the UF
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1348-1
plant. A clear permeate, enriched in salt com-
pounds, could be reused in the pickling step
after adjustment of the salt concentration with
NaCl (Fig. 1). Preliminary treatments are neces-
sary in order to remove the suspended materials;
a sedimentation step allows to reduce the
suspended solids of 90 %; then steel spring filters
(200–300 mm net size) could be employed to
remove large particles avoiding clogging phe-
nomena of UF membranes (Cassano et al. 2001).
References
Cassano A, Molinari R, Romano M, Drioli E (2001) Treat-
ment of aqueous effluents of the leather industry by
membrane processes. A review. J Membr Sci
181:111–126
Sharphouse JH (1983) Leather technicians handbook.
Leather Producers Association, Northampton
2 Leather Industry, Soaking

Leather Industry, water,

Soaking, imbibing
Fig. 1 Treatment of substances, purging
exhausted effluents of the skins
soaking step by UF process
exhausted
bath

UF

pickling
L
Leather Industry, Unhairing-Liming
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
The aim of the unhairing-liming step is to remove
from the raw skin all the components which are
not transformed into leather, such as the superfi-
cial epidermis including the hair and the subcu-
taneous adipose layer. The liming step introduces
chemicals such as lime (Ca(OH)2) and sodium
sulfide (Na2S) or sodium hydrosulfide (NaHS)
which open the fibrous structure of the skin. Con-
sequently, exhausted effluents are highly polluted
for the presence of sulfide, amines, organic matter
coming from degradation of hairs and epidermis,
and high concentration of alkalis. The COD of
exhausted effluents ranges between 20,000 and
40,000 mg/L of consumed oxygen.
The UF treatment of the exhausted unhairing
liquor has been one of the first membrane
approaches introduced in the leather industry
(Molinari 1995). It can be exploited to recover
sulfide and solubilized lime together with low
molecular weight proteic substances in the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1349-1
permeate stream in order to reuse the purified
solution for the preparation of a new liming
bath. High molecular weight proteic components,
coming from chemical degradation of hairs and
epidermis, are concentrated in the retentate
stream (Fig. 1).
Considering that 60–65 % of the initial sulfide
remains in the exhausted liquor and 5–10 % is
lost in the retentate, the quantity of sulfide that is
possible to recycle with an UF system is
55–60 %.
An innovating system based on the use of
enzymes and small quantities of sodium sulfide
(1.5 % instead of 10 %) has been proposed and
tested on industrial scale. In this approach the
enzymatic unhairing was combined to the contin-
uous cross-flow UF of the bath permitting to keep
constant the sulfide concentration in the
unhairing bath due to its permeation through the
UF membrane. The organic components
(products of degradation of the keratin and of
the interfibrillar proteins, fat substances, etc.)
are concentrated in the retentate stream. This
new approach is safer for workers and character-
ized by a reduced environmental impact because
hairs are not dissolved and can be removed sep-
arately (Cassano et al. 1998).
2 Leather Industry, Unhairing-Liming

proteic flour
desulfidation
desalination
drying
water,
Ca(OH)2, concentrated
Na2S proteic fractions
skins

exhausted
bath

UF

Permeate
(low M.W. species, sulfide)

preparation of new liming baths

Leather Industry, Unhairing-Liming, Fig. 1 Treatment of exhausted liming effluent by ultrafiltration

References Molinari R (1995) Application of membrane separation

Cassano A, Drioli E, Molinari R (1998) Integration of
ultrafiltration into unhairing and degreasing opera-
tions. J Soc Leath Technol Chem 82:130–135
techniques to the treatment of tanneries wastewaters.
In: Caetano A, De Pinho MN, Drioli E, Muntau H (eds)
Membrane technology: application to industrial waste-
water treatment. Kluwer, The Netherlands,
pp 101–122
L
Leather Industry
Alfredo Cassano
Institute on Membrane Technology, ITM-CNR,
Rende (CS), Italy
In the leather industry, the animal rawhide is
converted into finished leather, a durable and
flexible material, through a series of chemical
and mechanical treatments.
The steps in the production of leather between
curing (a salt treatment to prevent putrefaction of
the collagen) and tanning (a treatment of leather
stabilization with vegetable or mineral sub-
stances) are collectively referred to as beamhouse
operations. They include, in order, soaking,
unhairing/liming, deliming/bating, and pickling.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1350-1
All these processes are realized in chemical reac-
tors (tumblers) in which the skins react with dif-
ferent chemicals (acids, alkalis, chromium salts,
tannins, solvents, sulfides, dyes, auxiliaries, etc.)
in aqueous solutions (Fig. 1).
Wastewaters coming from different tanning
operations contain high concentrations of organic
and inorganic substances causing significant pol-
lution phenomena. Organic pollutants come from
the skins (it is calculated that the raw skin has
30 % loss of organic material during the working
cycle), or they are introduced during the working
cycle (e.g., tanning). Inorganic pollutants are a
residual of the used chemicals (i.e., chromium
salts) that are not completely fixed by the skins
owing to the low efficiency of the operations
(Cassano et al. 2001).
2 Leather Industry

Leather Industry, water,

Fig. 1 Scheme of tumbler skins,
chemicals

treated skins,
exhausted liquor

References

Cassano A, Molinari R, Romano M, Drioli E (2001) Treat-

ment of aqueous effluents of the leather industry by
membrane processes. A review. J Membr Sci
181:111–126
C
Chloromethylation and Amination
of Polymers (for AEM)
Pejman Ahmadiannamini
Biomedical Engineering, University of Arkansas,
Fayetteville, AR, USA
Chloromethylation (generally haloalkylation) of
polymeric membranes followed by an amination
reaction has been widely used for preparation of
anion exchange membranes (AEMs). Significant
efforts have been made to prepare AEMs from
insoluble polymeric films such as polyethylene
(PE), polypropylene (PP), polytetrafluoroethylene
(PTFE), and polyvinylidene fluoride (PVDF).
Such AEMs are typically prepared by grafting
vinyl monomers such as styrene onto polymeric
films and subsequent chloromethylation and
amination modifications. Also, soluble polymers
such as polystyrene (PS), polyether sulfone
(PES), polyether ketone (PEK), or their blends
or block copolymers have been widely used for
preparation of AEMs. In such case, charged moi-
eties can be introduced to the dissolved polymer
via chloromethylation and amination reactions,
either prior to the casting of polymer or after the
casting into a film. Posttreatment, i.e., cross-
linking of membranes, is often required to
improve the chemical stability of AEMs prepared
from soluble polymers (Xu 2005).
Chloromethyl groups can be introduced via
Friedel-Crafts mechanism typically by reacting
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1360-3
polymer with a chloromethylating agent, such as
chloromethyl methyl ether (CH3OCH2Cl) or
chlorotrimethylsilane (C3H9ClSi), using a metal-
lic chloride (e.g., FeCl3, ZnCl2, or SnCl4) as cat-
alyst. Cross-linking of benzene rings with
methylene bridges is encountered as a side reac-
tion which would result in lower ion exchange
capacity of final product according to the reaction
presented in Fig. 1 (Jones 1952):
Alternatively, chloromethylation of polymers
can be carried out using reaction mixtures which
produce chloromethyl methyl ether in situ. These
reaction mixtures are also known as
chloromethylating complexes and may be, for
example:
• Mixtures of paraformaldehyde and
hydrochloric acid
• Mixtures of formaldehyde polymers and alu-
minum chloride
• Mixtures of methylal, thionyl chloride, and
catalyst
• Mixtures of methylal, sulfuryl chloride plus
chlorosulfonic acid, or chlorosulfonic acid
only
• Mixtures of methylal, chlorosulfonic acid, and
an oxygen-containing polar liquid
Among these complexes, the most commonly
used are the ones that contain chlorosulfonic acid.
The reaction can be represented as (Boutier
et al. 1980):
2 Chloromethylation and Amination of Polymers (for AEM)

CH3OCH2Cl
R R CH2Cl
SnCl4

R + R CH2Cl R CH2 R

Chloromethylation and Amination of Polymers (for AEM), Fig. 1 Chloromethylation and methylene bridge
crosslinking of polymers

Chloromethylation R R
and Amination
of Polymers (for AEM),
Fig. 2 Amination reaction R1
of chloromethylated
N H
polymers
NH3 R2 R1
Cl− N+H3 R
N+H Cl−
R2
R1 R1

R N H N R3 R
H R2
CH2Cl

R1 R1
Cl− N+H2 N+ Cl−
R2
R3

CH3 OH þ CHOH þ SO3 HCl References

! CH3 OCH2 Cl þ H2 SO4
Positively charged groups are introduced to the
chloromethylated polymer via amination reaction.
The functional group of the AEMs can be weakly
basic, such as primary, secondary, or tertiary
amino groups which are obtained via reaction of
chloromethylated polymer with ammonia or with
primary or secondary amines, respectively. The
amination reaction with tertiary amines, known
as quaternarization, leads to AEMs with strongly
basic functional groups (quaternary ammonium)
(Helfferich 1995) (Fig. 2).
Boutier JL, Grammont PDA, Herbin JEE (1980) Process
for the chloromethylation of polymers for the produc-
tion of anionic exchange resins, United States Patent,
4,225,644
Helfferich FG (1995) Ion exchange. Dover Publications,
New York
Jones GD (1952) Chloromethylation of polystyrene. Ind
Eng Chem 44(11):2686–2693
Xu T (2005) Ion exchange membranes: state of their devel-
opment and perspective. J Membr Sci 263(1–2):1–29
P
Polyelectrolyte Membrane for OSN
Pejman Ahmadiannamini
Biomedical Engineering, University of Arkansas,
Fayetteville, AR, USA
Polymeric charged nanofiltration (NF) mem-
branes have received a growing interest for
water desalination and purification. Selective
properties of charged NF membranes can be
based upon not only the “sieving effect” but
also the “charge effect.” Thus, the surface charge
density of the membranes and the structure of the
functional groups in the selective layer are imper-
ative factors to determine their performance.
The range of NF applications has recently
been broadened to organic feeds in organic sol-
vent nanofiltration (OSN), also known as solvent-
resistant NF (SRNF). A more widespread use of
OSN requires solvent-resistant membranes that
preserve their separation characteristics under
more aggressive conditions of aprotic or strongly
swelling solvents and elevated temperatures
(Vandezande et al. 2008).
Alternate layer-by-layer (LbL) deposition of
polyelectrolytes (PEs) of opposite charges has
emerged as a versatile and inexpensive method
to prepare thin films in the nanometer range for
different applications (Decher 1997). A number
of parameters, such as PE type and molecular
weight of the PE, ionic strength, and pH of the
PE solutions, can influence the structure of the
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1361-6
PE multilayer (PEM) films deposited by the
LbL method. Films prepared via this method
are in particular attractive materials with con-
trolled thickness and surface properties for
OSN (Li et al. 2008; Ahmadiannamini
et al. 2012a).
PEs can be regarded as strong or weak
depending upon degree of ionization of charged
species. It is identified as strong when the
dissolved PE dissociates completely and as
weak when it is partially ionized. Charge density
of weak PEMs can be affected by more factors
than with strong ones, such as salt concentration
and pH. This offers more possibilities to control
membrane morphology and performance.
A higher charge density is expected to lead to
thinner deposited layers. Indeed, the self-
repulsion of the chains is increased, and such
polymer chains thus possess a larger cross-
sectional area in solution, thus covering a larger
surface upon adsorption on the substrate
(Schönhoff 2003).
Both weak and strong PEs have been used for
the buildup of PEM membranes. Comparison of
their NF and OSN performances reveals that con-
trary to the applications in aqueous NF, PEM
membranes constructed from weak PEs have
retentions comparable to those of membranes
prepared from strong PEs (Tables 1 and 2)
(Ahmadiannamini et al. 2012a).
Another important parameter which can influ-
ence properties of PEMs is the charge density
(ionic cross-linking) of the multilayer which is
2 Polyelectrolyte Membrane for OSN

Polyelectrolyte Membrane for OSN, Table 1 NF performance of PEM membranes in aqueous applications
Retention (%)
Membrane Permeance (l.m 2.bar 1.h 1) Cl SO42
(PAA pH 4.5/PDADMAC pH 4.5)4.5 12.15  4.34 4.4  4.3 24  14
(PSS/PDADMAC)4.5 20.83  0.86 15.5  1.4 92.3  0.9
(PDADMAC/SPEEK)5 15.6  1.04 15.9  4 93.9  1

Polyelectrolyte Membrane for OSN, Table 2 OSN performance of PEM membranes in solvent applications (RB in
IPA)
Membrane Permeance (l.m 2.bar 1.h 1) RB retention (%)
(PAA pH 4/PDADMAC pH 7)5 0.03 97.0  2.1
(PDADMAC/SPEEK)5 0.08 98.2

Polyelectrolyte Membrane for OSN, Table 3 Comparison of performance between PEM membranes and other OSN
membranes
RB/IPA RB/DMF
Membrane Permeance (l/m2.h.bar) Retention (%) Permeance (l/m2.h.bar) Retention (%)
Multilayered PEC 0.12–1.57 >99 0.06–0.2 94–98
Polypyrrole 1.42 98 0.03 90
PDMS 0.086 91 n.m. n.m.
Poly(sulfone) 0.14 77.5 n.m. n.m.
Poly(sulfone)/SPEEK 0.47 95.6 n.m. n.m.
Starmem™ 120 0.49 100 – –
Starmem™ 228 0.087 99.6 – –
Starmem™ 240 0.29 97.9 – –
MPF-50 0.72 96 – –
n.m. not measured
– unstable in the solvent

defined as the number of ion pairs per number of References

carbon atoms in the repeat unit (Krasemann and
Tieke 2000). PEMs with higher ionic cross-link
densities shrink less drastically in organic sol-
vents and show higher permeances.
A very complex interplay of different contri-
butions caused by mutual PE-solvent-solute-
membrane interactions has to be taken into
account. PEM membranes are stable in a wide
variety of organic solvents, and their perfor-
mance is better than that of the different commer-
cial membranes (Table 3), as very high retentions
are combined with superior fluxes
(Ahmadiannamini et al. 2012b).
Ahmadiannamini P, Li X, Goyens W, Joseph N,
Meesschaert B, Vankelecom IFJ (2012a) Multilayered
polyelectrolyte complex based solvent resistant
nanofiltration membranes prepared from weak
polyacids. J Membr Sci 394–395:98–106
Ahmadiannamini P, Li X, Goyens W, Meesschaert B,
Vanderlinden W, De Feyter S, Vankelecom IFJ
(2012b) Influence of polyanion type and cationic coun-
ter ion on the SRNF performance of polyelectrolyte
membranes. J Membr Sci 403–404:216–226
Decher G (1997) Fuzzy nanoassemblies: toward layered
polymeric multicomposites. Science
277(5330):1232–1237
Krasemann L, Tieke B (2000) Selective ion transport
across self-assembled alternating multilayers of
Polyelectrolyte Membrane for OSN 3

cationic and anionic polyelectrolytes. Langmuir Schönhoff M (2003) Layered polyelectrolyte complexes:
16(2):287–290 physics of formation and molecular properties. J Phys
Li X, De Feyter S, Chen D, Aldea S, Vandezande P, Du Condens Matter 15(49):R1781–R1808
Prez F, Vankelecom IFJ (2008) Solvent-resistant Vandezande P, Gevers LEM, Vankelecom IFJ (2008) Sol-
nanofiltration membranes based on multilayered poly- vent resistant nanofiltration: separating on a molecular
electrolyte complexes. Chem Mater level. Chem Soc Rev 37:365–405
20(12):3876–3883
H
Heavy Metal Recovery by Chelating
Agents and Membranes
Jose Sabate
Department d’Enginyeria Agroalimentaria i
Biotecnologia, Universitat Politecnica de
Catalunya, Castelldefels, Spain
Heavy metal concentration from wastewaters can
be carried out by several membrane operations.
Electrodialysis (ED), reversed osmosis (RO), and
nanofiltration (NF) membranes retain polyvalent
cations. Alternatively, heavy metals can be con-
centrated by polymer-enhanced ultrafiltration
(PEUF) as well.
Further, membrane separations, combined
with other process, can contribute to heavy
metal recovery from groundwater, contaminated
soils, sediments, sludge, etc (Dermont et al. 2008;
Hashim et al. 2011; Tsang et al. 2012). First of all,
heavy metals must be extracted from the solid
matrix using a washing solution containing a
suitable extractant. The huge amount of metal-
containing solution produced can be concentrated
by membrane technologies with the concomitant
production of a clean permeate solution, which
ideally should be reused.
Metal extraction efficiency depends on several
factors such as extractant/metal affinity,
extractant/metal ratio, leaching method, liquid/
solid ratio, pH, and extraction time. Heavy
metal extraction has mainly been done by
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1362-1
solutions of strong acids, chelating agents,
dendrimers, surfactants, or reducing or oxidizing
agents (Dermont et al. 2008). All of them but acid
extraction takes place under mild conditions
preventing structural changes in the matrix to be
decontaminated.
The most used chelating agents are EDTA
(ethylenediaminetetracetic), NTA
(nitrilotriacetic acid), and DTPA
(diethylenetriaminepentaacetic acid). They form
very stables chelates and they are very efficient in
removing heavy metal ions bound to mineral and
organic fraction of soil (Hashim et al. 2011). One
of their drawbacks is their low selectivity, which
involves high reagent consumption due to the
complexation of Ca and Fe. Further, they show
a low biodegradability, and biodegradable che-
lating agents such as EDDS ([S,S]-
ethylenediaminedisuccinic acid), IDSA
(iminodisuccinic acid), MGDA
(methylglycinediacetic acid), and citric acid
have been receiving increasing attention in recent
years.
Because of their molecular size, chelates can
be concentrated by nanofiltration, but previously,
colloids that can clog the NF membranes have to
be removed by microfiltration or ultrafiltration.
Recycling the chelating agent improves the eco-
nomical competitiveness of the process and
diminishes the environmental impact, especially
for nonbiodegradable chelating agents. That
involves separating metal and ligand in the con-
taminated washing solution. Ion exchange resins
2 Heavy Metal Recovery by Chelating Agents and Membranes
and selective precipitation of metal or chelating
agents by addition of chemical agents have been
proposed. Experiments at laboratory scale have
showed that some NF membranes are able to
reject Cu2+ while citric acid leaks. That can be
achieved in acidic conditions when the chelate is
broken and NF membrane is positively charged,
which favor the rejection of Cu2+ coions and the
leakage of neutral or slightly negatively charged
citric acid.
Some water-soluble polymers contain ligand
groups that can form chelates with heavy metals
as well. They can be retained by ultrafiltration
membranes. At low pH, metal ions are release
from the polymer and a new ultrafiltration oper-
ation allows one to separate them. The polymer
can be regenerated by alkali addition and reused.
This process is named polymer-enhanced ultra-
filtration (PEUF). Recently, dendrimers, highly
branched macromolecular compounds with suit-
able terminal functional groups, have been tested
for heavy metal recovery from contaminated soil.
Cross-References
▶ Heavy Metal Recovery by Membrane
Operations
▶ Heavy Metals Recovery by Polymer Enhanced
Ultrafiltration
▶ Nanofiltration
▶ Reverse Osmosis
▶ Ultrafiltration
References
Dermont G, Bergeron M, Mercier G, Richer-Laflèche
M (2008) Soil washing for metal removal: a review
of physical/chemical technologies and field applica-
tions. J Hazard Mater 152:1–31
Hashim MA, Mukhopadhyay S, Sahu JN, Bhaskar
Sengupta B (2011) Remediation technologies for
heavy metal contaminated groundwater. J Environ
Manage 92:2355–2388
Tsang DCW, Lo IMC, Surampalli RY (eds) (2012) Che-
lating agents for land decontamination technologies.
American Society of Civil Engineers, Reston
N
Nuclear Science and Technology,
Membrane in
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology
(Instytut Chemii i Techniki Ja˛drowej),
Warszawa, Poland
Recent achievements in the area of membrane
processes are being applied for solving the prob-
lems in nuclear science and technology. The most
important application of membrane processes is
the treatment of liquid radioactive waste, often
combined with the recovery of valuable materials
such as water, boric acid, metals, or radioactive
isotope of hydrogen – tritium. Separation of stable
isotopes and enrichment of uranium in the 235U
isotope for production of nuclear fuel, as well as
cleaning the exhaust gas from nuclear power
plants, are possible with membrane processes.
Reverse osmosis may be applied in nuclear desali-
nation; other membrane processes, like membrane
distillation, are also considered as an alternative to
energy-intensive distillation methods.
Separation of Isotopes
The issue of membrane in isotope separation
(▶ membrane for the isotope separation) is
discussed in the scientific literature from the
first application of molecular diffusion for
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1372-3
enrichment of uranium in its less abundant 235U
isotope for military purposes during the Second
World War. The method is still applied in several
installations producing the enriched uranium for
nuclear fuel for power reactors. The studies on
separation of isotopes of other elements like
hydrogen, oxygen, nitrogen, carbon, lithium,
chlorine, and lanthanides, by using different
membrane processes are carried out in many
laboratories.
Radioactive Waste Treatment
The application of membrane processes for radio-
active waste treatment (Membranes in nuclear
waste treatment) is a common industrial practice.
Nuclear waste processing by pressure-driven
membrane processes (nuclear waste processing
by pressure-driven membrane processes) is a
standard method applied in nuclear power plants
and nuclear centers; thermal membrane process
(nuclear waste processing by thermal processes),
namely, membrane distillation, was proposed for
liquid low and intermediate waste concentration.
Advanced researches are carried out to employ
liquid membranes for processing radioactive
waste, especially the waste from the back-end of
nuclear fuel cycle. Membrane contactors pose
new field of applications including such tech-
niques like supported liquid membranes (nuclear
waste processing by supported liquid membranes)
and membrane liquid–liquid extraction.
2 Nuclear Science and Technology, Membrane in
Separation of Tritium
Tritium is emitted by nuclear reactors and fuel
reprocessing plants in gaseous and liquid (HTO)
forms. The studies on application of polymeric
membranes for both gaseous tritium and tritiated
water separations are carried out in many labora-
tories. For separation of HTO, the membranes
from poli[bis(phenoxy) phosphazene] and car-
boxylated derivatives were used (Duncan and
Nelson 1999). Membranes made from
regenerated cellulose, polysulfone, and polytetra-
fluoroethylene were also tested for this purpose.
Separation factors aH2O/HTO in membrane pro-
cess were not higher than 1.04 for cellulose and
1.02 for polysulfone, while for PTFE membranes
were as high as 1.06–1.22 (Zakrzewska-Trznadel
2006).
Recently published papers cover the applica-
tion of polymeric gas separation (GS) membranes
for recovery of tritium compounds (HT, HTO)
(Le Digabel et al. 2003; Iwai et al. 1999; Ishida
et al. 2000). Such membranes like those
manufactured from glassy and amorphous poly-
mers, mainly polyimide and polycarbonate, as
well as polyphenylene oxide, assembled in mod-
ules (e.g., Mc Generon Inc., type B210, Ube
Industries, Ltd. Type NM-B05A, Parker, type
2112-NX-1-300) were considered.
The works performed on hydrogen isotope
separation by permeation methods concern
nuclear reactor safety and thus release of tritium
from nuclear water reactors and fuel reprocessing
plants. On the other hand, a lot of space is devoted
to researches on the security of the fuel cycle for
future fusion reactors (Basile et al. 1995). Vari-
ous systems are proposed: palladium alloy-based
separators, catalytic systems with metallic mem-
branes, integrated systems with ceramic catalytic
reactors, and electrolytic reactors.
Separation of Radioactive Gases
Apart from separation of tritium from radioactive
gaseous waste produced by nuclear reactors, the
other pollutants like noble gases may be sepa-
rated by membrane methods. In recent years,
the works showing the interest in membrane sep-
aration processes of noble gases (Nörenberg
et al. 2001) were published. Membranes used
for this purpose were polyimide hollow fibers
and flat-sheet filters made from polyethylene
terephthalate (PET) or oriented polypropylene.
The methods for selective separation of tritium
from the gases released from nuclear facilities
have been studied primarily in the context of
measuring the emission of this isotope (Sasaki
et al. 2003).
Membrane Methods for Nuclear
Desalination
Because seawater desalination is energy inten-
sive, the use of energy from nuclear reactors for
desalination systems seems to be justified. In
some cases membrane processes can be compet-
itive with thermal methods like multistage flash
evaporation, multiple effect distillation, or vapor
compression. There are several examples of
application of RO in such nuclear reactor-
desalting systems (IAEA Technical Reports
Series 2000; Kim et al. 2002). The employment
of membrane distillation to produce desalted
water with nuclear energy was also considered
(Khayet et al. 2006).
References
Basile A, Violante V, Santella F, Drioli E (1995) Mem-
brane integrated system in the fusion reactor fuel
cycle. Catal Today 25:321–326
Duncan JB, Nelson DA (1999) The separation of tritiated
water using supported polyphosphazene membranes.
J Membr Sci 157:211–217
IAEA Technical Reports Series No. 400 (2000) Introduc-
tion of nuclear desalination. A guidebook. IAEA,
Vienna
Ishida T, Hayashi T, Yamada M, Suzuki T, Okuno
K (2000) Design of a membrane atmosphere
detritiation system using super high permeation mod-
ule. Fusion Eng Des 49–50:839–846
Iwai Y, Yamanishi T, Nishi M (1999) A steady-state
simulation model of gas separation system by hollow
fiber type membrane module. J Nucl Sci Technol
36:95–104
Nuclear Science and Technology, Membrane in
Khayet M, Mengual JI, Zakrzewska-Trznadel G (2006)
Direct contact membrane distillation for nuclear desa-
lination, part II- experiments with radioactive solu-
tions. J Nucl Desalin 2:56–73
Kim SH, Kim GT, Yim SK, Choi KH, Yoon CH, Choo
KH, Choi SJ (2002) Application of energy efficient
reverse osmosis system for seawater desalination.
Desalination 144:361–365
Le Digabel M, Truan PA, Duret D, Laquerbe C, Perriat P,
Niepce JC, Pelletier T (2003) Application of gas sep-
aration membranes to detritiation systems. Desalina-
tion 148:297–302
3
Nörenberg H, Burlakov VM, Kosmella HJ, Smith GDW,
Briggs GAD, Miyamoto T, Tsukahara Y (2001)
Pressure-dependent permeation of noble gases (He,
Ne, Ar, Kr, Xe) through thin membranes of oriented
polypropylene (OPP) studied by mass spectrometry.
Polymer 42:10021–10026
Sasaki S, Tega E, Shimada A, Akahori S, Suzuki T,
Okuno K, Kondo K (2003) Basic characteristics of
hollow-filament polyimide membrane in gas separa-
tion and application to tritium monitors. J Radioanal
Nucl Chem 255:91–95
Zakrzewska-Trznadel G (2006) Tritium removal from
water solutions. Desalination 1–3:737–738
I
Isotope Separation, Membrane for
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology
(Instytut Chemii i Techniki Ja˛drowej),
Warszawa, Poland
The use of membranes for the separation of iso-
topes is one of the first practical applications for
membrane processes. The first application was
based on the effects that were described in 1846
by Thomas Graham, as a phenomenon of molec-
ular effusion, i.e., differentiated flow rate of gases
through small holes. When a mixture of two gases
in a closed vessel is allowed to permeate through
the porous barrier, assuming an equal concentra-
tion of the two gases, the molecules of the lighter
component strike the barrier more frequently than
the molecules of the heavier gas. If the holes of
the barrier are sufficiently small to avoid convec-
tion flow (flow by volume) of gas and large
enough to allow passage of the individual mole-
cules, then the lighter molecules escape more
readily through the pores and the permeate is
enriched in the light component. The efficiency
of partitioning is described by separation factor a
expressed as the ratio of mole fractions of sepa-
rated components after and before passing
through the porous barrier or as the square root
of the inverse ratio of the corresponding molecu-
lar weights:
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1373-3
rffiffiffiffiffiffiffi
yð1  xÞ M2
a¼ ¼
xð1  y Þ M1
where x and y are mole fractions of two separated
isotopes and M1 and M2 are molecular weights of
these components of the isotopic mixture.
In 1895 Rayleigh and Ramsey have separated
argon and nitrogen using this method, and in
1920 Aston employed molecular effusion for
enrichment of neon-22 isotope. Large improve-
ment of the technology was achieved by Gustav
Ludwig Hertz who developed the separating cas-
cade, which was composed of several diffusion
stages. They also used of the 24-stage cascade in
1932, which almost completely separated iso-
topes of neon, and by applying of the 48-stage
cascade, they have separated isotopes of hydro-
gen. In 1936 Wooldridge, Jenkins, and Smythe
have enriched isotopes of neon, hydrogen, and
carbon in methane with 34-stage cascade. The
most spectacular application of molecular effu-
sion was enrichment of uranium-235 in natural
uranium for military purposes within the frames
of Manhattan Project during the Second World
War. The all of the mentioned processes of sep-
aration of isotopes were carried out in the gas
phase. In case of uranium isotope separation, the
gas applied in the process was uranium
hexafluoride, UF6. The membrane material had
to be chemically resistant in this case, since the
uranium hexafluoride used to produce enriched
uranium-235 is highly corrosive (easily
converted into hydrofluoric acid and harmful
2 Isotope Separation, Membrane for
oxyfluorides as UO2F2). The important parame-
ters of the molecular effusion barrier are the pore
diameter and the permeation rate since according
to the theory of molecular effusion, the diffusion
transport through the membrane is selective when
the pore size is commensurate with the mean free
path of the molecules under the given conditions.
Also the large plants employing the molecular
effusion (which is also called molecular diffusion
or gaseous diffusion) were built in the United
States with the most famous K-25 plant in Oak
Ridge, Tennessee. The other systems were
constructed in 1950s at Oak Ridge, Paducah,
Kentucky, and Portsmouth, Ohio, in the United
States, Capenhurst in England, and at Pierrelatte
and Tricastin in France. There are also some
reports on gaseous diffusion plants in the former
USSR, Great Britain, Argentina, and in the Peo-
ple’s Republic of China (Kirk-Othmer 1997).
Today, the gaseous diffusion is an important
method for uranium-235 enrichment, despite the
competitiveness of the centrifugal methods. This
is used in the United States and France, including
Eurodif, led by France, Italy, Spain, and Belgium,
which holds the plants in Tricastin and Pierrelatte
(France).
For preparation of membranes, different
methods are applied: etching with strong acids
(alloys of gold and silver), sintering and extrusion
of fine metal powders and oxides of metals
(nickel, aluminum oxides), and the anodic oxida-
tion (aluminum oxides). Typical gas diffusion
membrane has a pore size of 0.006–0.04 mm
and operates at temperature of 60–200  C and at
pressure of 0.4–3.3 bar. Support layer of the
membrane is a porous material with a pore size
of 2–10 mm. Ceramic and metallic microporous
membranes were applied for separation of iso-
topes, including other than uranium, such as iso-
topes of argon, neon, and hydrogen. Although
information about the materials used for
manufacturing gaseous diffusion membranes are
very scarce, it is known that French technology
used sintered anode and aluminum, alloys of gold
and silver, nickel, Teflon, porcelain (Burggraaf
and Cot 1996), and zirconium (Hsieh 1996).
Attempts of using the polymeric membranes
for the separation of isotopes of hydrogen with
membranes made of polymers, such as polyeth-
ylene terephthalate (PET), polyethylene (PE),
polytetrafluoroethylene (PTFE), cellulose acetate
(CA), and plasticized polyvinyl chloride (PVC),
were taken by Marcea (1983). Although the
selectivity of polymers is lower than metallic
membranes, it is worthy to point out, since the
numerous benefits of their use, such as the
low-cost of membranes, the possibility of forma-
tion of capillaries resulting in large areas for
permeation, and no need of high pressures and
temperatures.
The studies on separation of hydrogen and
oxygen in the liquid phase (water) were carried
out in Pacific Northwest Laboratory, USA
(Nelson et al. 1996). Polymeric membranes
were used in Institute of Nuclear Chemistry and
Technology, (Poland). They were made of
regenerated cellulose, cellulose acetate
(Chmielewski et al. 1991), and polytetrafluor-
oethylene (Zakrzewska-Trznadel et al. 1996).
The economic assessment showed that mem-
brane permeation is competitive with other
methods of hydrogen and oxygen isotopes sepa-
ration. The demand for heavy oxygen water, due
to the development of PET diagnostic method,
has intensified the interest in new processes of
separating isotopes of oxygen, among
others – membrane method (Kim et al. 2004).
The following isotopes of chlorine (Campbell
1985), carbon (Fritz et al. 1987), lithium
(Whitworth et al. 1994) in aqueous solutions,
and uranium (Okamoto et al. 1980) in ammonia
were separated by means of various membrane
techniques and by using of different membranes.
Gadolinium and neodymium isotopes were sepa-
rated by means of a hybrid complexation/
nanofiltration (Chitry et al. 2001) processes. The
new complexing agents and ligands, which were
used in the hybrid process, were developed based
on DTPA (see also Chitry et al. 2001).
References
Burggraaf AJ, Cot L (1996) Membrane science and tech-
nology series, vol 4, Fundamentals of inorganic
Isotope Separation, Membrane for
membrane science and technology. Elsevier, Amster-
dam/Lausanne/New York/Oxford/Shannon/Tokyo
Campbell DJ (1985) Fractionation of stable chlorine iso-
topes during transport through semi-permeable mem-
branes. M.Sc. thesis, University of Arizona
Chitry F, Pellet-Rostaing S, Vigneau O, Lemaire M (2001)
Nanofiltration-complexation: a new method for isoto-
pic separation of heavy metals. Chem Lett
30(8):770–771
Chmielewski AG, Zakrzewska-Trznadel G, Miljević N,
Van Hook WA (1991) 16O/18O and H/D separation
factors for liquid/vapour permeation of water through
an hydrophobic membrane. J Membr Sci 60:319–329
Fritz SJ, Hinz DL, Grossman EL (1987) Hyperfiltration-
induced fractionation of carbon isotopes. Geochim
Cosmochim Acta 51:1121–1134
Hsieh HP (1996) Membrane science and technology
series, vol 3, Inorganic membranes for separation and
reaction. Elsevier, Amsterdam/Lausanne/New York/
Oxford/Shannon/Tokyo
Kim J, Park SE, Kim TS, Jeong DY, Ko KH (2004) Isoto-
pic water separation using AGMD and VEMD.
Nuklonika 49(4):137–142
3
Kirk-Othmer A (1997) Diffusion separation methods. In:
Ruthven DM (ed) Encyclopedia of separation technol-
ogy, vol 1. Wiley, New York/Chichester/Weinheim/
Brisbane/Singapore/Toronto
Marcea P (1983) Permeation of H2 and D2 through poly-
mers. Isotopenpraxis 19(5):153–156
Nelson DA, Duncan JB, Jensen GA, Burton SD
(1996) Isotopomeric water separations with supported
polyphosphazene membranes. J Membr Sci
112:105–113
Okamoto M, Oi T, Fujii Y, Kakihana H (1980) Dependen-
cies of pH and current density on the isotope effect
occured by the electromigration of uranyl ions in a
cation exchange membrane. Isotopenpraxis
16(2):58–61
Whitworth TM, Mariñas BJ, Fritz SJ (1994) Isotopic frac-
tionation and overall permeation of lithium by a thin-
film composite polyamide reverse osmosis membrane.
J Membr Sci 88:231–241
Zakrzewska-Trznadel G, Chmielewski AG, Miljević N
(1996) Separation of protium/deuterium and oxygen-
16/oxygen-18 by membrane distillation process.
J Membr Sci 113:337–342
M

Vo
Membranes in Nuclear Waste VRC ¼
Treatment VR

where Ao is the concentration of radioactivity in

Grażyna Zakrzewska-Kołtuniewicz
the waste before treatment; Ap, concentration of
Institute of Nuclear Chemistry and Technology
radioactivity in the waste after treatment; Vo,
(Instytut Chemii i Techniki Ja˛drowej),
initial volume of the waste; and VR, final volume
Warszawa, Poland
of the waste.
Pressure-driven membrane processes
(▶ Nuclear waste processing by pressure driven
Nuclear fuel cycle and application of radioiso-
membrane processes) are the most often used for
topes in research, medicine, and industry gener-
radioactive waste treatment. Such processes like
ate various types of liquid waste that needs
reverse osmosis, nanofiltration, ultrafiltration,
treatment before discharge to the environment.
and microfiltration have found application in
The choice of appropriate technology of
nuclear power plants for the treatment of liquid
processing depends on capital and operational
low and intermediate radioactive wastes, as well
costs; waste amount and their characteristics;
as for processing of institutional wastes. The
appointed targets of the process, e.g., the values
thermal process (nuclear waste processing by
of decontamination factors; and volume reduc-
thermal processes), namely, membrane distilla-
tion coefficients. Membrane processes can suc-
tion, was tested for concentration of low and
cessfully supersede many noneffective
intermediate radioactive wastes from applica-
conventional methods applied in nuclear indus-
tions of radioisotopes.
try. But in some instances, they can also comple-
The application of liquid membranes (LM) for
ment these methods while improving the
selective recovery of some specific radionuclides
parameters of effluents and purification economy.
from waste and process streams was studied
Efficiency of waste processing can be assessed
including different types of arrangements: bulk,
on the basis of the decontamination factor
emulsion, and supported liquid membranes
(DF) and volume reduction coefficient (VRC):
(nuclear waste processing by supported liquid
membranes). The latter uses membrane
Ao
DF ¼ contactors to immobilize liquid membrane inside
Ap
the pores; the other process, which applies the
membranes for contacting two phases, is mem-
brane liquid-liquid extraction (solvent

# Springer-Verlag Berlin Heidelberg 2015

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1374-3
2 Membranes in Nuclear Waste Treatment
extraction). Such a process is advantageous in
comparison with conventional extraction carried
out in the mixer-settler apparatus, since it uses
small volume of extracting agent and avoids
phase mixing and formation of emulsion. It was
tested for separation of actinides in the back end
of the fuel cycle (Pabby et al. 2009).
Electrical potential-driven membrane pro-
cesses using ion exchange membranes were also
found as an application for radioactive waste
treatment. They comprise such methods like elec-
troosmosis, electrodialysis, and membrane elec-
trolysis. Electroosmosis was used for dewatering
a radioactive sludge after filtration or gravita-
tional sedimentation (International Atomic
Energy Agency 1994). With this method, high
retention factors with minimal membrane fouling
were achieved.
Electrodialysis was studied for removal of
radioactive ions from low- and intermediate-
level radioactive wastes. Inactive compounds
like NaCl, Na2SO4, and Ca(NO3)2 prevalent in
the solution, were used as carriers of radioactive
ions, such as 24Na, 42K, 137Cs, and 90Y, present in
the waste in small quantities. The decontamina-
tion factors for radioactive ions as high as
105 were achieved in this process. Both poly-
meric and inorganic ion exchange membranes
with a good resistance to radiation were
employed. Electrodialysis was considered for
separation of molybdenum ions and CO32-and
HCO3 from liquid waste containing uranium in
hydrometallurgical uranium ore processing
(Lounis and Gavach 1997). It was used in com-
bination with diffusion dialysis for separation of
137
Cs and 90Sr from 3 M nitric acid solutions
(Mathur et al. 1998). Another application of elec-
trodialysis in nuclear technologies is salt splitting
(e.g., Na2SO4 decomposition) in the high saline
waste with recovery of acid and base
(International Atomic Energy Agency 1994).
The process gave 12–25 % solution of sodium
sulfate, 20 % NaOH, and 20 % H2SO4.
Sodium super ion-conducting ceramic
membranes – NaSICON – were applied for
separation of sodium from radioactive wastes
(Fountain et al. 2008) and Nafion membranes
for concentration of 137Cs. AFN ion exchange
membranes were used for the recovery of boric
acid from wastewater (Park and Lee 1995). Ion
exchange membranes obtained by radiation
grafting of polyacrylic acid on a matrix of poly-
ethylene and Teflon were tested for removal of
zirconium from solutions containing uranium
(El-Sayed et al. 1999). Novel anion exchange
membrane was applied to separate 125I and 36Cl
ions by electrodialysis (Inoue et al. 2004).
References
El-Sayed AH, Abd El-Rehim HA, Ali AMI, Nowier HG,
Aly HF (1999) Characterization and application of
radiation grafted membranes in treatment of interme-
diate active waste. Nucl Inst Methods Phys Res
B 151:393–398
Fountain MS, Kurath DE, Sevigny GJ (2008) Caustic
recycle from Hanford tank waste using NaSICON
ceramic membranes. Sep Sci Technol 43:2321–2342
Inoue H, Kagoshima M, Yamasaki M, Honda Y (2004)
Radioactive iodine waste treatment using electrodial-
ysis with an anion exchange paper membrane. Appl
Radiat Isot 61:1189–1193
International Atomic Energy Agency (1994) Advances in
technologies for treatment of low and intermediate
level radioactive liquid wastes. Technical report series
no. 370. IAEA, Vienna
Lounis A, Gavach C (1997) Treatment of uranium leach
solutions by electrodialysis for anion impurities
removal. Hydrometallurgy 44:83–96
Mathur JN, Murali MS, Balarama Krishna MV,
Ramahandhran V, Hanra MS, Misra BM (1998) Diffu-
sion dialysis aided electrodialysis process for concen-
tration of radionuclides in acid medium. J Radioanal
Nucl Chem 232:237–240
Pabby AK, Gupta SK, Sawanr SR, Rathore NS,
Janardan P, Changrani RD, Dey PK (2009) Evaluation
of membrane-based processing of radioactive nuclear
plant waste: case studies. In: Pabby AK, Rizvi SSH,
Sastre AM (eds) Handbook of membrane separations:
chemical, pharmaceutical, and biotechnological appli-
cations. CRC Press/Taylor %26 Francis Group, Boca
Raton, pp 933–943
Park JK, Lee KJ (1995) Separation of boric acid in liquid
waste with anion exchange membrane contactor.
Waste Manag 15:283–291
N
Nuclear Waste Processing:
Supported Liquid Membranes
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology
Instytut Chemii i Techniki Ja̧drowej, Warszawa,
Poland
Supported liquid membranes (SLM), also called
immobilized liquid membranes, have found a
number of applications in nuclear
industry – from uranium mining to reprocessing
of spent nuclear fuel. In supported liquid mem-
brane, two phases, feed and receiving solutions,
are separated by porous barrier with organic phase
inside the pores. In order to increase the mass
transport rate between the phases, the carrier,
which forms complex with one of the separated
species, is introduced to the organic phase. Such a
facilitated transport causes not only fast transport
rates but also results in higher selectivity of the
process.
SLM were studied for radioactive waste treat-
ment and for removal of actinides and fission
products from the waste after reprocessing of
nuclear fuel. Radionuclides, such as cesium,
strontium, cerium, and europium, were separated
from radioactive solutions to reduce the
radiotoxicity of the waste. Uranium plutonium
and americium removal from the wastes produced
in the back-end of fuel cycle, as well as the effec-
tive methods for actinides partitioning, were
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1375-2
broadly described in the literature. Example appli-
cations are collected in the Table 1.
The main drawback of immobilized liquid
membranes is their low stability associated with
loss of extractant via volatilization or dissolution
into contacting phase (Koltuniewicz and Drioli
2008). The advantages are high selectivity of the
method allowing a wide range of applications and
easy optimization of the membrane-extractant
system. Although the industrial application of
this process is far from implementation, ongoing
research on new extracting agents for actinides
takes place in many laboratories around the
world. A solution to the problem of loss of
extracting agent may be development of inclusion
membranes. Polymer inclusion membranes (PIM)
in some cases incorporate base polymer and a
suitable extractant, while in other cases a plasti-
cizer may be needed to be added (Bayou
et al. 2010). PIM have been successfully devel-
oped for extraction of radionuclides from radio-
active waste using various extracting agents like
TOPO, Cyanex 272, Cyanex 301, Cyanex
302, CMPO, TODGA, D2EHPA, and crown
ethers (Kusumocahyo et al. 2004; Kozlowski
et al. 2006; Bhattacharyya et al. 2011). Another
approach for the extraction of radionuclides with
selective organic reagents is application of mem-
brane solvent extraction carried out in membrane
contactors (Drioli et al. 2005).
2 Nuclear Waste Processing: Supported Liquid Membranes

Nuclear Waste Processing: Supported Liquid Membranes, Table 1 Supported liquid membranes for treatment of
radioactive waste
Separated Stripping
radionuclides Application Extracting agent (LM) solution Support Reference
Pu(IV) Separation of Tri-n-butyl phosphate 0.1 M Hollow fiber Rathore
plutonium from (TBP) NH2OH
HCl polypropylene et al. 2001
radioactive in 3 M HNO3 (Enka) membrane
waste
Pu(IV) Separation of 2-ethylhexyl 2- 0.05 M Polypropylene Kedari
plutonium from ethylhexyl phosphonic HNO3 and Enka 2E HF-PP et al. 1999
radioactive acid in n-dodecane 0.3 oxalic membrane
waste acid solution
U(VI) Recovery of Alamine 336 in toluene Distilled PTFE flat sheet Lakshmi
233
U, uranium from water membrane et al. 2004
6 M HCl at the
back-end of fuel
cycle
232
Th U/Th separation N,N-di(2-ethylhexyl) 0.01 M PTFE flat sheet Shailesh
in 4 M HNO3 in isobutyramide HNO3 membranes, et al. 2006
the presence (D2EHIBA) in 0.45 mm, 72 %
of137 Cs,85,89 Sr, n-dodecane porosity
and59 Fe (Sartorius)
U(VI) Actinides N,N,N0 ,N0 -tetra-2- 0.01 M PTFE flat sheet Panja
partitioning ethylhexyl-3-pentane- HNO3 membranes, et al. 2011
diamide (T2EHDGA) in 0.45 mm, 64 %
n-dodecane, 30 % porosity
iso-decanol as the
modifier
U(VI) Recovery of Tetraoctyldiglycolamide 0.1 M HNO3 PTFE flat sheet Panja
actinides at the (TODGA) in n-dodecane membranes et al. 2009
back-end of fuel
cycle from acidic
feeds
U(VI) Recovery of N,N,N0 ,N0 -tetra-2- 0.01 M PTFE flat sheet Panja
actinides at the ethylhexyl-3-pentane- HNO3 membranes et al. 2012
back-end of fuel diamide (T2EHDGA) in
cycle from acidic n-dodecane, 30 %
feeds iso-decanol as the
modifier
U(VI) Extracting of Aliquat 336 (N-methyl- Distilled PTFE flat sheet Mohapatra
uranyl ions from N,N-dioctyloctan-1- water membranes et al. 2006
6 M HCl ammonium chloride) (Sartorius)
environment
U(VI) Recovery of TBP in kerosene NaOH Hollow fiber Ramkul
uranium from membrane et al. 2007
nitrate media contactor
U(VI) Separation of Tri-n-octylphosphine Ammonium PTFE flat sheet Singh
uranium from oxide (TOPO) in carbonate membranes, et al. 2007
phosphoric acid n-dodecane 0.45 mm, 84 %
porosity
Am(III) Extraction Am TEHDGA in dodecane 0.1 M HNO3 PTFE flat sheet Panja
(III) from 1–6 M membranes et al. 2008
HNO3 (Sartorius)
0.20–5 mm
(continued)
Nuclear Waste Processing: Supported Liquid Membranes 3

Nuclear Waste Processing: Supported Liquid Membranes, Table 1 (continued)

Separated Stripping
radionuclides Application Extracting agent (LM) solution Support Reference
Am(III)/Nd Separation of N,N,N0 ,N0 -tetraoctyl Distilled Polypropylene Ansari
(III) Am3+ from 3 M diglycolamide water membrane 2.5  et al. 2008
HNO3 and from (TODGA) and N,N-di- 8 Liqui-Cel ®
simulated high- n-hexyl octanamide Extra-Flow
level waste (DHOA) as a modifier in hollow fiber
(SHLW) normal paraffin module (Celgard)
solution hydrocarbon (NPH) as
the carrier solvent
Am/Eu Separation of Bis(2,4,4- 0.1 M H2SO4 PTFE membrane Hoshi
actinides and trimethylpentyl) (Fluoropore, FP et al. 2000
lanthanides dithiophosphinic acid 045 Sumitomo
(Cyanex 301) Electric Ind.),
0.45 mm, 74 %
porosity
La, Ce Selective Tri-n-octylamine (TOA) 0.25 M Hollow fiber Ura
separation of La in kerosene Na2CO3 (Hoechst et al. 2005
(III) from Ce(IV) Celanese
Charlotte, NC
Liqui-Cel ® Extra-
Flow module,
Celgard with
PTFE membranes)
Ce(III) Separation of Ce Tri-n-butylphosphate 1 M HNO3 Cellulose nitrate El-Said
(III) from fission (TBP) in kerosene flat sheet et al. 2002
products during membrane
PUREX process (Sartorius),
(9 M HNO3, 2 M 0.2 mm, porosity
NaBrO3) 70 %
Ce(III) Separation of CMPO; TBP as a Aq. solutions Plate-and-frame Teramoto
cerium from modifier, in dodecane of trisodium module et al. 2000
low-level citrate and
radioactive disodium
waste citrate
Sc, Zr, Nb, Permeation of Bis(2-ethylhexyl) 0.75, 1.0, 2.3 PTFE flat sheet Ambe
Hf, Ce, Pm, rare earth hydrogen phosphate in and 4.0 M et al. 1998
Gd, Yb, Lu elements in SLM decalin HCl
Cs Separation of Di-t-butyl benzo Distilled Polypropylene Mohapatra
cesium from 18 crown 6 carrier water membrane et al. 2004
fission products
of irradiated
uranium
Cs Selective 1,3-Dipropyloxycalix[4] Deionized Polypropylene, Kim
extraction of arene crown ether water Celgard 2400 et al. 2001
cesium ion from (CCE1) and (Hoechst
aqueous 1,3-dipropyloxycalix[4] Celanese Co.),
solutions arene dibenzo crown pore size: 0.04 mm
ether (CCE2) in  0.12 mm,41 %
chloroform porosity
Cs Separation of Calix-[4]-bis Distilled Hollow fiber Kandwal
cesium in 3 M (2,3-naptho)-crown-6 as water module et al. 2011a
HNO3 carrier in
(2-nitrophenyloctyl)
ether and n-dodecane
(continued)
4 Nuclear Waste Processing: Supported Liquid Membranes

Nuclear Waste Processing: Supported Liquid Membranes, Table 1 (continued)

Separated Stripping
radionuclides Application Extracting agent (LM) solution Support Reference
Cs Separation of Chlorinated cobalt 8 M HNO3 Impregnated Mohapatra
cesium from dicarbollide (CCD) in PTFE flat sheet et al. 2010
other phenyl trifluoromethyl membranes,
radionuclides in sulfone (PTMS) 0.45 mm, 72 %
multicomponent porosity
nitric acid (Sartorius)
solution
Cs Recovery of Calix[4]arene- Distilled Polypropylene Kandwal
cesium from bis(2,3-naphtho)crown-6 water, NaOH hollow fiber et al. 2011b
pressurized neutralization
heavy water
reactor (PHWR)
simulated high-
level waste
(SHLW)
Sr Selective 4,40 (50 )di-tert-butyl- Distilled PTFE flat sheets, Rawet
removal of Sr2+ dicyclohexano-18- water pore size: 0.45 mm et al. 2006
from aqueous crown-6 (DtBuCH18C6)
nitrate medium in 1-octanol
Sr Selective Sr Di-tert-butyl- Distilled PTFE membrane Raut
separation from dicyclohexano-18- water et al. 2012
pressurized crown-6 (DTBCH18C6)
heavy water dissolved in a mixture of
reactor simulated 80 % 2-nitrophenyl ether
high-level waste and 20 % n-dodecane
(SHLW)
Sr Separation of 4,4_(5_)di-tert- butyl- Distilled Hollow fiber Kandwal
strontium from dicyclohexano-18- water, NaOH membranes et al. 2012
3 M HNO3 crown-6 (DTBCH18C6) neutralization
90
Sr/Y Y separation Bis-(2-ethylhexy) 3 M HNO3 Nuclear track Happel
from its parent phosphate (HDEHP), microfilters et al. 2003
90
Sr in 0.1 tributylphosphate (TBP)
MHNO3 for
generator
production
90
Y Yttrium 2-ethylhexyl-2- 0.5 M HNO3 PTFE membranes Ramanujam
separation from ethylhexyl phosphonic or 0.5 M HCl et al. 2001
high-level waste acid (KSM017
for application equivalent to PC 88A)
for nuclear
medicine
Tc Removal of Tc 2-nitrophenyl octyl ether 1.5 M HNO3 Flat sheet Chen
(VII) from water (NPOE) polymeric et al. 2001
and concentrated membranes
alkaline
solutions
Tc Separation of Tri-octyl phosphine 0.9 % NaCl Celgard-2400 Yassine
99m
Tc from 99Mo oxide (TOPO) in polypropylene 2000
kerosene film, 0.02 mm,
38 % porosity
Co Separation of 2-ethylhexyl hydrogen H2SO4 PTFE filters Youn
cobalt ions from 2-ethylhexyl (Millipore Co., et al. 1995
water solutions phosphonate HEH(EHP) 0.50 mm, 85 %
in kerosene porosity)
Nuclear Waste Processing: Supported Liquid Membranes
References
Ambe S, Yashiki K, Maeda H, Enomoto S, Ozaki T, Ambe
F (1998) Multitracer study on permeation of rare ele-
ments through a supported liquid membrane.
J Radioanal Nucl Chem 236:181–185
Ansari SA, Mohapatra PK, Raut DR, Adya VC, Thulasidas
SK, Manchanda VK (2008) Separation of Am(III) and
trivalent lanthanides from simulated high-level waste
using hollow fiber-supported liquid membrane. Sep
Purif Technol 63:239–242
Bayou N, Arous O, Amara M, Kerdjoudj H (2010) Elabo-
ration and characterization of a plasticized cellulose
triacetate membrane containing trioctylphosphine
oxide (TOPO): application to the transport of uranium
and molybdenum ions. C R Chim 13:1370–1376
Bhattacharyya A, Mohapatra PK, Hassan PA, Manchanda
VK (2011) Studies on the selective Am3+ transport,
irradiation stability and surface morphology of polymer
inclusion membranes containing Cyanex-301 as carrier
extractant. J Hazard Mater 192:116–123
Chen J, Boerrigter H, Veltkamp AC (2001) Technetium
(VII) transport across supported liquid membranes
(SLMs) containing 2-nitrophenyl octyl ether (NPOE).
Radiochim Acta 89:523–528
Drioli E, Criscuoli A, Curcio E (2005) Membrane
contactors: fundamentals, applications and potentiali-
ties. Elsevier, Amsterdam
El-Said N, Rahman NA, Borai EH (2002) Modification in
Purex process using supported liquid membrane sepa-
ration of cerium(III) via oxidation to cerium(IV) from
fission products from nitrate medium by SLM. J
Membr Sci 198:23–31
Happel S, Streng R, Vater P, Ensinger W (2003) Sr/Y
separation by supported liquid membranes based on
nuclear track micro filters. Radiat Meas 36:761–766
Hoshi H, Tsuyoshi A, Akiba K (2000) Separation of amer-
icium from europium using liquid membrane impreg-
nated with organodithiophosphinic acid. J Radioanal
Nucl Chem 243:621–624
Kandwal P, Dixit S, Mukhopadhyay S, Mohapatra PK
(2011a) Mass transport modeling of Cs(I) through hol-
low fiber supported liquid membrane containing calix-
[4]-bis(2,3-naptho)-crown-6 as mobile carrier. Chem
Eng J 174:110–116
Kandwal P, Ansari SA, Mohapatra PK (2011b) Transport
of cesium using hollow fiber supported liquid mem-
brane containing calix[4]arene-bis(2,3-naphtho)crown-
6 as the carrier extractant: part II. Recovery from sim-
ulated high level waste and mass transfer modeling.
J Membr Sci 384:37–43
Kandwal P, Ansari SA, Mohapatra PK (2012) A highly
efficient supported liquid membrane system for near
quantitative recovery of radio-strontium from acidic
feeds. Part II: scale up and mass transfer modeling in
hollow fiber configuration. J Membr Sci
405–406:85–91
Kedari CS, Pandit SS, Ramanujam A (1999) Selective
permeation of plutonium(VI) through supported liquid
5
membrane containing 2-ethyljexyl 2-ethylhexyl
phosphonic acid as ion carrier. J Membr Sci
156:187–196
Kim JK, Kim JS, Shul YG, Lee KW, Oh WZ (2001) Selec-
tive extraction of cesium ion with calix[4]arene crown
ether through thin sheet supported liquid membrane.
J Membr Sci 187:3–11
Koltuniewicz AB, Drioli E (2008) Membranes in clean
technologies. Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim
Kozlowski CA, Kozlowska J, Pellowski W, Walkowiak
W (2006) Separation of cobalt-60, strontium-90 and
cesium-137 radioisotopes by competitive transport
across polymer inclusion membranes with organophos-
phorous acids. Desalination 198:149–156
Kusumocahyo SP, Kanamori T, Sumaru K, Aomatsu S,
Matsuyama H, Teramoto M, Shinbo T (2004) Devel-
opment of polymer inclusion membrane based on cel-
lulose triacetate: carrier-mediated transport of cerium
(III). J Membr Sci 244:251–257
Lakshmi DS, Mohapatra PK, Mohan D, Manchanda VK
(2004) Uranium transport using a PTFE flat-sheet
membrane containing alamine 336 in toluene as the
carrier. Desalination 163:13–18
Mohapatra PK, Lakshmi DS, Mohan D, Manchanda VK
(2004) Selective transport of cesium using a supported
liquid membrane containing di-t-butyl benzo 18 crown
6 as the carrier. J Membr Sci 232:133–139
Mohapatra PK, Lakshmi DS, Mohan D, Manchanda VK
(2006) Uranium pertraction across a PTFE flatsheet
membrane containing Aliquat 336 as the carrier. Sep
Purif Technol 51:24–30
Mohapatra PK, Bhattacharyya A, Manchanda VK
(2010) Selective separation of radio-cesium from acidic
solutions using supported liquid membrane containing
chlorinated cobalt dicarbollide (CDD) in phenyltri-
fluoromethyl sulphone (PTMS). J Hazard Mater
181:679–685
Panja S, Ruhela R, Misra SK, Sharma JN, Tripathi SC,
Dakshinamoorthy A (2008) Facilitated transport of Am
(III) through a flat-sheet supported liquid membrane
(FSSLM) containing tetra(2-ethyl hexyl)diglycolamide
(TEHDGA) as carrier. J Membr Sci 325:158–165
Panja S, Mohapatra PK, Tripathi SC, Manchanda VK
(2009) Studies on uranium(VI) pertraction across a N,
N, N’, N’-tetraoctyldiglycolamide (TODGA)
supported membrane. J Membr Sci 337:274–281
Panja S, Mohapatra PK, Tripathi SC, Manchanda VK
(2011) Facilitated transport of uranium(VI) across
supported liquid membranes containing T2EHDGA
as the carrier extractant. J Hazard Mater 188:281–287
Panja S, Mohapatra PK, Kandwal P, Tripathi SC
(2012) Uranium(VI) pertraction across a supported liq-
uid membrane contacting a branched diglycolamide
carrier extractant: part III mass transfer modelling.
Desalination 285:213–218
Ramkul P, Prapasawad T, Pancharoen U, Pattaveekongk
W (2007) Separation of radioactive metal ions by
6 Nuclear Waste Processing: Supported Liquid Membranes
hollow fiber-supported liquid membrane and perme-
ability analysis. J Chin Inst Chem Eng 38:489–494
Ramanujam A, Achuthan PV, Dhami PS, Kannan R,
Gopalakrishnan V, Kansra VP, Iyer RH, Balu
K (2001) Separation of carrier-free 90Y from high
level waste by supported liquid membrane using
KSM-17. J Radioanal Nucl Chem 247:185–191
Rathore NS, Sonawane JV, Kumar A, Venugopalan AK,
Singh RK, Bajpai DD, Shukla JP (2001) Hollow fiber
supported liquid membrane: a novel technique for sep-
aration and recovery of plutonium from aqueous acidic
wastes. J Membr Sci 189:119–128
Raut DR, Mohapatra PK, Manchanda VK (2012) A highly
efficient supported liquid membrane system for selec-
tive strontium separation leading to radioactive waste
remediation. J Membr Sci 390–391:76–83
Rawat N, Mohapatra PK, Lakshmi DS, Bhattacharyya A,
Manchanda VK (2006) Evaluation of supported liquid
membrane containing a macrocyclic ionophore for
selective removal of strontium from nuclear waste solu-
tion. J Membr Sci 275:82–88
Shailesh S, Pathak PN, Mohapatra PK, Manchanda VK
(2006) Transport studies of uranium across a supported
liquid membrane containing N, N-di(2-ethylhexyl)
isobutyramide (D2EHIBA) as the carrier. J Membr
Sci 272:143–151
Singh SK, Misra SK, Sudersanan M, Dakshinamoorthy A,
Munshi SK, Dey PK (2007) Carrier-mediated transport
of uranium from phosphoric acid medium across
TOPO/n-dodecane-supported liquid membrane.
Hydrometallurgy 87:190–196
Teramoto M, Sheng Fu S, Takatani K, Ohnishi N, Fukui T,
Arai K (2000) Treatment of simulated lo level radioac-
tive wastewater by supported liquid membranes: uphill
transport of Ce(III)using CMPO carrier. Sep Purif
Technol 18:57–69
Ura P, Prakom R, Weerawat P, Milan HJ (2005) Purely
extraction and separation of mixture of cerium(IV) and
lanthanum(III) via hollow fiber supported liquid mem-
brane. J Ind Eng Chem 11:926–931
Yassine T (2000) Separation of 99mTc from 99Mo by using
TOPO – kerosene supported liquid membrane.
J Radoanal Nucl Chem 246:665–669
Youn IJ, Lee Y, Lee WH (1995) Analysis of permeation
rate of cobalt ions across a supported liquid membrane
containing HEH(EHP). J Membr Sci 100:69–75
N
Nuclear Waste Processing: Pressure-
Driven Membrane Processes
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology
(Instytut Chemii i Techniki Ja˛drowej),
Warszawa, Poland
The pressure-driven membrane processes such as
reverse osmosis (RO), nanofiltration (NF), ultra-
filtration (UF), and microfiltration (MF) are the
most commonly used membrane methods of
radioactive waste processing. The reasons for a
wide use of membrane methods are numerous:
they are mature technologies with long design
and operation experience, well proven in nuclear
industry, with broad spectrum of membranes and
membrane modules developed. The variety of
pressure-driven membrane processes covers
wide spectrum of media: from ionic species to
large particles (Fig. 1). Therefore, they are suit-
able for large number of applications, being flex-
ible in process configurations and system
optimization. They can be easily integrated with
other conventional methods to form efficient
treatment systems. Pressure-driven membrane
processes are especially convenient for the con-
centration of large volumes of low and interme-
diate level radioactive waste with low salinity
and low radioactive species content.
Reverse osmosis, well-developed technology,
has found many applications in nuclear industry.
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1376-2
It is used for removal of radionuclides from var-
ious streams in nuclear power plants: reactor
coolant, floor drains, reactor outage waste, spent
resin sluice water, the waste from steam genera-
tor chemical cleaning, and fuel cooling pond
water. It can be applied for the liquid waste
from research activities and medical applications
(Fig. 2), as well as for cleaning the defense and
reprocessing effluents (IAEA Technical Reports
Series 2004). Since RO rejects all dissolved mat-
ters from water solution, the product from RO
modules – high-purity water – may be recycled
within the nuclear power plant. Big variety of RO
systems is available in the market and various
polymeric materials are used for membrane
manufacturing.
Nanofiltration is able to separate monovalent
ions from multivalent ions or organic compounds
from monovalent ions. The best known applica-
tion of NF is boric acid recovery from reactor
cooling water (Zakrzewska-Trznadel 2008). NF
can be applied for removal of dissolved uranium
ions from wash solutions discharged from fuel
fabrication plants. Integrated with macromolecu-
lar ligands, NF was applied for separation of
lanthanides and actinides (Chitry et al. 2001a)
and separation of neodymium and gadolinium
isotopes (Chitry et al. 2001b).
Ultrafiltration is a good pretreatment method
before reverse osmosis. It is used for removal of
colloid matters and particles to avoid the fouling
of RO membranes, as well as alpha-emitting sub-
stances, namely, actinides, which are often in
2 Nuclear Waste Processing: Pressure-Driven Membrane Processes

Nuclear Waste Processing: Pressure-Driven Membrane Processes, Fig. 1 Pressure-driven membrane

processes – range of application

Nuclear Waste
Processing: Pressure-
Driven Membrane
Processes, Fig. 2 Three-
stage RO plant for the
treatment of institutional
radioactive waste at
Radioactive Waste
Management Plant at
Swierk, Poland

colloidal form. Combined with chelating com-
pounds or dispersed sorbents that bind small
ions, UF can be applied for removal of dissolved
radioactive metal ions from diluted aqueous solu-
tions. UF membranes reject complexed or sorbed
ions allowing uncomplexed ions to pass through
as permeate. Ultrafiltration may be employed for
the treatment of water from fuel storage ponds,
cleaning the laundry wastes, solvent wash
liquors, and plutonium evaporator overheads
from reprocessing lines or purification of
effluents from fuel fabrication plants. The decon-
tamination factors reported in the literature are in
the range of 1000 for a emitters and 100 for b and
g species, and the overall volume reduction of the
order of 104 is achieved with UF systems. Inor-
ganic, ceramic membranes in the region of UF
pore size are offered in the market, which
enhance the potential of the process.
Microfiltration is applied as a pretreatment
stage before RO or UF; it can be also used sepa-
rately for the concentration of radioactive
Nuclear Waste Processing: Pressure-Driven Membrane Processes
suspensions and dewatering of concentrated
sludge. It may be applied with conjunction of
precipitation process to remove various kinds of
radionuclides. Both polymeric and inorganic
membranes are employed for MF process.
In spite of intensive studies in the field of
membrane technologies and continuous develop-
ment of novel processes, the pressure-driven
membrane processes remain the leading mem-
brane methods in nuclear industry Zakrzewska-
Kołtuniewicz (2015).
References
Chitry F, Pellet-Rostaing S, Gozzi C, Lemaire M (2001a)
Separation of lanthanides(III) by nanofiltration-
complexation in aqueous medium. Sep Sci Technol
36(4):605–618
Chitry F, Pellet-Rostaing S, Vigneau O, Lemaire
M (2001b) Nanofiltration-complexation: a new
3
method for isotopic separation of heavy metals.
Chem Lett 30(8):770–771
IAEA Technical Reports Series No 431 (2004) Applica-
tion of membrane technologies for liquid radioactive
waste processing. International Atomic Energy
Agency, Vienna
Zakrzewska-Kołtuniewicz G (2015) Advancement in
membrane methods for liquid radioactive waste
processing: current opportunities, challenges, and the
global scenario. In: Pabby AK, Rizvi SSH, Sastre AM
(eds) Handbook of membrane separations: Handbook
of membrane separations: chemical, pharmaceutical,
and biotechnological applications. CRC Press/Taylor &
Francis Group, Boca Raton/London/New York, pp
665–708
Zakrzewska-Trznadel G (2008) Radioactive waste
processing: advancement in pressure driven processes
and current world scenario. In: Pabby AK, Rizvi SSH,
Sastre AM (eds) Handbook of membrane separations:
chemical, pharmaceutical, and biotechnological appli-
cations. CRC Press/Taylor & Francis Group, Boca
Raton/London/New York, pp 843–882
N
Nuclear Waste Processing: Thermal
Processes
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology
Instytut Chemii i Techniki Ja˛drowej, Warszawa,
Poland
Despite many potential benefits posed by mem-
brane distillation (MD), the scale of applications
of this process is still limited. Temperature
gradient-driven membrane processes were devel-
oped for concentrating liquid radioactive waste
from institutional applications (Chmielewski
et al. 2000; Fig. 1).
As the MD process is characterized by high
retention of nonvolatile solutes, large decontam-
ination factors are expected for radionuclides,
which are present in liquid radioactive effluents
in mainly ionic form. The process was tested in
laboratory scale and in the pilot plant. High
decontamination was achieved for radionuclides,
such as 192Ir, 170Tm, 140La, 134Cs, 133Ba, 192mIn,
110m
Ag, and 65Zn, which were completely
retained by the membrane, as well as for 137Cs
and 60Co, which were predominant components
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1377-2
of institutional radioactive waste. The decontam-
ination factors for these radionuclides were
44 and 4,336, respectively (Zakrzewska-
Trznadel et al. 1999). In the closed-loop mem-
brane apparatus, the specific conductivity of the
retentate does not change, while specific conduc-
tivity of distillate decreases (Fig. 2). In the same
time, radioactivity of the retentate is also stable
(however, small sorption in the unit is observed),
and the radioactivity of distillate is on the natural
background level (Fig. 3). The distillate produced
by MD module is clean water, which can be
reused in the nuclear plant.
The novel process of MD is advantageous, not
only because of high decontamination factors and
retention factors but also due to the simplicity of
the apparatus applied and its ability to utilize
waste heat from power sources such as nuclear
reactors. The other advantages of MD are a pos-
sibility of running the process to high-solute con-
centrations, sufficient for direct immobilization
of the waste, a high concentration in one-stage
operations, elimination of high pressures, and
reduction of sorption of radioactive species inside
the membrane pores since pores are filled with
water vapor. MD can be easily integrated with
2 Nuclear Waste Processing: Thermal Processes

other processes to form hybrid systems

Nuclear Waste Processing: Thermal Processes,
Fig. 1 Pilot plant for liquid radioactive waste concentra-
tion at Institute of Nuclear Chemistry and Technology,
Warsaw
(Zakrzewska-Trznadel 2008). Membranes
manufactured from PTFE, PP, or PVDF are
used in the process. The average pore size of the
membrane is 0.2–1.0 mm and the volume porosity
is 70–80 %.
Different configurations were tested: shell-
and-tube capillary, spiral-wound modules, and
plate-and-frame systems with flat sheet mem-
branes (Khayet et al. 2005). All arrangements of
MD are possible to use: direct contact, air gap,
sweep gas, and vacuum membrane distillation;
however, the most convenient configuration for
industrial applications, as well as this selected for
radioactive waste processing, seems to be the
direct contact MD.
Beneficial solution appears application of
membrane distillation in nuclear desalination,
both for radioactive waste treatment and to pro-
duce desalted water (Khayet et al. 2006). Ther-
mally driven process was also proposed for
separation of light isotopes of hydrogen and oxy-
gen for production of heavy water used in
CANDU type reactors, and heavy-oxygen water
for applications in nuclear medicine, i.e. PET
examinations (Zakrzewska-Trznadel et al. 1996;
Chmielewski et al. 2002).

Nuclear Waste 10000

Processing: Thermal
Processes, retentate
Fig. 2 Specific
conductivity of retentate 1000
(µS/cm)

and distillate vs. time

during the concentration of
radioactive waste 100
distillate

10
0 4 8 12 16 20
time (h)
Nuclear Waste Processing: Thermal Processes 3

Nuclear Waste 1000

Processing: Thermal
Processes,
Fig. 3 Specific
radioactivity of retentate retentate
and distillate vs. time 100
during the concentration of

(Bq/dm3)
radioactive waste

10

distillate
1
0 4 8 12 16 20
time (h)

References desalination: part II- experiments with radioactive

Chmielewski AG, Zakrzewska-Trznadel G,
Harasimowicz M, Van Hook WA (2000) The method
of radioactive waste treatment. Patent PL nr 179430
Chmielewski AG, Dembinski W, Zakrzewska-Trznadel G,
Miljević N, Van Hook A (2002) Stable isotopes – some
new fields of application. Polish Academy of Sciences,
Lodz
Khayet M, Mengual JI, Zakrzewska-Trznadel G (2005)
Direct contact membrane distillation for nuclear desa-
lination part I – review of membranes used in mem-
brane distillation and methods for their
characterization. J Nucl Desalination 1:435–449
Khayet M, Mengual JI, Zakrzewska-Trznadel G (2006)
Direct contact membrane distillation for nuclear
solutions. J Nucl Desalination 2:56–73
Zakrzewska-Trznadel G (2008) Radioactive waste
processing: advancement in pressure driven processes
and current world scenario. In: Pabby AK, Rizvi SSH,
Sastre AM (eds) Handbook of membrane separations:
chemical, pharmaceutical, and biotechnological appli-
cations. CRC Press Taylor & Francis Group, Boca
Raton, pp 843–882
Zakrzewska-Trznadel G, Chmielewski AG, Miljević
N (1996) Separation of protium/deuterium and
oxygen-16/oxygen18 by membrane distillation pro-
cess. J Membr Sci 113:337–342
Zakrzewska-Trznadel G, Harasimowicz M, Chmielewski
AG (1999) Concentration of radioactive components
in liquid low-level radioactive waste by membrane
distillation. J Membr Sci 163:257–264
S
Superhydrophobicity
Wolfgang M. Sigmund1,2 and Shu-Hau Hsu1
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
Superhydrophobicity is a surface phenomenon
that indicates a very low affinity to water, and,
in turn, the surface is very difficult to be wetted.
A generally accepted definition of superhydro-
phobicity is to have a water contact angle above
150 and a start-rolling angle lower than 10 at
room temperature and ambient pressure. There-
fore, water droplets on superhydrophobic sur-
faces typically form spherical beads (Fig. 1),
and can be easily shaken away from the surface.
For explanation on contact angle, please refer to
the section of Young’s Model. This extreme
water repellency widely exists in a variety of
natural species. Some crucial functions for these
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1378-5
species are provided through this property, such
as the reduction of surface contamination and the
ability of performing underwater respiration or
sustaining the impact from raindrops. More
details can be found in the section of lotus effect
and hairy superhydrophobic surface.
Superhydrophobic surfaces with the highest
contact angles are the combination of surface
chemistry and topography. The surface energy
has to be low enough to reduce the adhesion
between water and solid, and furthermore it has
to be rough enough to lower the solid area which
is in contact with water. Multiple scales of rough-
ness, namely, hierarchical structures, with addi-
tional nanosized roughness existing on the top of
a micron-sized feature, are often needed to
achieve superhydrophobicity. More details can
be found in the section of the Cassie-Baxter
Model.
Since 2000, interest in superhydrophobicity
has not only increased concerning the science
behind this unique phenomenon but also
concerning the design and engineering of such
superb anti-wetting surfaces. The most prominent
2 Superhydrophobicity

and removed while water droplets roll off the

surface. The consumption of water and energy
is minimized to keep the surface smudge free.
Other potential applications are also related to
the field of energy conservation or environmen-
tally friendly technologies, such as anti-
biofouling, anticorrosion, drag reduction, and
deicing surface.

References

Hsu SH, Sigmund WM (2010) Artificial Hairy Surfaces

Superhydrophobicity, Fig. 1 Water droplet forms a
with a nearly perfect hydrophobic response, Langmuir,
bead on superhydrophobic surface (Image by Hsu SH
26(3):1504–1506
and Sigmund W, University of Florida)
Hsu SH, Woan K, Sigmund WM (2011) Biologically
inspired hairy structures for superhydrophobicity,
effect of superhydrophobicity is the self-cleaning MSE-R: Reports 72, 10:189–201
ability, where dirt can be effortlessly picked up
Y

Young’s Model gSV ¼ gSL þ gLV cos yC (1)

This was first described in Thomas Young’s

Wolfgang M. Sigmund1,2 and Shu-Hau Hsu1
1 essay in 1805. If the value of the static contact
Department of Materials Science and
angle is 0  yc  90 , the liquid tends to spread
Engineering, University of Florida, Gainesville,
on the surface. It is usually referred to as hydro-
FL, USA
2 philic or oleophilic surface in terms of aqueous or
Department of Energy Engineering, Hanyang
oily liquids, respectively. If the value of the con-
University, Seoul, Republic of Korea
tact angle is 90 < yc  180 , the wet area tends
to shrink. It is then referred to as hydrophobic or
oleophobic surface in terms of aqueous or oily
Young’s model is commonly used to illustrate the
liquid, respectively. Surfaces with the water con-
wettability of solid surfaces. To better understand
tact angle between 150 and 180 are usually
this behavior, surface tension or interfacial ten-
called superhydrophobic.
sion has to be introduced. Surface tension is a
tensor that acts perpendicularly to a line on the
surface and is caused by the imbalance of attrac-
tive forces at the surface where surface atoms, Cross-References
molecules, or ions are surrounded by a reduced
number of similar species than those in the inte- ▶ Superhydrophic
rior or have larger distances to their nearest
neighbors. This causes liquid molecules at the
surface to be in an energetically unfavorable
References
state, and therefore the surface generates a force
to minimize its free surface area. When a Hsu SH (2010) Biologically inspired hairy surfaces for
waterdrop rests on a perfectly smooth solid sur- liquid repellency. Doctoral dissertation, University of
face, it forms a spherical cap whose shape is Florida
determined by the balance of the interfacial ten- Young T (1805) An essay on the cohesion of fluids. Phil
Trans R Soc Lond 95:65–87
sions between three different phases (liquid/air/
solid) (Fig. 1). The contact angle (yc) between the
water sphere and solid can be addressed as

# Springer-Verlag Berlin Heidelberg 2013

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1379-2
2 Young´s Model

Young’s Model, Fig. 1 A gLV

drop of water on solid
surface. The contact angle
(yc) is the balance of three Liquid
different interfacial gSL qc gSV
tensions (Hsu 2010) Substate
W
Wenzel Model
Wolfgang M. Sigmund1,2 and Shu-Hau Hsu3
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
3
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
Young’s equation is an oversimplified expression,
and is only valid for ideally flat surfaces that are
atomically smooth and chemically homogeneous.
Conversely, very few solids are atomically flat.
Wetting on rough surfaces was first considered
by Wenzel (1936). In the Wenzel state, where the
roughness grooves are completely filled with liq-
uid, the contact angle (yw) can be described by
 
g  gSL
cos yw ¼ Rf SV
gLV
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1380-2
where Rf is the surface roughness factor, which is
defined as
Actual area
Rf ¼ (2)
Projected area
Combining Wenzel equation with Young’s equa-
tion yields
cos yw ¼ Rf cos yC (3)
Since the roughness factor is always larger than
unity in practical situations, it is obvious that the
apparent angle on a roughened surface will
become smaller if its intrinsic contact angle on a
smooth surface is less than 90 . Similarly, the
apparent contact angle will be larger, if its intrinsic
contact angle is larger than 90 (Fig. 1).
References
Hsu SH (2010) Biologically inspired hairy surfaces for
(1) liquid repellency. Doctoral Dissertation, University of
Florida
Wenzel RN (1936) Resistance of solid surfaces to wetting
by water. Ind Eng Chem 28:988–994
2 Wenzel Model

Liquid
qw

Substate

Wenzel Model, Fig. 1 Liquid droplet on a rough surface. The contact angle can be predicted by Wenzel model (Hsu
2010)
C
Cassie-Baxter Model
Wolfgang M. Sigmund1,2 and Shu-Hau Hsu1
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
The Wenzel regime is usually recognized as
homogeneous wetting, since the liquid
completely penetrates into the grooves. While
under some circumstances, especially the
increase of the surface roughness, vapor pockets
may be trapped underneath the liquid yielding a
composite interface. This heterogeneous wetting
is usually described by the Cassie-Baxter
(CB) model, from which the apparent contact
angle (yCB) is given by equation: (Cassie and
Baxter 1944)
cos yCB ¼ f s cos yc þ f v cos yv
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1381-4
where yc is the intrinsic contact angle on the
original smooth surface and fs and fv are the area
fractions of the solid and vapor on the surface,
respectively. Since f s þ f v ¼ 1 and yv = 180
(implying that a suspended liquid droplet in air is
a perfect sphere), Eq. 1 can be rewritten as
follows:
cos yCB ¼ f s ð cos yc þ 1Þ  1 (2)
From Eq. 2, it can be found that droplets will have
a higher apparent contact angle if less area is in
contact with the solid substrate. The CB equation
simply indicates the contact angle can be
increased even when the intrinsic contact angle
of a liquid on the original smooth surface is less
than 90 .
New developments in the field show that there
may need to be taken other considerations for
contact angles and contact angle hysteresis. It is
suggested that the contact line model is a better
approach to predict the superhydrophobicity of
(1) surfaces (Gao and McCarthy 2007, 2009)
(Fig. 1).
2 Cassie-Baxter Model

Liquid

q cs

Substate

Cassie-Baxter Model, Fig. 1 Vapor pockets are trapped Cassie-Baxter model (Hsu et al. 2011, reproduced with
between the grooves and the liquid droplet. This state is permission from Elsevier Ltd.)
essential for superhydrophobicity and is described by

References Gao L, McCarthy TJ (2009) An attempt to correct the

Cassie ABD, Baxter S (1944) Wettability of porous sur-
faces. Trans Faraday Soc 40:546–550
Gao L, McCarthy TJ (2007) How Wenzel and Cassie were
wrong. Langmuir 23:3762–3765
faulty intuition perpetuated by the Wenzel and Cassie
“Laws”. Langmuir 25:7249–7255
Hsu SH, Woan K, Sigmund W (2011) Biologically
inspired hairy structures for superhydrophobicity.
Mater Sci Eng 72:189–201
H
Hairy Superhydrophobic Surface
Wolfgang M. Sigmund1,2 and Shu-Hau Hsu1
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
Superhydrophobicity not only exists on lotus-like
leaves but also on surfaces comprising high-
aspect ratio soft hairs. Although the piliferous
exterior is found in almost all water-repellent
arthropods and has been noted for over
100 years, (Comstock 1887) compared to the
Lotus effect, studies based on this structure are
relatively limited. The superhydrophobicity is
dominated by both surface roughness and chem-
istry, so as the hairy superhydrophobic surfaces.
Surface roughness arises from the arrangement of
hairs, and, similar to the water-repellent leaves,
hairs are also covered with a layer of epicuticular
wax that renders the exterior hydrophobic and
prevents the penetration of water. The wax layer
is not only important in water repellency but also
in water retention within the insect’s structure;
removal of the waxy layer will result in rapid
desiccation of the insects (Wigglesworth 1945).
The hairs in almost all water-repellent arthro-
pods are generally arranged as a series of “G”
shapes. Most of the hairs are not only inclined but
curled with their tips parallel to the bodies, which
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1382-3
in turn provides a greater resistance to wetting.
The array of tilted pillars increases the pressure
required to penetrate into the grooves, as the free
space between the tilted pillars is reduced, mak-
ing them favorable to resisting water.
A horizontal array of cylindrical pillars also pro-
vides a greater water resistance (Extrand 2002).
Overall, a series of inclined and parallel pillar
arrays is energetically unfavorable for a liquid
to intrude between the pillars parallel to the
interface.
Figure 1 shows an example of typical hairy
superhydrophobic surface, water strider’s body
and its leg (Hsu 2010). Two different sets of
body hair can be usually found from the arthro-
pods. Longer hairs, termed macrotrichia, are less
dense with lengths of 20 mm and diameters of
around1mm, and shorter hairs, termed
microtrichia, are approximately 2 mm long and
100 nm wide. Longer hairs taper to a point from
the base and incline at an angle of 30–45 with
their tips parallel to the body surface. Shorter
hairs are however highly dense and are more
randomly oriented. The hair is also patterned
with nanoscaled grooves with widths of around
400 nm, thus providing a structure with hierar-
chical roughness. Many arthropods possessing
hairy integument are reported to have contact
angles reaching over 160 , and it provides crucial
living functions for the species, such as underwa-
ter respiration, walking on water, or surviving
under rain impact (Bush et al. 2008). More details
2 Hairy Superhydrophobic Surface

Hairy Superhydrophobic Surface, Fig. 1 SEM images water repellency. (a) The hair on strider’s abdomen is
of the hair layer of the water strider’s body. The hair tips tilted at around 30–45 relative to the body surface. (b)
are bent inward toward the body to enhance the degree of The hair on strider’s leg (Hsu 2010)

Hairy Superhydrophobic
Surface, Fig. 2 A water
droplet forms a spherical
bead on Lady’s Mantle leaf

on underwater respiration can be found in the Herminghaus 2004). Water droplets are pinned
section of plastron effect. by the hydrophilic trichomes causing high con-
Hairy leaves with a feature similar to lotus tact angle but roll-off angle.
effect are also common. These plants, i.e.,
Lady’s Mantle (Alchemilla vulgaris), exhibit a
plurality of flexible hairs, termed trichomes, on
Cross-References
their leaves and stems (Fig. 2). Water droplets on
the fuzzy leaves can be suspended by the tri-
▶ Lotus Effect
chomes, which effectively prevent the droplets
▶ Plastron Effect
from wetting the leaf. Although the leaf itself
▶ Young’s Model
shows an excellent hydrophobicity, those tri-
chomes are found to be hydrophilic (Otten and
Hairy Superhydrophobic Surface
References
Bush JWM, Hu DL, Prakash M (2008) The integument of
water-walking arthropods: form and function. Adv
Insect Physiol 34:117–192
Comstock JH (1887) Note on the respiration of aquatic
bugs. Am Nat 21:577–578
Extrand CW (2002) Model for contact angles and hyster-
esis on rough and ultraphobic surfaces. Langmuir
18:7991–7999
3
Hsu SH (2010) Biologically inspired hairy surfaces for
liquid repellency. Doctoral dissertation, University of
Florida
Otten A, Herminghaus S (2004) How plants keep dry: a
physicist’s point of view. Langmuir 20:2405–2408
Wigglesworth VB (1945) Transpiration through the cuti-
cle of insects. J Exp Biol 21:97–114
H

Hydrophobicity phobos, simply stands for water and fear in Attic

Wolfgang M. Sigmund1,2 and Shu-Hau Hsu1
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
Greek. A hydrophobic surface tends not to be
dissolved or wetted by water. Water forms dis-
tinct droplets on a hydrophobic surface, and their
contact angles increase as its hydrophobicity
increases. For more details, please refer to the
section of Young’s Model.

Cross-References
Hydrophobicity is the term frequently used in
surface chemistry describing the tendency of ▶ Super-hydrophobicity
moving away from water or aqueous environ-
ment. The name, the combination of hydro- and

# Springer-Verlag Berlin Heidelberg 2014

E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1383-3
L
Lotus Effect
Wolfgang M. Sigmund1 and Shu-Hau Hsu2
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
Lotus leaf (Nelumbo nucifera) has become the
epitome of natural superhydrophobic surfaces
and has long been considered as a sacred symbol
of purity for thousand years in oriental culture
due to its impressive self-cleaning feature, where
leaves remain unsmudged even being immersed
into muddy water. Water contact angle on lotus
leaf is reported above 160 with few degrees of
roll-off angle. Therefore, lotus effect is some-
times a synonym for superhydrophobicity or
self-cleaning nowadays. Although the effect has
long been noticed for several generations, a sys-
tematically detailed investigation was not carried
out until 1997 where more than 200 water-
repellent plants were studied via scanning elec-
tron microscopy (Neinhuis and Barthlott 1997).
The study reveals the secret of lotus leaf, which,
not surprisingly, attributes to its combination of
surface roughness and chemical substances.
Hydrophobicity and self-cleaning of lotus leaf
are believed as a mechanism to resist harmful
microorganism bounding to the leaf surface,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1384-3
since water is usually required for the
germination.
The lotus leaf is covered by small protrusions
(Fig. 1a) called papillae with their average diam-
eter and height about 10 mm. The papillae are
further covered by an additional layer of epicu-
ticular waxes, generated from epidermal cells
(Fig. 1b). These wax crystals are presented in
submicron size and in crystalline tubules with
water contact angles of about 95–110 , which is
considered hydrophobic. The epicuticular waxes
play a practically important role as they are not
only to provide hydrophobicity but to generate an
additional roughness in a smaller length of scale
other than micron-sized bumps. The absence of
wax crystals, i.e., dropping hot water onto the
leaf, will totally eliminate the superhydro-
phobicity (Liu et al. 2009). The kind of hierarchi-
cal roughness on superhydrophobic surfaces
seems to play a crucial role, but the detailed
mechanism is not yet completely clear.
A general benefit suggested is to repel both
macro- and microscope water droplets
(Nosonovsky and Bhushan 2007). Surfaces with
only one scale of roughness repelled macroscopic
droplets fairly well, while the condensation may
easily form microscopic droplets between the
grooves of the surface structure.
Cross-References
▶ Young Equation
2 Lotus Effect

Lotus Effect, Fig. 1 SEM micrographs of lotus leaf showing its relatively rough surface covered by small micron-sized
protrusions (a) and submicron-sized wax crystals (b) (Hsu 2010)

References Neinhuis C, Barthlott W (1997) Characterization and dis-

Hsu SH (2010) Biologically inspired hairy surfaces for
liquid repellency. Doctoral dissertation, University of
Florida
Liu Y, Chen X, Xin JH (2009) Can superhydrophobic
surfaces repel hot water? J Mater Chem 19:5602–5611
tribution of water-repellent, self-cleaning plant sur-
faces. Ann Bot 79:667–677
Nosonovsky M, Bhushan B (2007) Multiscale friction
mechanisms and hierarchical surfaces in nano- and
bio-tribology. Mater Sci Eng R 58:162–193
P
Plastron Effect
Wolfgang M. Sigmund1 and Shu-Hau Hsu2
1
Department of Materials Science and
Engineering, University of Florida, Gainesville,
FL, USA
2
Department of Energy Engineering, Hanyang
University, Seoul, Republic of Korea
Plastron, meaning shielding, was first used in
1910 by zoologist, F. Brocher, referring to a
layer of gas adhering closely to the body surface
between the hairs of underwater Coleoptera fam-
ily (Brocher 1909). This air layer serves as an air
supply for a variety of arthropods while
performing living activities underwater. A well-
known example is the water spider (Argyroneta
aquatica), which spends its entire life living
underwater (Fig. 1). The hairy structure of the
water spider is thus necessary not only to lower
the contact area with the water surface but to
enable them to breathe when submerged. This
activity is consequently termed plastron respira-
tion. The gases, oxygen and carbon dioxide, are
supplied and removed through the diffusion
across the bubble surface from the ambient
water. The air layer is maintained by an array of
hair with their tips forming pillars lying roughly
parallel to the body. The curvature pressure and
the mechanical strength of hairs sustain the inter-
face, while higher ambient hydraulic pressure
may buckle the hairs causing the collapse of the
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1385-2
plastron air. Earlier observations found that the
collapsing point for most insects occurs in the
pressure between 1 and 5 atm (Thorpe and Crisp
1947). With more sophisticated imaging equip-
ment, calculations, however, estimated that the
hairs should be stable at a pressure up to 40 atm
(Hinton 1976).
Nowadays plastron is commonly used to
describe the thin air layer trapped on submerged
surfaces in Cassie-Baxter state. The air layer
trapped by the superhydrophobic surface is ther-
modynamically unstable. Except for a few spe-
cies that actively maintain the trapped air for
breathing the air dissolves into the water. The
lotus leaf loses its plastron air within an hour
when immersed to the depth of half meter. The
metastable underwater superhydrophobicity
limits its potential applications, such as drag
reduction or anticorrosion. The lifetime of plas-
tron is controlled by the mass flux of air into
water and is driven by partial gas pressure differ-
ence between the interface. The decay of plastron
generally has two distinct phases. At the initial
phase, air diffuses into water through the planar
interface, and its mass flux shows exponential
depth dependence. With further thinning to a
critical thickness, the plastron forms into spheri-
cal cup-shaped air bubbles resulting in a rapid
decay driven by the Laplace pressure (Poetes
et al. 2010). The lifetime of plastron varies with
its surface energy and topography, while detailed
studies are still very limited to date.
2 Plastron Effect

Hinton HE (1976) Plastron respiration in bugs and beetles.

J Insect Physiol 22:1529–1550
Poetes R, Holtzmann K, Franze K, Steiner U (2010) Meta-
stable underwater superhydrophobicity. Phys Rev Lett
105:166104
Seymour RS, Hetz SK (2011) The diving bell and the
spider: the physical gill of Argyroneta aquatica.
J Exp Biol 214:2175–2181
Thorpe WH, Crisp DJ (1947) Studies on plastron respira-
tion.1. The biology of aphelocheirus [Hemiptera,
Aphelocheiridae (Naucoridae)] and the mechanism of
plastron retention. J Exp Biol 24:227–269

Plastron Effect, Fig. 1 Air clinging to the hydrophobic

hairs on the abdomen of a spider away from the diving bell
(Seymour and Hetz 2011)

References

Brocher F (1909) Recherches sur la respiration des

insectes aquatiques adultes. Les Dyticide’s. Ann Biol
Lacustre 4:383–398
P
Porous Silicon
Cameron Shearer
Institute of Physical Chemistry, University of
Muenster, Muenster, North Rhine-Westphalia,
Germany
Porous silicon (pSi), as its name suggests, is bulk
silicon that has been etched by some means to
form pits (pores) on its surface. Porous silicon is
produced through the chemical, photochemical,
or electrochemical etching of flat, crystalline sil-
icon with fluoride solutions (Canham 1997;
Schmeltzer and Buriak 2005). Galvanostatic
anodization of flat silicon is the method most
often employed to fabricate pSi because it pro-
vides greater reliability and selectivity to the sur-
face produced. Aqueous hydrofluoric acid
(HF) in ethanol is a common etchant used. The
ethanol component is used to reduce the surface
tension of the etching solution and allow full
wetting of the silicon substrate (Schmeltzer and
Buriak 2005). The etching process is undertaken
at room temperature in a specially designed etch-
ing cell (Fig. 1) made of the fluoride-resistant
Teflon. The pores produced are highly one
dimensional and are of random shape (Fig. 2).
The fabricated pores formed can be in a range
of tuneable sizes from micropores (<5 nm) to
mesopores (5–50 nm) to macropores (>50 nm).
The pore morphology is affected by the current
density, silicon dopant (e.g., boron or phosphorus
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1391-3
density), illumination, and HF concentration dur-
ing etching (Canham 1997). Increasing the cur-
rent density causes lateral etching and hence
increasing diameter. Increasing HF concentration
increases the number of F anions at the solution-
surface interface resulting in a quicker reaction
between the F anion and the holes, producing
pores with smaller diameters and increasing
porosity (Canham 1997). Etching time affects
the depth of the etch with longer times yielding
deeper pores (Lehmann 2002).
HF etching of silicon yields a Si-H-terminated
surface. These surfaces can be modified using a
number of different chemical reactions; the most
common are hydrosilylation and oxidation
followed by from which a range of surface chem-
istries can be achieved (Schmeltzer and Buriak
2005; Jane et al. 2009). Porous silicon is an ideal
biomaterial due to its biodegradability, large
internal surface area, and biocompatibility that
has found application in biosensing, tissue engi-
neering, and drug delivery applications (Anglin
et al. 2004; Jane et al. 2009).
Porous silicon membranes are thin layers of
pSi with pores open at either end. Fabrication of
pSi membranes has been achieved by etching
through an entire Si wafer (Searson 1991), by
etching a thin layer of pSi followed by macro-
scopically etching from the back side (Cruz
et al. 2005), and by the “lift-off” of a pSi layer
(Velleman et al. 2010). The “lift-off” procedure
involves the etching of a pSi film to a desired
depth followed by the electropolishing of the
2 Porous Silicon

Porous Silicon,
Fig. 1 Schematic of the
etching cell used for the
anodic etching of silicon

Porous Silicon, Fig. 2 SEM images of (a) top-down view of porous silicon showing the irregularly shaped pores
produced and (b) side-on view of porous silicon still supported on bulk silicon (at bottom)

Porous Silicon,
Fig. 3 Photographs of pSi
membranes (a) attached to
the silicon wafer and (b)
lifted off the silicon wafer
Porous Silicon
bottom of the film to liberate it from the bulk
Si. Electropolishing is achieved by increasing
the current density and/or decreasing the HF con-
centration. The brittle nature of pSi membranes
makes them unsuitable for commercial mem-
brane applications. However, the small pores
make interesting systems for fundamental trans-
port investigations such as gas (Solanki
et al. 2004; Cruz et al. 2005) and fluid
(Velleman et al. 2010, Fig. 3).
Cross-References
▶ Biodegradable
▶ Biointerface
▶ Porous Alumina
▶ Silicon
References
Anglin EJ, Schwartz MP, Ng VP et al (2004) Engineering
the chemistry and nanostructure of porous silicon
3
fabry-perot films for loading and release of a steroid.
Langmuir 20(25):11264–11269
Canham L (1997) Properties of porous silicon. The insti-
tution of electrical engineers. United Kingdom,
London
Cruz S, Honig-dOrville A, Muller J (2005) Fabrication
and optimization of porous silicon substrates for dif-
fusion membrane applications. J Electrochem Soc
152(6):C418–C424
Jane A, Dronov R, Hodges A, Voelcker NH (2009) Porous
silicon biosensors on the advance. Trends Biotechnol
27(4):230–239
Lehmann V (2002) Electrochemistry of silicon: instru-
mentation, science, materials and applications.
Weinheim, Germany
Schmeltzer JM, Buriak JM (2005) Recent developments
in the chemistry and chemical applications of porous
silicon. In: Rao CN, M€ uller A, Cheetham AK (eds)
The chemistry of nanomaterials: synthesis, properties
and applications. Wiley, Weinheim, pp 518–550
Searson PC (1991) Porous silicon membranes. Appl Phys
Lett 59(7):832–833
Solanki CS, Bilyalov RR, Poortmans J et al (2004) Self-
standing porous silicon films by one-step anodizing.
J Electrochem Soc 151(5):C307
Velleman L, Shearer CJ, Ellis AV et al (2010) Fabrication
of self-supporting porous silicon membranes and
tuning transport properties by surface functiona-
lization. Nanoscale 2(9):1756–1761
A
Aligned Carbon Nanotube
Cameron Shearer
School of Chemical and Physical Sciences,
Flinders University, Adelaide, South Australia,
Australia
Synonyms
A-CNT; Horizontally aligned carbon nanotube;
Vertically aligned carbon nanotube
Main Text
Carbon nanotubes (CNTs) are allotropes of car-
bon in which the carbon atoms form a hexagonal
sheet of sp2 bonds (analogous to graphite) which
is seamlessly rolled up into a cylinder that can be
microns long but is only nanometers in diameter
(Yamamoto et al. 2008). Following typical syn-
thesis procedures, CNTs exist as a tangled web of
randomly oriented fibers. For many applications,
the CNTs are required to be aligned with either
horizontal or vertical alignment (Fig. 1).
Horizontally aligned CNTs are of particular
importance in the generation of field effect tran-
sistors and conductive wires based upon CNTs.
CNTs can be horizontally aligned via a range of
processes including spin coating, filtering, mag-
netic field alignment, and drying-induced and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli , L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1392-2
chemical vapor deposition (CVD) (Dai 2001;
Joselevich et al. 2008). Horizontal CNTs can
form a dense, flexible, stable mat (called a
“bucky paper”) which can potentially be used as
a membrane as the space between the CNTs is
generally quite small (<50 nm) (Dumée
et al. 2010; Sears et al. 2010).
Vertically aligned CNTs can be prepared via
the CVD growth of CNTs on pre-patterned sub-
strate supported catalyst nanoparticles. Verti-
cally aligned CNTs produced via this method
have been grown greater than 1 mm in length
(Joselevich et al. 2008). Alignment is enhanced
via the use of a strong electric field such as in
plasma-enhanced CVD. Vertical alignment is
of importance in the fields of field emission,
chemical sensing, and CNT nanofiltration
membranes (Endo et al. 2008; Shearer
et al. 2012). CNT nanofiltration membranes
are of particular interest as molecular dynamics
simulations have shown that water can flow
through CNTs at a remarkable rate (Hummer
et al. 2001), while the flow of contaminates is
restricted by the nano-size of the CNT inner
pore (1 nm). The fabrication of such a mem-
brane required vertically aligned CNTs,
encased within an impermeable matrix such
that flow can only occur through the CNT
inner pore. This is experimentally quite diffi-
cult, but a few reports with promising results
have been published (Majumder et al. 2005;
Holt et al. 2006; Wu et al. 2010).
2 Aligned Carbon Nanotube

Aligned Carbon Nanotube, Fig. 1 SEM image CNTs produced via CVD showing (a) randomly entangled, (b)
horizontally aligned, and (c) vertically aligned

Cross-References Endo M, Strano M, Ajayan P (2008) Potential applications

of carbon nanotubes. In: Jorio A, Dresselhaus G,
Dresselhaus MS (eds) Topics in applied physics: car-
▶ Chemical Sensor bon nanotubes. Springer, Berlin, pp 13–61
▶ Field Effect Transistor Holt J, Park H, Wang Y et al (2006) Fast mass transport
▶ Field Emission through sub-2-nanometer carbon nanotubes. Science
▶ Membrane 312:1034
Hummer G, Rasaiah JC, Noworyta JP (2001) Water con-
duction through the hydrophobic channel of a carbon
nanotube. Nature 414(6860):188–190
Joselevich E, Dai H, Liu J et al (2008) Carbon nanotube
References synthesis and organization. In: Jorio A, Dresselhaus G,
Dresselhaus MS (eds) Carbon nanotubes, topics in
Dai H (2001) Nanotube growth and characterization. In: applied physics. Springer-Verlag, Berlin, pp 101–164
Dresselhaus MS, Dresselhaus G, Avouris P (eds) Car- Majumder M, Chopra N, Andrews R, Hinds BJ
bon nanotubes, topics in applied physics. Springer- (2005) Enhanced flow in carbon nanotubes. Nature
Verlag, Berlin, pp 29–53 438:44
Dumée LF, Sears K, Sch€ utz J et al (2010) Characterization Sears K, Dumée L, Sch€ utz J et al (2010) Recent develop-
and evaluation of carbon nanotube bucky-paper mem- ments in carbon nanotube membranes for water puri-
branes for direct contact membrane distillation. fication and gas separation. Mater Lett 3(1):127–149
J Membr Sci 351(1–2):36–43 Shearer C, Fahy A, Barr M et al (2012) Improved field
emission stability from single-walled carbon
Aligned Carbon Nanotube
nanotubes chemically attached to silicon. Nanoscale
Res Lett 7(1):432
Wu J, Paudel KS, Strasinger C et al (2010) Programmable
transdermal drug delivery of nicotine using carbon
nanotube membranes. Proc Natl Acad Sci
107(26):11698–11702
3
Yamamoto T, Watanabe K, Hernández E (2008) Mechan-
ical properties, thermal stability and heat transport in
carbon nanotubes. In: Jorio A, Dresselhaus G,
Dresselhaus MS (eds) Carbon nanotubes. Springer,
Berlin, pp 165–194
B
Biointerface
Cameron Shearer
School of Chemical and Physical Sciences,
Flinders University, Adelaide, South Australia,
Australia
Institute of Physical Chemistry, University of
Muenster, Muenster, North Rhine-Westphalia,
Germany
Synonyms
Biorecognition substrate
A biointerface is an interface between biological
material (e.g., cells, tissue) and a (commonly)
synthetic substrate. Biointerfaces call for
advanced design and preparation in order to
match the sophisticated (bio) recognition ability
of biological systems. Specifically this requires
combined topographic, chemical, and viscoelas-
tic patterns on surfaces to match proteins at the
nm scale and cells at the micrometer scale
(Kasemo 2002).
Biointerfaces are typically used in the fields of
immunology, surgery, pathology, pharmacology,
and many others either for the proliferation of
cells for further application or investigative
study or as a platform for cell manipulation.
These studies have become even more topical
upon completion of the human genome project,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1393-3
which has set the formidable challenge of eluci-
dating the function of the vast amount of genomic
information within the genotype of an individual.
A potential medical application of a
biointerface is in the ex situ growth of skin/
bone/organ tissue for subsequent transplantation.
For example, burn victims can have their own
replacement skin grown in a laboratory via the
proliferation of their own epidermal cells upon a
biointerface in a laboratory. Biointerfaces them-
selves can potentially be installed in situ to assist
in cell regeneration, such as after surgery. For this
purpose, biodegradable biointerfaces are of par-
ticular interest as they perform their function of
assisting cell regeneration and are then degraded
naturally into nontoxic products which are then
excreted (Hook et al. 2006).
The scientific study of cells is important to
improve fundamental understanding of their
working process. Biointerfaces are often used as
experimental platforms to study various proper-
ties of cells. For instance, neuronal cells are elec-
trically excitable cell that processes and transmits
information through electrical and chemical sig-
nals. The growth of these cells on specially
designed biointerfaces has allowed scientists to
directly investigate their signal transmission pro-
cess (Robinson et al. 2012).
The fabrication of various biointerfaces is of
particular interest for stem cell research. Stem
cells can differentiate into a variety of different
cell types depending upon their environment
(Pittenger et al. 1999). Therefore, the careful
2 Biointerface

design of particular biointerfaces can promote References

stem cell differentiation into a desired cell type.
For example, stem cells adsorbed on harder sur- Engler AJ, Sen S, Sweeney HL, Discher DE (2006) Matrix
elasticity directs stem cell lineage specification. Cell
faces tend to differentiate into bone-like cells
126(4):677–689
(Engler et al. 2006). Hook AL, Thissen H, Voelcker NH (2006) Surface manip-
ulation of biomolecules for cell microarray applica-
tions. Trends Biotechnol 24(10):471–477
Kasemo B (2002) Biological surface science. Surf Sci
Cross-References 500(1–3):656–677
Pittenger MF, Mackay AM, Beck SC et al (1999)
Multilineage potential of adult human mesenchymal
▶ Biosensor stem cells. Science 284(5411):143–147
▶ Stem Cell Robinson JT, Jorgolli M, Shalek AK et al (2012) Vertical
▶ Tissue Engineering nanowire electrode arrays as a scalable platform for
intracellular interfacing to neuronal circuits. Nat
Nanotechnol 7(3):180–184
B
Biosensor-Based Membrane
Cameron Shearer
School of Chemical and Physical Sciences,
Flinders University, Adelaide, South Australia,
Australia
Institute of Physical Chemistry, University of
Muenster, Muenster, North Rhine-Westphalia,
Germany
Synonym
Membranes for biosensors
A biosensor is an analytical device used for the
quantitative and qualitative detection of a specific
analyte. A biosensor broadly consists of three
main components: the biological sensing element
which specifically interacts with the analyte, the
transducer which is used to convert the signal
from the bioelement-analyte interaction into a
signal which is readable and reportable by the
third component, the reading device (Fig. 1).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1394-3
Membrane-based biosensors operate by
reporting changes in ionic conduction through a
molecular membrane. These membranes consist
of one or more lipid bilayer membranes, mimick-
ing cell walls, upon a conducting (often gold)
substrate (Cornell 2002). Many schemes have
been reported for modulating the membrane ion
conduction in response to the presence of a spe-
cific target analyte. The most common
membrane-based biosensor was introduced by
Cornell et al. where a mobile biological ion chan-
nel, initially gramicidin A, is tethered to an anti-
body of interest (Cornell et al. 1997). Under
standard conditions, the ion channel is mobile
throughout the membrane and predominantly
exists in a dimer arrangement with a substrate-
immobilized ion channel. Upon introduction of
the target analyte, the analyte binds to both an
immobilized antibody and the antibody tethered
to the ion channel resulting in a conformational
change of the ion channels, reducing conductance
through the membrane (Cornell et al. 1997; Cor-
nell 2002). From the change in conductance, a
quantitative value of the amount of analyte pre-
sent can be calculated. Membrane biosensors are
2 Biosensor-Based Membrane

Biosensor-Based Membrane, Fig. 1 Schematic of basic mechanism of a membrane-based biosensor based upon the
change in conductance upon interaction between an antibody tethered to the ion channel and target analyte (antigen)

promising for a range of diagnostic studies as the References

lipid membrane environment is ideal for the long-
term storage of biological sensing elements Cornell BA (2002) Membrane-based biosensors,
Chapter 15. In: Frances SL, Chris ART (eds) Optical
(Oh et al. 2008).
biosensors. Elsevier, Amsterdam, pp 457–495
Cornell BA, Braach-Maksvytis VLB, King LG
et al (1997) A biosensor that uses ion-channel
Cross-References switches. Nature 387(6633):580–583
Oh SY, Cornell B, Smith D et al (2008) Rapid detection of
influenza a virus in clinical samples using an ion chan-
▶ Biosensor nel switch biosensor. Biosens Bioelectron
▶ Cell Membrane 23(7):1161–1165
▶ Lipid Bilayer
P
Polyacrylonitrile (PAN)
Alexey Volkov
A.V.Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Polyacrylonitrile (PAN) is semicrystalline ther-
moplastic polymer (see Fig. 1 for structural for-
mula of PAN), which is synthesized by radical
polymerization in the presence of conventional
initiators, for example, peroxides. There are six
different technologies of production of monomer,
acrylonitrile: (a) from ethylene via ethylene
oxide and ethylene cyanohydrins, (b) oxidative
ammonolysis of propylene or propane, (c) from
acetylene and hydrocyanic acid, (d) from ethyl-
ene via acetaldehyde and hydroxynitrile, (e) from
propylene and nitrogen oxide, and (f) from ethyl-
ene, hydrocyanic acid, and oxygen. PAN has a
good resistance in a wide range of organic sol-
vents: insoluble in hydrocarbons, chlorinated
hydrocarbons, ketones, diethyl ether, and aceto-
nitrile (Mark 2009). Major application of PAN is
textile fibers.
When homopolymer PAN is heated above
180–200  C, the autocatalytic reaction of cycli-
zation takes place through a free radical mecha-
nism (see Fig. 2). Further heat treatment leads to
carbonization of initial material. PAN-based
fibers are the main raw material for carbon fiber
production. Polymer softening temperature is
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1398-1
close to the one at which cyclization starts; there-
fore, PAN can be only processed to fibers by dry
or wet spinning. Besides homopolymer, PAN
copolymers can be used in order to improve car-
bon fiber quality. Carbon fibers have a number of
advantages like low density, high stiffness, good
chemical and temperature resistance. As a result
carbon fibers are widely used in production of
novel light-weight composite materials with
high mechanical properties for different applica-
tions like aerospace industry, machinery and mil-
itary applications, sports, and other applications
(Gupta et al. 1991).
Different copolymers of acrylonitrile offer a
large family of materials for different applica-
tions. Acrylonitrile-butadiene rubber with acry-
lonitrile content from 20 % to 50 % is known as
nitrile rubber that has high oil and abrasion resis-
tance. Copolymer of acrylonitrile with butadiene
and styrene is a famous ABS plastic that is exten-
sively used in different applications such as the
automotive industry (e.g., bumpers), different
plastic carcass, parts, and goods. Acrylonitrile
and butadiene provide good hardness, while
incorporated rubbery particles offer shock absor-
bance that makes this material less brittle. In
addition, polar groups of acrylonitrile also pro-
vide interchain bonding to improve mechanical
properties and good dimension stability. ABS has
Polyacrylonitrile (PAN), [ CH2 CH ]n
Fig. 1 Structural formula
of polyacrylonitrile C N
2 Polyacrylonitrile (PAN)

Polyacrylonitrile (PAN),
T >200°C
Fig. 2 Radical mechanism
of polyacrylonitrile · ·
N N N N· N N N N· N
cyclization

good chemical stability and low water adsorption
and can be operated at low and high temperatures.
ABS can be processed with standard methods
(Rosato et al. 2000).
PAN has been widely used as a membrane
material. Regarding transport properties, PAN
belongs to the group of extra low permeable
(barrier) polymers (e.g., P(CO2)~10 Barrer).
Due to high chemical stability, PAN is used for
fabrication of micro- and ultrafiltration mem-
branes both for aqueous and nonaqueous applica-
tions. These flat membranes are fabricated on a
nonwoven by a phase inversion process. It is
worth to mention, that PAN ultrafiltration mem-
branes are attractive for use as an efficient porous
support for fabrication of thin film composite
membranes for gas and vapor separations,
pervaporation and organic solvent nanofiltration.
Several companies have manufactured thin film
composite membranes based on PAN porous sup-
ports over the years.
References
Gupta AK, Paliwal DK, Bajaj P (1991) Acrylic precursors
for carbon fibers. J Macromol Sci C 31:1–89
Mark JE (2009) Polymer data handbook, 2nd edn. Oxford
University Press, New York
Rosato DV, Rosato MG, Rosato DV (2000) Concise ency-
clopedia of plastics. Kluwer
P
Polyacrylonitrile Membrane
George Dibrov
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
The majority of commercial methods of produc-
tion of polyacrylonitrile (PAN) are based on free
radical polymerization of acrylonitrile (Fig. 1).
Chemical and physical properties of PAN
(Andrady 1999, Scharnagl and Buschatz 2001):
• Melting point: 317  C
• Glass transition temperature: 87–125  C
• Decomposition temperature: >250  C
• Density: 1.17 g/cm3
• Solubility: DMF, DMSO, DMAc, NMP,
dioxanone, chloroacetonitrile, dimethyl phos-
phite, dimethyl sulfone, ethylene carbonate,
y-butyrolactone, conc. sulfuric and nitric
acid, and conc. salt solutions of LiBr or
NaCNS in water
• Water uptake: 1–2.4 % (25  C, 65 % rel.
humidity)
• Good resistance against mineral acids and
weak alkaline solutions, moderate against
strong alkalines
• Permeability coefficient P(m3(STP)
m
(s

m2
Pa) 1
109) of unplasticized film at
25 oC: P(O2) = 0.00015, P(CO2) = 0.00060,
P(H2O) = 230
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1399-1
PAN membranes have attracted much atten-
tion due to a variety of excellent characteristics,
which include thermal stability and tolerance to
most solvents, atmosphere, bacteria, and photo
irradiation. Therefore, their exploitation also
covers many fields in micro- and ultrafiltration,
pervaporation, nanofiltration, reverse osmosis
like water treatment, enzyme immobilization,
hemodialysis, concentration of whey or protein,
concentration of oil/water mixtures, etc. PAN
membranes demonstrate high stability against
chemical cleaning agents and resistance to
sodium hypochlorite, citric acid, weak alkaline
solutions, hydrolysis, and oxidation. PAN is
highly crystalline and relatively hydrophilic
(calc. surface tension is 44 dynes/cm) and is
usually copolymerized with more hydrophilic
monomers to improve processability and to
make it less brittle.
Preparation of PAN membranes is possible by
phase inversion from its solutions. PAN mem-
branes for ultra- and microfiltration are devel-
oped by GKSS (Scharnagl and Buschatz 2001).
Different membrane morphologies varying from
large finger-like pores to homogeneous micropo-
rous structures can be obtained. The change from
the finger-like pores to globular ones enhances
the pressure stability of membranes, which is
favorable to the use of membranes as supporting
material for composite membranes.
The flux of the membranes can be adjusted
between 100 up to nearly 2000 l
(m2
h

2 Polyacrylonitrile Membrane
Polyacrylonitrile
Membrane, Fig. 1 The
chemical structure of the
polyacrylonitrile
repeat unit
bar) 1 with high rejection. By varying the forma-
tion parameters, a wide spectrum of membranes
with different average pore diameters
(d50 = 2–70 nm) can be produced. PAN mem-
branes are used in a plate-and-frame module
developed in the GKSS research center and now
sold by Amafilter. This module is applicable to
nano-, ultra-, and microfiltration and also appro-
priate for high values of suspended solids. For
water reuse, the PAN membranes are also used in
Rochem FM-modules.
Microza ® hollow fiber ultrafiltration modules
produced by Pall Corporation feature unique
double-skinned polyacrylonitrile (PAN) mem-
branes with dense internal layer. The modules
are used in a range of pharmaceutical applica-
tions especially in purification and processing of
aqueous enzymes and protein solutions, raw
water pretreatment to pharmaceutical water puri-
fication plant. UF membranes from PAN and its
copolymers are also produced by Millipore and
Applied Membranes Inc.
PAN can be chemically cross-linked with and
without the change in the porous structure of the
membrane (Nunes and Peinemann 2001). The
surface of PAN membranes can be modified by
plasma or conversion of nitrile groups (Ulbricht
2006).
Cross-References
▶ Plasma Functionalization by Stephanie
Roualdes
▶ Polyacrylonitrile (PAN) by A. Volkov
References
Andrady AL (1999) In: Mark JE (ed) Polymer data hand-
book. Oxford University Press, pp 254–257
Nunes SP, Peinemann K-V (2001) Membrane technology
in the chemical industry. Wiley-VCH Verlag GmbH,
Weinheim, p 26
Scharnagl N, Buschatz H (2001) Polyacrylonitrile (PAN)
membranes for ultra- and microfiltration. Desalination
139:191–198
Ulbricht M (2006) Advanced functional polymer mem-
branes. Polymer 47:2217–2262
P
Polydimethylsiloxane (PDMS)
Alexey Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russia
Polydimethylsiloxane (PDMS) is the most known
organosilicon rubbery polymer and its glass tran-
sition temperature is about 150  C. PDMS,
often referred to as “silicone rubber,” can be
polymerized from different monomers by hydro-
lysis and anionic, cationic, emulsion, and radia-
tion polymerization process (Mark 2009). This
polymer is a transparent material with high ther-
mal and UV resistance. As an oligomer, PDMS is
widely used as lubricants, greases, heat transfer
liquids, and hydraulic liquids due to its viscoelas-
tic properties (Mark 2009) (Fig. 1).
PDMS can be poured in a mold and then cross-
linked for its hardening allowing to obtain an
exact replica of the objects of different sizes and
shapes with imprinted features on macro- and
micro-levels (known as “soft lithography”).
Hydrosilylation reaction between polymeric
chain and cross-linker like tetrakis
(dimethylsiloxy)silane by thermal or UV initia-
tion allows to cross-link PDMS and, thus, control
polymer solvent resistance and mechanical prop-
erties. As an example, Young’s modulus of
PDMS can be varied in the range of
50–8000 kPa by changing of cross-linker content
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1400-1
and conversion degree of cross-linking reaction.
As a result, PDMS is widely used as a sealing
material (e.g., O-rings) with adjustable hardness
and solvent stability.
High inertness in physiological environment
makes it possible to use this material in different
biomedical applications including soft matrix for
drug delivery, microfluidics devices,
microstamping of biological compounds, cos-
metics, wound dressing, parts of different
devices, coating of catheters, and silicone breast
implants. PDMS is a hydrophobic material with a
contact angle of distilled water of about 110 . By
plasma oxidation or UV radiation, the polymer
surface can be hydrophilized allowing to
decrease water contact angle down to 0 for
improvement of cells adhesion, assembling of
microdevices (adhesion between PDMS replica
and glass substrate by covalent bonds), and its
wetting by physiological fluids (Nahmias and
Bhatia 2009; Ratner et al. 1996).
PDMS is used as adhesive material, particu-
larly, pressure-sensitive materials. Due to good
dielectric properties, PDMS is also used for
dielectric encapsulation. PDMS is extensively
utilized as a polymer matrix for further incorpo-
ration of different kinds of fillers (including fab-
rication of mixed matrix membranes);
incorporated fillers can provide additional cross-
linking since strong polymer adsorption of filler
surface leads to lower macro-chain mobility
(known as a “physical cross-linking”).
2 Polydimethylsiloxane (PDMS)

Polydimethylsiloxane CH3 References

(PDMS), Fig. 1 Structural
[ Si O ]n
formula of PDMS
CH3
PDMS exhibits the highest values of gas and
vapor permeabilities among rubbery polymers.
By this reason, it has been extensively studied
as a membrane material for different applica-
tions, namely, gas and vapor separation
(Freeman et al. 2006), organophilic
pervaporation (e.g., bioalcohols recovery from
fermentation broth) (Vane 2005), and organic
solvent nanofiltration (Volkov et al. 2008).
PDMS can be used to fabricate hollow fiber,
tubular, unsupported sheet, or thin-layer
supported sheet membranes. Several companies
have manufactured thin PDMS supported mem-
branes over the years.
Freeman B, Yampolskii Y, Pinnau I (2006) Materials
science of membranes for gas and vapor separation.
Wiley, Chichester
Mark JE (2009) Polymer data handbook, 2nd edn. Oxford
University Press, Oxford
Nahmias Y, Bhatia SN (2009) Microdevices in biology
and medicine. Artech House, Norwood
Ratner BD, Hoffman AS, Schoen FJ, Lemons JE
(1996) Biomaterials science: an introduction to mate-
rials in medicine. Elsevier Science, Amsterdam
Vane L (2005) A review of pervaporation for product
recovery from biomass fermentation processes.
J Chem Technol Biotechnol 80:603–629
Volkov AV, Korneeva GA, Tereshchenko GF
(2008) Organic solvent nanofiltration: prospects and
application. Russ Chem Rev 77:983–993
P
Polydimethylsiloxane Membrane
George Dibrov
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
Poly(dimethylsiloxane) [PDMS] is often
referred to as the “silicone rubber.” In the
PDMS structure (Fig. 1), the (–Si–O–Si–) back-
bone is highly flexible compared to many other
rubbery polymers, and interactions between the
individual PDMS segments are relatively weak.
Consequently, PDMS has one of the lowest
glass-transition temperatures for polymers of
127  C, which allows long-range segmental
motions even at very low temperatures resulting
in one of the lowest diffusivity selectivity for
permeation.
PDMS can be used to fabricate hollow fiber;
tubular, unsupported sheet; or thin layer-
supported sheet membranes. PDMS also has
very interesting properties as a membrane mate-
rial, and these properties have been utilized for a
long time in membrane technology practice. Sil-
icone rubber is extremely permeable and has
adequate vapor/inert gas selectivity for the most
applications (Table 1). The values may vary for
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1401-1
different types of prepolymer solution and cross-
linking agent and the chosen ratio. Mixed gas
permeabilities deviate from the pure gas
permeabilities.
The differences in permeability of vapor
molecules through PDMS are mostly governed
by their solubility coefficients rather than their
diffusivity coefficients. Penetrant solubility in
rubbery polymers frequently increases with
pressure, particularly for organic vapor pene-
trants, leading to a corresponding increase in
permeability. As a result of the interaction
between these factors, the permeability coeffi-
cients of low-sorbing penetrants, such as H2,
which do not plasticize PDMS and have essen-
tially pressure-independent solubility coeffi-
cients, decrease very slightly with increasing
penetrant pressure. In contrast, the permeabil-
ity coefficients of more soluble penetrants, such
as C3H8, which induce significant plasticization
and have solubility coefficients that also
increase with pressure, increase with increasing
pressure (Merkel et al. 2000).
PDMS is the current benchmark hydrophobic
pervaporation membrane material used, for
instance, in the removal of VOC components
from aqueous streams. Several companies have
manufactured thin PDMS-supported membranes
over the years. At present, Membrane
2 Polydimethylsiloxane Membrane

Polydimethylsiloxane to 10. Butanol–water separation factors for

Membrane, Fig. 1 The CH3
PDMS also cover a fairly broad range, from
chemical structure of the
poly(dimethylsiloxane)-
40 to 60. PDMS will, at least for the near term,
Si−O
repeating unit continue to be the dominant organic membrane
material for the recovery of alcohols from water
CH3
n (Vane 2005).
PDMS coatings are applied on a large scale in
solvent-resistant nanofiltration to separate low
Polydimethylsiloxane Membrane, Table 1 Perme-
ability and selectivity data of different gasses and vapors in molecular weight components from solvents
PDMS RTV 615 (General Electric), measured at 40  C such as toluene. PDMS coatings are applied to
(Blume et al. 1991). 1 barrer = 1
10 10 cm3(STP)
cm
plug defects in gas separation membranes. In all
(cm
sec
cmHg) 1 these examples, the high permeability of PDMS
Permeability, Ideal selectivity is exploited (de Jong et al. 2006).
Gas/vapor barrer over N2
N2 280 –
O2 600 2
CO2 3200 12 References
H2O 23,000 80
C2H5OH 45,000 160 Blume I, Schwering PJF, Mulder MHV, Smolders CA
Chloroform 283,000 1000 (1991) Vapour sorption and permeation properties of
poly(dimethylsiloxane) films. J Membr Sci 61:85–97
Toluene 1,460,000 5200
de Jong J, Lammertink RGH, Wessling M (2006) Mem-
branes and microfluidics: a review. Lab Chip
6:1125–1139
Merkel TC, Bondar VI, Nagai K, Freeman BD, Pinnau
I (2000) Gas sorption, diffusion, and permeation in
Technology and Research (MTR), Inc., of Menlo poly(dimethylsiloxane). J Polym Sci B 38:415–434
Park, CA, is the leading supplier, manufacturing Vane LM (2005) A review of pervaporation for product
spiral wound modules out of their supported sil- recovery from biomass fermentation processes.
icone rubber membranes. Ethanol–water separa- J Chem Technol Biotechnol 80:603–629
tion factor for PDMS membranes ranges from 4.4
L
Liquid Permeability
Alexey Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences (TIPS
RAS), Moscow, Russian Federation
Liquid permeability is a liquid flux normalized by
driving force – applied pressure difference across
the membrane. Liquid permeability can be
expressed in volumetric or gravimetric
units – [l/(m2
h
bar)] or [kg/(m2
h
bar)], respec-
tively. This parameter is used to characterize the
membrane productivity and passage of pure sol-
vent or solution, in liquid separation process such
as micro-, ultra-, and nanofiltration, reverse and
forward osmosis, or hybrid processes like mem-
branes for fuel cell. For commercial membranes
liquid permeability is usually given by manufac-
turers along with value of molecular weight cut-
off (MWCO); the last one is characterized the
ability of the membrane to reject the solutes
with certain molecular weight. Since it is already
normalized by driving force of the process, liquid
permeability shall be most likely constant value
for specific membrane in certain range of oper-
ated pressures at constant feed composition and
temperature. Due to its uniformity, this parameter
allows to compare performance of diverse num-
ber of membranes between each other, tested in
accordance with different filtration protocols.
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1402-1
In some cases, the liquid permeability can be a
function of transmembrane pressure, especially if
the membrane material of top layer has a notice-
able affinity to the solvent like for organic solvent
nanofiltration. Then, increase of pressure differ-
ence across the membrane could lead to partial
compaction of swollen polymer matrix resulting
in some decline of liquid permeability (Volkov
et al. 2008). This is typically a reversible effect,
and the membrane recovers its transport proper-
ties, while the pressure is reduced again. How-
ever, if it is accompanied by collapsing of the
membrane porous structure or transformation of
membrane morphology (e.g., as a result of chem-
ical cleaning), the change in liquid permeability
is irreversible. In a case of membrane fouling,
there could be a combination of reversible and
irreversible decline in liquid permeability, and
partial recovery of membrane performance is
possible after regeneration stage (Drioli and
Giorno 2010).
Liquid permeability can be determined from
filtration experiments in dead-end or cross-flow
regimes. Ideally, no difference between two
regimes shall be expected for filtration of pure
solvents or dilute solutions of solutes with no
specific interaction with membrane material.
Meanwhile, it is preferable to carry out the filtra-
tion test in cross-flow membrane cell with high
linear velocity in order to minimize concentration
polarization effect or membrane fouling during
the filtration of real mixtures (e.g., ground or
wastewater).
2 Liquid Permeability

References Volkov AV, Korneeva GA, Tereshchenko GF

(2008) Organic solvent nanofiltration: prospects and
Drioli E, Giorno L (2010) Comprehensive membrane sci- applications. Russ Chem Rev 77:983–993
ence and engineering, vol 1. Elsevier, Kidlington
M
Membrane Collapsing
Alexey Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis Russian Academy of Sciences
(TIPS RAS), Moscow, Russian Federation
Membrane collapsing is irreversible changing in
the membrane structure (porous structure) as a
result of external factors. Membrane collapsing is
mostly typical for the membranes with a porous
structure that artificially forms during the mem-
brane casting (e.g., by phase inversion). Mem-
brane collapsing can take place mainly in two
following cases: (i) drying or non-proper replace-
ment of solvent/non-solvent contained in the
membrane and (ii) high transmembrane pressure
that exceeds mechanical stability of used mem-
brane material. The former one is mostly typical
for NF or RO membranes. To preserve a fine
(porous) structure of selective layer, RO/NF
membranes are commonly impregnated by non-
volatile solvent like glycerin or supplied in a wet
state (in preserve solution) (Mallevialle and
Odendaal 1996). Once the membrane is dried,
the membrane cannot retrieve its initial filtration
characteristics due to dramatic irreversible
changes within the structure of selective layer.
Therefore, the membranes are installed in a wet
state and then preserve agent is washed out during
filtration of pure water (membrane pretreatment).
If the membrane should be operated in
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1403-2
nonaqueous media, it is recommended to replace
the preserve solution by a number of solvents or
its mixtures in order to provide stepwise change
of solvent surface tension. Non-proper solvent
exchange could lead to noticeable deviation in
membrane performance (Volkov et al. 2008).
Since the porous structure of the selective or
support layers could have a limited mechanical
stability, the membrane manufacturers usually
provide the information about the maximum
transmembrane pressure at which the membrane
still exhibits the claimed characteristics. It should
be mentioned that increase of polymer segments
mobility (e.g., transition from glassy to rubbery
state) or membrane swelling (polymer plasticiza-
tion) may also lead to membrane collapsing; it is
commonly observed for high-pressure gas sepa-
ration or organic solvent nanofiltration (Nunes
and Peinemann 2006). Figure 1 illustrates typical
example of collapsing of membrane porous struc-
ture as a result of applying of high transmem-
brane pressure that exceeds the mechanical
stability of the support layer.
In a case of the polymer with intrinsic micro-
porosity, the change in porous structure is
referred as partial relaxation of free-volume
structure also called as a physical aging. Mem-
brane can be also collapsed as a whole construc-
tion if high pressure is applied on shell side
(outside) of hollow fiber membrane.
2 Membrane Collapsing

Membrane Collapsing, Fig. 1 Collapsing of membrane porous structure: initial membrane (left), collapsed mem-
brane after TMP of 20 bar (right)

References Nunes SP, Peinemann K-V (2006) Membrane technology:

in the chemical industry. WILEY-VCH, Wenheim
Mallevialle JA, Odendaal PE (1996) Water treatment Volkov AV, Korneeva GA, Tereshchenko GF (2008)
membrane processes. American Water Works Associ- Organic solvent nanofiltration: prospects and applica-
ation, Denver tions. Russ Chem Rev 77:983–993
M
Membrane Compaction
Alexey Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Federation, Russian Academy
of Sciences (TIPS RAS), Moscow, Russia
Membrane compaction can be considered as a
compression of the membrane under applied
pressure resulting in decline of transport charac-
teristics of the membrane. Membrane compac-
tion is quite commonly observed phenomena,
especially decrease of initial membrane transport
parameters in pressure driving processes like gas
separation or membrane filtration. Typically,
increase pressure drop across the membrane
leads to more pronounced effect of membrane
compaction. If the membrane is already
compacted at the operated pressure, steady-state
performance can be expected. However, the flux
decline over the time can be also attributed to
membrane fouling, which is known as a partial
blockage of membrane surface and/or pores
inside of the membrane by components of the
feed. Unfortunately, it is difficult to distinguish
the effect of membrane compaction from mem-
brane fouling, especially, during the operation
with multicomponent mixtures.
For minimization of the time required for pre-
liminary membrane compaction, it is
recommended to start experiment with the
highest pressure and then stepwise decrease the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1404-2
transmembrane pressure. Membrane compaction
cannot be avoided, but its effect on membrane
performance can be controlled; moreover, the
initial membrane compaction has a greater
impact on the membrane. From this end, the
membrane manufactures quite often provide the
protocol of preliminary membrane conditioning
that has to be followed in order to guarantee
claimed membrane characteristics.
Membrane compaction as a physical compres-
sion can have reversible, partially reversible or
irreversible effect on membrane structure. The
membrane collapsing is one of the examples of
irreversible membrane compaction, and this
effect is attributed to mechanical destruction of
porous structure of the membrane as a result of
applied pressure. Increase of polymer segment
mobility (e.g., transition from glassy to rubbery
state) or membrane swelling (polymer plasticiza-
tion) may also lead to more pronounced effect of
membrane compaction under applied pressure; it
is commonly observed for high-pressure gas sep-
aration or organic solvent nanofiltration (Nunes
and Peinemann 2006). Figure 1 illustrates an
example of reversible membrane compaction,
when the membrane is recovering its transport
properties with a decrease of the transmembrane
pressure; as can be seen, the normalized liquid
permeability is a function of pressure here.
2 Membrane Compaction

Membrane Compaction, 40
Fig. 1 Effect of reversible
membrane compaction on
the ethanol permeability
through dense membrane of

PEtOH, 10−7 kg·m/m2·h·bar

30
PTMSP: three filtration
series in which the
transmembrane pressure
was reduced from 200 (■),
20
150 (●), or 100 bar (~),
respectively (Grekhov
et al. 2012)

10

0
0 50 100 150 200
Pressure, bar

References measurements in a wide range of trans-membrane

pressures. J Membr Sci 390–391:160–163
Grekhov A, Belogorlov A, Yushkin A, Volkov A (2012) Nunes SP, Peinemann K-V (2006) Membrane technology:
New express dynamic technique for liquid permeation in the chemical industry. WILEY-VCH, Wenheim
P
Pressure Decay Method
Alexey Volkov
A.V. Topchiev Institute of Petrochemical
Synthesis, Russian Federation, Russian Academy
of Sciences (TIPS RAS), Moscow, Russia
Pressure decay method is one of the standard
experimental techniques for characterization of
membranes and membrane materials in terms of
sorption, diffusivity, or permeance; this method
has a rather high sensitivity (Ferrari et al. 2010;
Mulder 1996). The principle of this method is
based on estimation of amount of molecules
sorbed or permeated through the membrane by
monitoring of pressure decay in a chamber with a
constant known volume, where the membrane is
placed. The amount of gas or vapor sorbed by
membrane material at a given pressure is deter-
mined by the difference between initial and
actual pressures; for sorption experiments, the
actual pressure is equilibrium one. Mass flow
through the membrane is determined by monitor-
ing of pressure decay in a chamber above the
membrane with a constant volume (upstream
side) in time. This technique is more commonly
used for measurement of gas transport due to
higher values of compression coefficients, and
the schematic view of this experimental setup is
shown in Fig. 1.
If the volume of upstream side Vupstream is
already calibrated and known, the mole flow of
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1405-1
the gas J through the membrane surface A over
the time period Dt can be described as a function
of pressure drop in the following equation with
approximation of ideal gas law:

V upstream
Dp
J mole=m2
h ¼
R
T
A
Dt
where R is universal gas constant and T is tem-
perature. The method accuracy can be improved
by avoiding any temperature fluctuations (e.g., in
case of gas expansion) during single measure-
ment and proper selection of highly sensitive
and accurate pressure indicator(s) for required
pressure range.
The drawback of this method is that the driv-
ing force across the membrane is continuously
changing during the single test since the upstream
side is isolated from the gas supply. However, it
is possible to consider a constant transmembrane
pressure difference if the pressure drop for single
test is negligible in comparison with absolute
pressure in upstream side. On the other hand,
such a pressure drop value should be sufficiently
high enough to eliminate the undesired effect of
temperature fluctuation and instrumental noise.
From this end, the upstream side typically
includes two or more vessels with different cali-
brated volumes (see Fig. 1), so the overall volume
can be adjusted by connecting one of the vessels
or its combination to the main line in order to
measure the membranes with different
2 Pressure Decay Method
V2
PI V3
V1
Upstream
Downstream
Pressure Decay Method, Fig. 1 Schematic view of
experimental setup to measure gas flow with pressure
decay method: PI pressure indicator, V1 calibrated volume
of pipelines and fittings, V2 calibrated vessel volume, V3
calibrated vessel volume
permeance at the same experimental setup within
desired experimental error.
Pressure decay method is also used as a rapid
test for evaluation of the integrity of micro- and
ultrafiltration membranes as well as membrane
modules (AWWA Staff 2005). The upper side of
wetted membrane is pressurized with a gas,
which is below its bubble point pressure. Broken
membrane or not proper sealing would be indi-
cated by noticeable rate of pressure decay.
Recently, a new self-calibration technique based
on principles of pressure decay method was pro-
posed for the express determination of liquid flux
through flat-sheet membranes in a pressure range
of 30–150 bar (Grekhov et al. 2012).
References
AWWA Staff (2005) Microfiltration and ultrafiltration
membranes for drinking water, 1st edn. American
Water Works Association
Ferrari MC, Galizia M, De Angelis MG, Sarti GC
(2010) Vapor sorption and diffusion in mixed matrices
based on Teflon AF 2400. In: Freeman B, Yampolskii
Y (eds) Membrane gas separation. Wiley, New York,
pp 125–142
Grekhov A, Belogorlov A, Yushkin A, Volkov A (2012)
New express dynamic technique for liquid permeation
measurements in a wide range of trans-membrane
pressures. J Membr Sci 390–391:160–163
Mulder M (1996) Basic principles of membrane technol-
ogy. Kluwer, Dordecht/Boston/London
S
Solvent Swollen Polymer
Annarosa Gugliuzza
Institute on Membrane Technology - Research
National Council, ITM-CNR, Rende (CS), Italy
Swollen polymers are classically named as gels,
although the nature of the dissolved solvent
allows distinguishing between three main classes
of compounds: aerogel or xerogel when the net-
work spaces are full of air, hydrogel, and organic
gel when embedding water or oil. The swelling is
defined as a penetration of a solvent into the
polymer network that causes an abrupt change
in the volume (Gugliuzza and Drioli 2007), mov-
ing the boundary from unsolvated glassy region
to solvated and expanding rubbery domain. This
event occurs when there are unbalanced osmotic
forces and viscoelastic restoring forces, while it is
stopped when these forces reach the equilibrium.
The opposite event is when the solvent releases
from the polymer matrix, thereby causing
deswelling.
Both the neutral and ionic polymers can swell,
and different forces can take place during expan-
sion, such as hydrophilic/hydrophobic and/or
ionic interactions. The degree of crystallinity,
cross-linking, as well as the strength of attractive
and repulsive forces can seriously affect the
intensity of the swelling (Flory and Rehner
1943).
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1407-2
Thermodynamically, the behavior of a swol-
len polymer can be described by the total free
energy (DGtotal), expressed as the sum of the free
energy of mixing (DGmix) and the elastic free
energy (DGel). An additional energetic term,
such as the ionization free energy (DGion), must
be also included when the polymer is a polyelec-
trolyte. Kinetically, the swelling event can be
studied on the basis of the solvent diffusion rate
and can be classified as Fickian or non-Fickian
depending on the polymer chain relaxation
(Crank and Park 1951). In a Fickian diffusion,
the solvent rate is usually slower than relaxation
rate of the segment chains (Case I transport),
while in a non-Fickian diffusion, the solvent
moves quicker than chain relaxation (Case II
transport) or with a comparable rate (anomalous
transport) (Berens and Hopfenberg 1978).
A somewhat simplified and empirical equa-
tion to study the diffusion through the polymers is
Mt
¼ ktn (1)
M1
where Mt and M1 are the mass uptake at time t
and equilibrium, t and n are constants related to
polymer-solvent systems. The type of diffusion
can be established from the diffusional constant
n. Value equal to 0.5 indicates Fickian diffusion;
0.5 < n < 1.0 values are typical of anomalous
transport, while values equal to 1 are estimated
for Case II transport.
2 Solvent Swollen Polymer
Better models have been proposed to study the
non-Fickian diffusion. The following relation has
been, for example, proposed for systems wherein
Mt/M1 ratio is 0.60 (Crank and Park 1951):
Mt
reversibly be controlled (Chaterji et al. 2007;
¼ 1  Aek2 t (2)
M1
A is a constant and is calculated together with k2
from the slopes and intercepts of the plot of ln
(1-Mt/M1) versus time t at times later than those
corresponding to Mt/M = 0.60.
Instead, relation 3 well describes the anoma-
lous transport:
Mt 1 redefining the limits of biomedical devices. Prog
¼ k 1 t þ k 2 t2 (3)
M1
where K1t expresses the relaxation-controlled
process, while k2t1/2 quantifies the dependence
of the transport on diffusion.
A discontinuity of the volume transition can
be observed in many gels, thereby leading the
polymer from a swelled to a shrunk state and
vice versa, depending on the predominance of
unbalanced hydrophobic/hydrophilic and/or
ionic forces. Formation or destruction of
hydrogen bonding as well as the interactions
with counterions in specific chemical environ-
ments can decide the expansion or the collapse
of the polymer network, making smart gels/mem-
branes whereby a transport phenomenon can
Diaconu et al. 2012).
References
Berens AR, Hopfenberg HB (1978) Diffusion and relaxa-
tion in glassy polymer powders: 2. Separation of dif-
fusion and relaxation parameters. Polymer
19:489–496
Chaterji S, Kwon IK, Park K (2007) Smart polymeric gels:
Polym Sci 32(8–9):1083–1122
Crank J, Park GS (1951) Diffusion in high polymers: some
anomalies and their significance. Trans Faraday Soc
47:1072–1084
Diaconu G, Gugliuzza A, Schäfer T (2012) Characteriza-
tion of PAA/PDDA-based stimuli responsive mem-
branes. Procedia Eng 44:1260–1261
Flory PJ, Rehner J (1943) Statistical mechanics of cross-
linked polymer networks II. Swelling. J Chem Phys
1:521–527
Gugliuzza A, Drioli E (2007) PVDF and HYFLON AD
membranes: ideal interfaces for contactor applications.
J Membr Sci 300:51–62
M
Membranes for Seawater
Desalination
Davide Mattia
Department of Chemical Engineering, University
of Bath, Bath, UK
Membranes for seawater desalination include
several different membrane types based on the
diverse technologies used to produce drinkable
water from seawater.
Conventional seawater desalination technolo-
gies include multistage flash, multi-effect distil-
lation, and vapor compression (collectively
known as thermal desalination) and ion
exchange. Membrane-based seawater desalina-
tion processes include reverse osmosis
(RO) where the saline feed is forced through a
semipermeable membrane under an external
pressure gradient, forward osmosis (FO) where
water permeates through a semipermeable mem-
brane due to a concentration gradient, and elec-
trodialysis where ions permeate through anionic
and cationic semipermeable membranes under an
external electric field.
Currently, reverse osmosis (RO) plants
account for about 70 % of installed plants world-
wide, with thermal desalination totaling around
30 % and electrodialysis and ion exchange less
than 5 %. Total desalination installed capacity
amounts to about 108 m3/day, equivalent to
about 1 % of the water supply worldwide.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1413-1
Economic analyses have shown that RO plants
are competitive compared to thermal installations
(Abou Rayan and Khaled 2003), with higher
rejection of most solutes, except boron (Cotruvo
et al. 2010). This advantage has been further
increased in more recent plants with the installa-
tion of energy recovery devices and more effi-
cient pumps (Fritzmann et al. 2007).
Reverse osmosis membrane technology has
significantly evolved from the first products in
the 1950s in terms of materials, form, and mod-
ules (Lee et al. 2011). Today, the RO membrane
market is dominated by thin-film composite
(TFC) membranes consisting of a support layer
with large porosity, a microporous interlayer, and
a thin selective layer on the upper surface facing
the saline feed. This complex structure ensures
not only robustness but also ease of processabil-
ity. Furthermore, it has enabled the use of inter-
facial polymerization methods to reduce the
thickness of the selective layer to minimize trans-
port resistance. The material of the selective bar-
rier layer is generally made of aromatic
polyamides, with significant research and com-
mercial investments in finding other suitable
polymer compositions. Surface modification of
the selective layer is extensively employed to
increase chemical resistance and reduce fouling.
Most commercial RO membranes are sold in
the spiral wound module configuration, which
offers high specific membrane surface area, ease
of scale-up, and interchangeability, and can be
easily produced from flat sheet TFC membrane
2 Membranes for Seawater Desalination
(Pearce 2007). Larger modules can also reduce
operating and capital costs (Ng et al. 2008), with
16- and 18-in. modules now being offered on the
market.
RO membranes require extensive
pretreatment steps to remove solids, organic
foulants, and, in some cases, chlorine. RO mem-
branes operate at pressures varying from 40 to
70 bar to overcome the osmotic pressure of the
saline feed and resistance due to concentration
polarization buildup over time. Due to the high
pressures applied, RO membranes suffer from
compaction as well as significant fouling buildup
over time. These factors all contribute to the high
energy cost of operating RO plants, despite sig-
nificant innovation in the last 50 years which has
brought RO operations close to the thermody-
namic limit (Elimelech and Phillip 2011).
Forward osmosis as a desalination method was
first proposed in the 1970s, but the first industrial
FO plant has opened only in 2012 in Oman. FO
uses a draw solution that has a higher osmotic
pressure than seawater to extract water from the
saline feed into the draw solution through a semi-
permeable membrane. Intense research and
development is now being focused on novel
membranes and draw solutions. Membranes for
FO differ from those for RO mainly due to effects
of concentration polarization and the need to
prevent reverse draw solute permeation. Cellu-
lose acetate membranes, originally developed for
RO, have made a comeback for FO uses, partic-
ularly due to their hydrophilic surface and good
chemical stability (Alsvik and Hägg 2013).
A combination of the two techniques has been
recently proposed (Klaysom et al. 2013), though
its economic viability and social acceptance are
uncertain (Elimelech and Phillip 2011). In this
FO-RO hybrid system, wastewater is used as feed
in a first FO unit with seawater used as draw
solution. The latter is, therefore, diluted before
entering the RO stage. The RO concentrate is
then fed to a second FO unit as draw solution
and, as a consequence, diluted before discharge.
To close the cycle, the wastewater feed from the
first FO unit is concentrated, thereby reducing its
discharge volume as well.
In electrodialysis (ED) an external electric
field is used to separate dissolved ions in the
saline feed, riving them to oppositely charged
ions through ion selective membranes. ED sys-
tems consist of a series of cation and anion
exchange membranes separated by spacers
through which the concentrate streams and the
demineralized water separately flow out of the
membrane module. Fouling, which occurs at the
electrodes due to the accumulation of ions, can be
removed by periodical reversal of the electrodes’
polarity.
The charge-based separation mechanism is
effective at removing not just salt ions but also
nitrates and other charged species (Voutchkov
2013). On the other hand, removal of charge
neutral contaminants, such as nutrients or organic
substances, is less effective than RO systems. ED
is economically competitive compared to RO
when TDS of the water source is less than
3,000 mg/L, so far mainly limiting its use to
brackish water desalination.
ED membranes tend to be thicker than RO
ones and prepared mixing an ion exchange resin
with a polymer binder. Requirements for the
selection of the resin and binders are low electri-
cal resistance, resistance to osmotic swelling, and
long life expectancy (Murray 1995). The latter
aspect is crucial as most commercial ED mem-
branes are sold as sealed filter cartridges.
Recent developments and future directions:
Alongside continuous optimization of polymeric
membranes, there is intense research in novel
membrane materials or membrane designs.
A promising area of research is the incorporation
of carbon nanotubes in thin-film composite mem-
branes to enhance permeability with no compro-
mise on salt rejection (Mattia et al. 2014). In fact,
in these RO CNT-TFC membranes, the selectiv-
ity is still determined by the selective layer of the
TFC, whereas the CNTs, embedded in it, provide
a high flux conduit for permeated water mole-
cules. Other nanotube materials, such as boron
nitride and silicon carbide, have shown promise
in molecular dynamic simulations.
Another emerging class of materials for
RO-based desalination is represented by
graphene at its derivative, graphene oxide. Initial
Membranes for Seawater Desalination
reports on desalination using graphene oxide
membranes show high permeability and salt
rejection (Nair et al. 2012), while molecular
dynamic simulations have investigated the possi-
bility of high flux/high rejection through nano-
meter scale defects in a graphene layer (Cohen-
Tanugi and Grossman 2012).
In either case it should be noted that the
increase in permeability promised by these
novel membranes does not automatically trans-
late in a decrease in the energy cost of RO desa-
lination. The latter, in fact, is related to the
pressure gradient across the membrane that, as
discussed, is already close to the thermodynamic
limit. Higher permeability membranes, though,
could reduce the footprint of RO plants and
decrease the amount of chemicals for membrane
cleaning accordingly (Elimelech and Phillip
2011).
Other potential RO membrane materials, at an
earlier developmental stage, include aquaporins
and polymer dendritic structures (Lee
et al. 2011).
Cross-References
▶ Concentration Polarization
▶ Draw Solution
▶ Fouling
▶ Nanotube Membranes
▶ Thin Film Composite Membranes
References
Abou Rayan M, Khaled I (2003) Seawater desalination by
reverse osmosis (case study). Desalination
153(1–3):245–251
3
Alsvik I, Hägg M-B (2013) Pressure retarded osmosis and
forward osmosis membranes: materials and methods.
Polymers 5(1):303–327
Cohen-Tanugi D, Grossman JC (2012) Water desalination
across nanoporous graphene. Nano Lett
12(7):3602–3608
Cotruvo J, Voutchkov N, Fawell J, Payment P, Cunliffe D,
Lattemann S (2010) Desalination technology: health
and environmental impacts. CRC Press, Boca Raton
Elimelech M, Phillip WA (2011) The future of seawater
desalination: energy, technology, and the environ-
ment. Science 333(6043):712–717
Fritzmann C, Löwenberg J, Wintgens T, Melin T (2007)
State-of-the-art of reverse osmosis desalination. Desa-
lination 216(1–3):1–76
IDA Desalination Yearbook (2012–2013) International
desalination association and global water intelligence
Klaysom C, Cath TY, Depuydt T, Vankelecom IFJ
(2013) Forward and pressure retarded osmosis: poten-
tial solutions for global challenges in energy and water
supply. Chem Soc Rev 42(16):6959–6989
Lee KP, Arnot TC, Mattia D (2011) A review of reverse
osmosis membrane materials for
desalination – development to date and future poten-
tial. J Membr Sci 370(1–2):1–22
Mattia D, Lee KP, Calabrò F (2014) Water permeation in
carbon nanotube membranes. Curr Opin Chem Eng
4:32–37
Murray P (1995) Electrodialysis and electrodialysis
reversal – manual of water supply practices, M38.
American Water Works Association, Denver
Nair RR, Wu HA, Jayaram PN, Grigorieva IV, Geim AK
(2012) Unimpeded permeation of water through
helium-leak – tight graphene-based membranes. Sci-
ence 335(6067):442–444
Ng HY, Tay KG, Chua SC, Seah H (2008) Novel 16-inch
spiral-wound RO systems for water reclamation – a
quantum leap in water reclamation technology. Desa-
lination 225(1–3):274–287
Pearce G (2007) Water and wastewater filtration: mem-
brane module format. Filtr Sep 44(4):31–33
Voutchkov N (2013) Desalination engineering – planning
and design. McGraw-Hill, New York
B
Blue Energy
Wang Rong1, S. T. V. Sim2 and Anthony Gordon
Fane2
1
School of Civil and Environmental Engineering,
Singapore Membrane Technology Centre,
Nanyang Environment and Water Research
Institute, Nanyang Technological University,
Singapore, Singapore
2
Singapore Membrane Technology Centre,
Nanyang Environment and Water Research
Institute, Nanyang Technological University,
Singapore, Singapore
Introduction
The energy crisis is becoming one of the most
pervasive problems facing the world today
plagued with rapid economic growth and expo-
nential increase in the global population. The key
solution is sustainable energy that combines
renewable energy with high energy efficiency to
balance the growing energy needs without jeop-
ardizing the earth’s climate. Of great interest is
the potential of “blue energy” associated with
osmotic power that can be harvested from the
salinity gradient between two water streams
such as seawater and freshwater, as seawater is
globally distributed (Lewis et al. 2011), available
all day and all year round. Two emerging mem-
brane techniques, pressure retarded osmosis
(PRO) and reverse electrodialysis (RED), are
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1416-3
the primary methods proposed for recovering
the osmotic energy.
PRO Working Principles
Three osmotic processes are illustrated in Fig. 1:
(a) Reverse osmosis (RO) that utilizes hydraulic
pressure (DP) to overcome the osmotic pres-
sure gradient (Dp) across a semipermeable
membrane (DP > Dp), leading to the net
water movement from the concentrated feed
(F) to the permeate (P) side.
(b) Pressure retarded osmosis (PRO) that applies
a hydraulic pressure lower than the osmotic
pressure gradient to the high-salinity stream
(draw solution (DS)) (DP < Dp), giving a net
water flux in the direction toward the draw
solution.
(c) Forward osmosis (FO) that uses the osmotic
pressure gradient as the driving force without
hydraulic pressure (DP = 0). Water flows
from a less concentrated feed (F) to a more
concentrated draw solution (DS).
PRO is an intermediate osmotic process
between RO and FO. As long as the osmotic
pressure difference across the semipermeable
membrane is greater than the applied pressure
on a high-salinity stream, water will continuously
flow from a low-salinity stream at a low pressure
into the pressurized high-salinity stream. The
increased volume of pressurized water is able to
drive a turbine for power generation (Thorsen
2 Blue Energy

Blue Energy, a b c
Fig. 1 Osmotic processes ΔP ΔP
using semipermeable
membranes: (a) RO; (b)
PRO; (c) FO (arrow
indicates the direction of
water flow)

P F F DS F DS

ΔP > Δπ 0 < ΔP < Δπ Δπ > ΔP = 0

Blue Energy,
Fresh water Fresh water @ low pressure
Fig. 2 Schematic of PRO
process for power
generation membrane
Water flow

Brine
P Diluted
Brine @ high pressure brine
Pump Turbine
generator

et al. 2009), resulting in the recovery of the
chemical potential energy from the difference in
osmotic pressures of the two water streams, as
shown schematically in Fig. 2.
RED Working Principles
Unlike PRO, RED primarily depends on ion
transport through the membranes when waters
of different salinities are placed on opposite
sides of either cation or anion exchange mem-
branes. These membranes are stacked in an alter-
nating pattern between a cathode (reduction
electrode) and an anode (oxidation electrode)
(Post et al. 2007). Another distinctive difference
is that the RED system is not pressurized like
PRO to obtain the osmotic energy mechanically.
Instead, direct electrical energy can be harvested
from the movement of the electrons required to
maintain electroneutrality of the overall solution
as the ions from the saline solution are
transported toward either the anode or cathode
electrodes, as shown schematically in Fig. 3.
Specifically, electroneutrality is maintained
via reduction at the cathode and oxidation at the
anode via an external electric circuit that results
in electrons being transferred from the anode to
the cathode. Electrical energy can then be
harnessed directly when an external load is
connected to the circuit through the electrical
current (movement of electrons) and the potential
difference over the electrodes. Although the
applied electrical potential difference will reduce
the driving force of the ions when the external
load is connected to the circuit, ions will continue
to be transported toward the cathode and anode as
long as the electrochemical potential difference is
greater than the electrical potential difference.
Challenges and Potential Large-Scale
Applications
The PRO process requires a robust membrane
that can withstand high-operating pressures and
achieve a reasonable high water flux (Chou
et al. 2012), while RED requires not only a mem-
brane of minimal electrical resistance but also the
whole stack design with a low electrical resis-
tance. Normally, seawater and freshwater are
used as a pair for both PRO (Lewis et al. 2011;
Thorsen et al. 2009; Ramon et al. 2011) and RED
(Ramon et al. 2011; Długołecki et al. 2010) pro-
cesses to harvest salinity gradient energy. Other
salinity gradient pairs such as concentrated brine
from seawater desalination (Enomoto et al. 2010)
or hypersaline lakes such as the Dead Sea (Loeb
Blue Energy
e−
Less Saline Solution
(River water)
C
External
Load
A
Less Saline Solution
(River water)
e−
Blue Energy, Fig. 3 A simple RED process showing the transport of ions where A is an anion exchange membrane and
C is a cation exchange membrane
1976, 2001; Lacey 1980) are also possible
resources for utilization. It is expected that
large-scale applications for PRO and RED
would be near river estuaries, hypersaline lakes,
or seawater desalination plants. In particular, the
co-location of PRO/RED with seawater desalina-
tion plants would allow the recovered energy
from the RO brines to be used to desalinate the
water.
In the oil and gas and mining industries, large
amounts of water streams with high total
dissolved salts (TDS) are produced from the
hydraulic methods used in the harvesting of gas
from coal beds (McBeth et al. 2003), oil from
subsurface formation (Ahmadun et al. 2009), or
from mining activities (Balaba and Smart 2012).
Thus, the recovery of osmotic energy from such
produced water streams is also possible for large-
scale applications.
References
Ahmadun F-R, Pendashteh A, Abdullah LC, Biak DRA,
Madaeni SS, Abidin ZZ (2009) Review of technolo-
gies for oil and gas produced water treatment, J Hazard
Mater 170:530–551
Balaba RS, Smart RB (2012) Total arsenic and selenium
analysis in Marcellus shale, high-salinity water, and
hydrofracture flowback wastewater, Chemosphere
89:1437–1442
3
Cathode Electrode
Na+ Cl− Na+ Cl− Saline Solution
(Sea water)
Anode Electrode
Chou S, Wang R, Shi L, She Q, Tang CY, Fane AG
(2012) Thin-film composite hollow fiber membranes
for pressure retarded osmosis (PRO) process with high
power density, J Membr Sci 389:25–33
Długołecki P, Da˛browska J, Nijmeijer K, Wessling
M (2010) Ion conductive spacers for increased power
generation in reverse electrodialysis, J Membr Sci
347:101–107
Enomoto H, Fujitsuka M, Hasegawa T, Kuwada M,
Tanioka A, Minagawa M (2010) A feasibility study
of pressure-retarded osmosis power generation system
based on measuring permeation volume using reverse
osmosis membrane, Electr Eng Jpn 173:1129–1138
Lacey RE (1980) Energy by reverse electrodialysis, Ocean
Eng 7:1–47
Lewis A, Estefen S, Huckerby J, Musial W, Pontes T,
Torres-Martinez J (2011) In: Edenhofer O, Pichs-
Madruga R, Sokona Y, Seyboth K, Matschoss P,
Kadner S, Zwickel T, Eickemeier P, Hansen G,
Schlomer S, Stechow CV (eds) IPCC special report on
renewable energy sources and climate change mitiga-
tion. Cambridge University Press, Cambridge/New York
Loeb S (1976) Production of energy from concentrated
brines by pressure-retarded osmosis: I. Preliminary
technical and economic correlations, J Membr Sci
1:49–63
Loeb S (2001) One hundred and thirty benign and renew-
able megawatts from Great Salt Lake? The possibili-
ties of hydroelectric power by pressure-retarded
osmosis, Desalination 141:85–91
McBeth IH, Reddy KJ, Skinner QD (2003) Chemistry of
trace elements in coalbed methane product water,
Water Res 37:884–890
Post JW, Veerman J, Hamelers HVM, Euverink GJW,
Metz SJ, Nymeijer K, Buisman CJN (2007) Salinity-
gradient power: Evaluation of pressure-retarded osmo-
sis and reverse electrodialysis, J Membr Sci
288:218–230
4 Blue Energy

Ramon GZ, Feinberg BJ, Hoek EMV (2011) Membrane- Thorsen T, Holt T (2009) The potential for power
based production of salinity-gradient power, Energy production from salinity gradients by pressure retarded
Environ Sci 4:4423–4434 osmosis, J Membr Sci 335:103–110
F
Forward Osmosis Membrane Reactor as reverse osmosis (RO) or membrane distillation
1,2 2
Rong Wang , Laurentia Setiawan and Anthony
Gordon Fane2
1
School of Civil and Environmental Engineering;
Singapore Membrane Technology Center,
Nanyang Environment and Water Research
Institute; Nanyang Technological University,
Singapore, Singapore
2
Singapore Membrane Technology Center,
Nanyang Environment and Water Research
Institute, Nanyang Technological University,
Singapore, Singapore
Introduction
The forward osmosis membrane bioreactor
(FOMBR) is a new type of membrane bioreactor
(MBR) technology, which combines two basic
processes – biological degradation of organic
wastes and membrane separation using forward
osmosis (FO) – into a single process for various
wastewater treatments (Zhang et al. 2012). Spe-
cifically, in a FOMBR, suspended solids and
microorganisms responsible for biodegradation
are separated from the treated water using a FO
membrane module, where water is extracted from
the mixed liquor through a semipermeable FO
membrane to a high osmotic pressure draw solu-
tion (Achilli et al. 2009). The output from the
FOMBR is a mixture of treated water permeate
and the draw solution. A posttreatment step, such
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1417-2
(MD), can be used to produce purified water and
to regenerate the draw solution.
Compared with conventional MBRs, where
pressure-driven membrane filtration units are
used, the FOMBR enjoys important advantages
including potentially lower energy requirement
and better water quality, because the separation
does not entail the use of hydraulic pressure, and
the salt-rejecting dense membrane is an absolute
barrier to suspended solids and also retains
organic species. In addition, the use of the dense
membrane allows retention of recalcitrant
organics which are eventually degraded, as
organic retention time (ORT) can be significantly
longer than the hydraulic retention time (HRT).
A greatly enhanced removal of micropollutants is
also expected, which is a distinct advantage if the
effluent is considered for reclamation and reuse.
Configurations of FOMBR
Similar to conventional MBRs, the FOMBR can
be operated under two configurations. One is the
submerged FOMBR as shown schematically in
Fig. 1 and the other is side-stream FOMBR, as
illustrated in Fig. 2 (Yap et al. 2012). In both
configurations, the driving force for water trans-
fer is the osmotic pressure gradient across a salt-
rejecting dense membrane. When water is
extracted into the draw solution, the diluted
draw solution is, subsequently, sent to a
2 Forward Osmosis Membrane Reactor

Forward Osmosis Purified water

Membrane Reactor,
Fig. 1 Submerged
FOMBR
Draw solution
Feed Draw regeneration
solution process

FO membrane
module
Diluted draw
solution
Air
Sludge

Retentate

Purified water
Wastewater
in
Draw
solution
Feed Draw solution
Air
regeneration process

Bioreactor FO membrane

Sludge out Diluted draw solution

Forward Osmosis Membrane Reactor, Fig. 2 Side-stream FOMBR

regeneration device (e.g., RO or MD) to recover Firstly, an appropriate membrane is essential to

the purified water. The commonly used FO mem-
brane has an RO-like or nanofiltration (NF)-like
selective layer that has high rejection toward
organic/inorganic compounds in the wastewater
including ions. Normally two-phase flow around
fiber bundles (for a hollow fiber module) or
between vertical flat plates (for a flat sheet mem-
brane module) by air scouring is used to control
membrane fouling and module blocking.
Major Challenges for Large-Scale
Applications
There are three major technical challenges that
impede large-scale applications of FOMBRs.
improve the performance of the FOMBR. Com-
monly used FO membranes consist of a dense-
selective layer supported by a porous substrate.
The membrane should exhibit high water flux and
high salt rejection and be able to limit feed-side
fouling and internal concentration polarization
(ICP), which is a unique phenomenon in the for-
ward osmosis process, causing the reduction of the
effective osmotic driving force. The strategy to
overcome the problem is to design the support
layer of the FO membrane as thin and porous as
possible to reduce mass transfer resistance, and
thus, less severe ICP is expected (Wang
et al. 2010). Fouling is a common issue in a con-
ventional MBR as the wastewater is a complex
system containing microorganisms, extracellular
Forward Osmosis Membrane Reactor
polymeric substances (EPS), and soluble macro-/
microorganics and inorganics. FOMBR, on the
other hand, has an additional potential scaling
issue caused by inorganic salts due to solute accu-
mulation (Zhang et al. 2012).
Secondly, the bioprocess must be optimized to
handle accumulated recalcitrant organics, nutri-
ents, and elevated salt concentrations, as the FO
membrane possesses a dense-selective layer with
high retentions to the organic species and salts.
The accumulation of organic matters improves
the biological degradation which may enhance
the removal of micropollutants. The salt accumu-
lation, however, (i) could have adverse effects on
biological treatment and cause microbial inhibi-
tion (Zhang et al. 2012; Nawaz et al. 2013);
(ii) reduces the osmotic driving force available,
resulting in the reduction of water flux; and (iii)
increases the concentration of sparingly soluble
salts, and spontaneous chemical precipitation
may occur when the saturation limits are
exceeded, leading to scaling on the FO
membranes.
The third challenge relates to draw solute
selection and regeneration. A proper draw solu-
tion is necessary to provide high osmotic pressure
and low salt back diffusion (Cath et al. 2006).
When the salts from the draw solution diffuse to
the feed tank, the driving force will be reduced,
3
leading to flux decline and toxic effects on the
microbial community. In addition, the draw solu-
tion must be able to be regenerated easily and
economically for reuse (Cornelissen et al. 2008).
References
Achilli A, Cath TY, Marchand EA, Childress AE
(2009) The forward osmosis membrane bioreactor: a
low fouling alternative to MBR processes. Desalina-
tion 239:10–21
Cath TY, Childress AE, Elimelech M (2006) Forward
osmosis: principles, applications, and recent develop-
ments. J Membr Sci 281:70–87
Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin
J-J, Oo H, Wessels LP (2008) Membrane fouling and
process performance of forward osmosis membranes
on activated sludge. J Membr Sci 319:158–168
Nawaz MS, Gadelha G, Khan SJ, Hankins N (2013)
Microbial toxicity effects of reverse transported draw
solute in the forward osmosis membrane bioreactor
(FO-MBR). J Membr Sci 429:323–329
Wang R, Shi L, Tang CY, Chou S, Qiu C, Fane AG
(2010) Characterization of novel forward osmosis hol-
low fiber membranes. J Membr Sci 355:158–167
Yap WJ, Zhang J, Lay WCL, Cao B, Fane AG, Liu
Y (2012) State of the art of osmotic membrane bio-
reactors for water reclamation. Bioresour Technol
122:217–222
Zhang J, Loong WLC, Chou S, Tang C, Wang R, Fane AG
(2012) Membrane biofouling and scaling in forward
osmosis membrane bioreactor. J Membr Sci
403–404:8–14
H
High-Rejection Seawater Reverse
Osmosis Membrane
Tzyy Haur Chong1, Rong Wang1 and Anthony
Gordon Fane2
1
Singapore Membrane Technology Center,
Nanyang Environment and Water Research
Institute; School of Civil and Environmental
Engineering, Nanyang Technological University,
Singapore, Singapore
2
Singapore Membrane Technology Center,
Nanyang Environment and Water Research
Institute, Nanyang Technological University,
Singapore, Singapore
Introduction
Seawater desalination to convert seawater to
potable water by reverse osmosis
(RO) membranes has become a pivotal technol-
ogy to meet the increasing water demand. The
RO membrane has a unique property that allows
passage of water with little hindrance while
presenting a virtually impermeable barrier to
salts and other components. Over the years, it
has evolved from the first-generation asymmetric
cellulose acetate (CA) membrane to the current
generation thin film composite (TFC) membranes
with better salt retention and higher water perme-
ability, which has significantly improved the
water quality and reduced the energy consump-
tion and costs of seawater desalination.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1418-1
Structure of TFC RO Membrane
and Separation Mechanism
TFC RO membrane, prepared using interfacial
polymerization technique, is composed of an
active skin layer (thickness 200 nm and pore
size of <0.1 nm) commonly made from cross-
linked aromatic polyamides, a polysulfone
porous support layer (thickness 50 mm), and a
polyester nonwoven fabric substrate (thickness
100 mm), as shown in Fig. 1 (Kurihara and
Tomioka 2010; Uemura et al. 2012).
The active layer determines the separation
properties, whereas both the support layer and
substrate merely provide mechanical support for
the active layer to withstand high-operating pres-
sures of up to 7 MPa. The physicochemical prop-
erties associated with the separation function are
characterized by pore size, surface morphology
or roughness, surface charge, and hydrophobicity
(Bellona et al. 2004). Retention of compounds is
based on solute-membrane interaction mecha-
nisms, namely, steric hindrance, electrostatic
repulsion for charged solutes, and hydrophobic-
hydrophobic and dipole-dipole interactions. The
transport mechanism for RO membranes can be
described by the widely accepted solution-
diffusion model (Wijmans and Baker 1995).
Challenges for RO Membrane Desalination
The commercially available TFC RO membranes
have excellent salt retention properties, typically
greater than 99.5 % (Baker 2004). However,
boron removal, which is usually less than 95 %,
2 High-Rejection Seawater Reverse Osmosis Membrane
High-Rejection Seawater
Reverse Osmosis
Membrane,
Fig. 1 Structure of
composite RO membrane
(Uemura et al. 2012)
is a major challenge to RO membranes to meet
the recommended value of below 0.5 mg/L in
drinking water by the World Health Organization
(Jonsson and Macedonio 2010; Misdan
et al. 2012). Boron exists naturally in seawater
(pH 7–8) in the form of uncharged boric acid with
pKa value of 9.2 and at concentration of
5 mg/L. Below pH 9, the non-hydrated boric
acid is poorly rejected due to the lack of electric
double layer repulsive force between the nega-
tively charged membrane surface and boric acid.
Current practice for boron removal in seawater
desalination is either to install a second pass RO
or ion exchange column to further purify the
water or to increase the pH to above 9 so that
the membrane can easily reject the hydrated boric
acid. The latter is least preferred as it can promote
membrane scaling by hardness in the water.
Another concern is the incomplete retention of
trace organic micro-pollutants such as endocrine-
disrupting compounds, pesticides, pharmaceuti-
cally active compounds, etc. (Bellona
et al. 2004). In general, due to the nature of the
membrane, charged/hydrophilic molecules have
better retention than uncharged/hydrophobic
molecules. However, predictive models to
account for the organic solute transport through
the membrane are still lacking.
In addition, true retention is an intrinsic prop-
erty of the membrane, though the observed reten-
tion is strongly influenced by the process
parameters such as operating pressure, tempera-
ture, pH, and membrane fouling. For instance,
when a membrane is fouled, the solutes no longer
Active skin layer
Support layer
Substrate
freely move in the concentration polarization
boundary layer, instead need to diffuse through
the tortuous paths in the fouling layer. Conse-
quently, the hindered back-diffusion effect
causes greater accumulation of solutes at the
membrane wall, thus resulting in the increase of
solute passage (Fane et al. 2009). Hence, a high-
retention membrane needs to possess good anti-
fouling properties to ensure consistent perfor-
mance in long-term operation.
Future Direction
Incorporation of nano-materials and biomaterials
into the active layer is seen to be the innovative
way to produce the next generation of high-
permeability and high-retention seawater RO
membranes, i.e., nanocomposite or biomimetic
membranes (Matsuura and Fane 2013). In addi-
tion, a thorough understanding on the molecular
structures of membrane and its interaction with
solutes via molecular simulation is necessary to
allow better manipulation of surface properties
such as the extent of cross-linking, chain-packing
density, and chain stiffness in order to enhance
the performance of RO membranes.
References
Baker RW (2004) Membrane technology and applica-
tions. Wiley, Chichester
Bellona C, Drewes JE, Xu P, Amy G (2004) Factors
affecting the rejection of organic solutes during
NF/RO treatment – a literature review. Water Res
38:2795–2809
High-Rejection Seawater Reverse Osmosis Membrane
Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
brane processes. In: Drioli E, Giorno L (eds) Mem-
brane operations: innovative separations and
transformations. Wiley-VCH, Weinheim, pp 121–138
Jonsson G, Macedonio F (2010) Fundamentals in reverse
osmosis. In: Drioli E, Giorno L (eds) Comprehensive
membrane science and engineering, vol 2. Elsevier,
Oxford, pp 1–22
Kurihara M, Tomioka H (2010) Preparation of industrial
RO, NF membranes, and their membrane modules and
applications. In: Drioli E, Giorno L (eds) Comprehen-
sive membrane science and engineering,
vol 2. Elsevier, Oxford, pp 23–34
3
Matsuura T, Fane AG (2013) Editorial: new directions in
desalination. Desalination 308:1
Misdan N, Lau WJ, Ismail AF (2012) Seawater reverse
osmosis (SWRO) desalination by thin film composite
membrane – current development, challenges and
future prospects. Desalination 287:228–237
Uemura T, Kotera K, Henmi M, Tomioka H (2012) Mem-
brane technology in seawater desalination: history,
recent developments and future prospects. Desalin
Water Treat 33(1–3):283–288
Wijmans JG, Baker RW (1995) The solution-diffusion
model: a review. J Membr Sci 107:1–21
A
Amphoteric Ion Exchange
Membrane
Tongwen Xu
Collaborative Innovation Centre of Chemistry for
Energy Materials, School of Chemistry and
Material Science, University of Science and
Technology of China, Hefei, P.R. China
Amphoteric ion exchange membrane is a kind
of membrane containing random arrangements of
both cation and anion exchange groups. When
firstly proposed by Söllner in 1932 (Söllner
1932), amphoteric ion exchange membranes
mainly refer to membranes having a combination
of weak acidic (cation exchange) and weak basic
(anion exchange) groups. Nowadays, they are
expanded to include membranes containing a
combination of weak acidic (or weak basic)
with strong basic (or acidic) functionalities or a
combination of strong acidic and basic groups.
Basically, there are four types (Sata 2004):
(1) membranes in which both anion and cation
exchange groups are distributed at random during
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1419-4
the preparation procedures, such as copolymeri-
zation, (2) snake cage-type amphoteric mem-
branes, (3) polysalt membranes, and
(4) membranes prepared by a “layer-by-layer”
method. The amphoteric ion exchange mem-
branes can show superior antifouling properties,
peculiar selectivity, and permeability and hence
are useful in the biomedical and industrial fields,
such as medical devices (e.g., hemodialysis
membrane), separation of ionic drugs and pro-
teins, and depletion of electrolytes by
nanofiltration or piezodialysis as well as high
performance gel actuator. Membrane having
properly combined anion and cation exchange
groups shows selective permeability for inor-
ganic salts and, therefore, is able to separate a
low molecular organic substance from an inor-
ganic salt, acid, or alkali as well as salt from acid
or salt from alkali (Eguchi et al. 1981). Mean-
while, some of the membranes have composi-
tions that show hydrogen ion permselectivity
relative to sodium ions in electrodialysis
(Yamane et al. 1965) (Fig. 1).
2 Amphoteric Ion Exchange Membrane

References

Eguchi T, Mori S, Shimokawa M (1981) Process for

preparing a composite amphoteric ion exchange mem-
brane. US patent US874,687
Sata T (2004) Ion exchange membranes: preparation,
characterization, modification and application. Royal
society of Chemistry, Cambridge
Söllner K (1932) Uber mosaikmembranen. Biochem
Z 244:390
Yamane R, Izuo R, Mizutani Y (1965) Permselectivity of
the amphoteric ion-exchange membranes(2). Denki
Kagaku (J Electrochem Soc Jpn) 33:589–593

Amphoteric Ion Exchange Membrane,

Fig. 1 Transport number of hydrogen ions relative to
sodium ions (PNaH) and current efficiency of cations to
the composition of amphoteric ion exchange membranes.
(○,●): quaternized membranes (N-methyl pyridinium and
sulfonic acid groups); (D, ~): tertiary amino groups mem-
brane; (pyridinium hydrochloride and sulfonic acid
groups); (●, ~): PNaH; (○, D): current efficiency (%).
Electrodialysis was carried out at a current density of
20mAcm–2 using a mixed solution of 0.25 N sodium
chloride and 0.25 N hydrochloric acid for 60 min at
25.0  C (Yamane et al. 1965)
A
Anion-Exchange Resin
Tongwen Xu
Collaborative Innovation Centre of Chemistry
for Energy Materials, School of Chemistry and
Material Science, University of Science and
Technology of China, Hefei, P.R. China
Anion-exchange resin contains positively
charged groups, such as –NH3+,
NRH2+,

NR2H+,
NR3+,
PR3+,
SR2+, etc., which
are fixed to the membrane backbone and allow
the exchange of anions but repulse cations. As
shown in Fig. 1, the active groups existed in the
body of resin determine its chemical behavior. It
has a highly developed structure of pores on the
surface, which could easily trap and release ions.
There are two main types of anion-exchange
resins differing in their active groups: strongly
basic and weakly basic. (1) Strongly basic resins
are highly ionized, and their chemical behavior is
similar to that of a strong base which can be used
over the entire pH range. They can react with
anions in solution and convert an acid solution
to pure water. The exhausted resin can be
regenerated with concentrated sodium hydroxide
(NaOH) and converted to the hydroxide form.
(2) The degree of ionization of weakly basic
resin is strongly influenced by pH because it is
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1420-4
like a weak base. The weak base resin does not
have a hydroxide ion form as does the strong base
resin. Consequently, its regeneration needs only
to neutralize the absorbed acid and does not need
to provide hydroxide ions. Less expensive
weakly basic reagents such as ammonia (NH3)
or sodium carbonate can be employed.
The selectivity of a resin for a given ion is
measured by the selectivity coefficient (K), as for
the reaction
R
A
þ B
¼ R
B
þ A

The K can be expressed as K = (concentration of
B
in resin/concentration of A
in resin) 
(concentration of A
in solution/concentration
of B
in solution).
In general, introducing ionic groups could
start with a monomer containing a moiety, a
polymer film, or start with polymers or polymer
blends (Helfferich 1962; Strathmann 2004). As
summarized in our recent book chapter, the spe-
cific implementation methods include
(1) amidoalkylation of cross-linking polystyrene,
(2) copolymerization of (chloromethyl) styrene,
(3) chloroacetylation of polymers, (4) acetylation
of cross-linked polystyrene, and (5) grafting
vinylbenzyl ammonium chloride onto inert poly-
mers (Xu 2009).
2 Anion-Exchange Resin

Anion-Exchange Resin,
Fig. 1 Diagram of anion-
backbone
exchange resin
–
– + +

+ + active group
– –
–
+ active group (fixed group)
–
+ –
free ion
+

References Strathmann H (2004) Ion-exchange membrane separation

processes. Elsevier Science
Helfferich FG (1962) Ion exchange. Dover Publications Xu T(2009) Advances in membrane science and technol-
ogy. Nova Science
R
Regeneration of the Ion-Exchange
Resin
Tongwen Xu
Collaborative Innovation Center of Chemistry for
Energy Materials, School of Chemistry and
Material Science, University of Science and
Technology of China, Hefei, P.R. China
Regeneration of the ion-exchange resin is the
procedure for recovering the ion-exchange capa-
bilities of exhausted ion-exchange resins. Most
ion-exchange resins are used in columns.
Ion-exchange operation is basically discontinu-
ous: a loading phase, called service run, is
followed by regeneration of the exhausted resins
(Calmon 1986). Regeneration ratio is calculated
as the total amount of regenerant (in equivalents)
divided by the total ionic load (also in equiva-
lents) during one cycle. It is also equal to the
number of eq./L regenerant per eq./L of resin
operating capacity. A (theoretical) regenerant
ratio of 1.00 (i.e., 100 %) would correspond to
the stoichiometric quantity. Nevertheless, all
resins need a certain excess of regenerant above
the stoichiometric quantity. The regeneration
ratio is influenced by the technological process,
the type and amount of regenerant, etc. There are
two main methods for the regeneration process
(Dardel and Arden 2008): (1) co-flow
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1422-3
regeneration, where the fluids are flowing from
the top to the bottom of the column both during
the service run and during regeneration (Fig. 1),
and (2) reverse flow regeneration, where the
fluids are flowing alternatively upward and
downward during service and regeneration
(Fig. 2). Traditional regenerants are salts (such
as NaCl, KCl, NH4Cl), acids (HCl, H2SO4,
HNO3, acetic acid, citric acid), and alkali
(NaOH, KOH, NH3, Na2CO3). For instance,
NaCl is normally used to regenerate SAC resins
in the softening process. SAC resins need to be
regenerated with a strong acid for the purpose of
decationization, and SBA resins are always
regenerated with NaOH in the demineralization
process. The disadvantages of the use of tradi-
tional regenerants are the low regeneration effi-
ciency and the discharge of large amount of
wastewater, leading to serious environmental
pollution and resource waste. Improvement
methods include (1) the recovery of the
discharged wastewater; nanofiltration can be uti-
lized for recovery of the wastewater, or the waste
can be used to produce composite flocculant;
(2) the modification of the regenerants; alcohol,
ketone, and surfactant are added, or new
regenerants are developed; and (3) the strength-
ening of the regeneration process. Ultrasonic,
microwave, electrodialysis, or thermal treatment
is applied for the strengthening.
2 Regeneration of the Ion-Exchange Resin

Exhaustion Regeneration

lon leakage
Regenerated resin Exhausted resin

Regeneration of the Ion-Exchange Resin, Fig. 1 Illustration of co-flow regeneration (CFR) (Dardel and Arden
2008)

a Exhaustion Regeneration

Clean zone: almost no leakage

Regenerated resin Exhausted resin

b Exhaustion Regeneration
Clean zone: almost no leakage

Regenerated resin Exhausted resin

Regeneration of the Ion-Exchange Resin, Fig. 2 Illustration of reverse flow regeneration (RFR), including (a)
upflow loading and downflow regeneration and (b) downflow loading and upflow regeneration (Dardel and Arden 2008)
Regeneration of the Ion-Exchange Resin
References
Calmon C (1986) Recent developments in water treatment
by ion exchange. React Polym Ion Exch Sorbents
4(2):131–146
3
Dardel F, Arden TV (2008) Ion exchangers. In: Ullmann’s
encyclopedia of industrial chemistry
François Dardel and Thomas V. Arden (2008) Ion
Exchangers In: Ullmann’s Encyclopedia of Industrial
Chemistry, Wiley-VCH, Weinheim. doi:10.1002/
14356007.a14_393.pub2
T
Titania Membranes
Toshinori Tsuru
Department of Chemical Engineering, Hiroshima
University, Higashi-Hiroshima, Japan
Titania membranes show excellent chemical
resistance and can be used in both acidic and
basic pHs, and moreover, they show interesting
photocatalytic activity. Titania ultrafiltration
membranes have been commercialized by several
companies. At present, extensive efforts have
focused on the preparation of porous membranes
having small pore sizes in the NF range (1–2 nm).
Since pore sizes are believed to be controlled by
the sizes of the packed particles, controlling the
sol size is a crucial process for membrane
processing. Anderson et al. [24] prepared nano-
sized TiO2 and ZrO2 particles (3–5 nm) by car-
rying out hydrolysis and condensation reactions
of metal tert-amyloxide with a small amount of
water (molar ratio of H2O/Ti = 3
5) in
tert-amyl alcohol solutions. Hydrolysis and con-
densation reactions of metal alkoxides are written
as follows:
TiðORÞ4 þH2 O!TiðORÞ3 ðOHÞþ
ROH ðhydrolysisÞ
TiðORÞ4 þTiðORÞ3 ðOHÞ!ðROÞ3 TiOTiðORÞ3 þ
ROH ðcondensationÞ
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1423-2
Since both reactions take place by nucleo-
philic substitution, the electronegativity and the
size of alkoxy groups are important. By using a
large branched alkoxy group (tert-amyl alkox-
ide), the reaction rate can be reduced, resulting
in small-sized sols. An amorphous phase
predominated in the xerogel dried at room tem-
perature and fired at 300  C, and phase transition
from amorphous to anatase and from anatase to
rutile occurred from 300–400  C to 400–600  C,
respectively. Therefore, it is important to control
firing temperature in order to obtain controlled
pore sizes of membranes. Titania membranes
which were coated on porous alumina mem-
branes and fired at 200  C showed approximately
a 100 % rejection of polyethylene glycol
200 (PEG200, M. W. 200), depending on operat-
ing conditions (Xu et al. 1993). Another strategy
for controlling MWCOs is the appropriate choice
of sol diameters, which is used at the final coating
for the separation of the top layer. (Tsuru et al.
2001) successfully prepared a variety of MWCOs
for TiO2 membranes at the same firing tempera-
ture of 450  C using sol solutions having different
sizes of sol diameters, as shown in Fig. 1. M1,
M2, and M3 show MWCOs approximately
500, 600, and 800, while M4 shows nearly no
rejection for a-dextrin (MW 972).
On the other hand, Société des Céramiques
Techniques (SCT) claimed that they had com-
mercialized TiO2 NF membranes having an
MWCO of 1,000 (Sarrade et al. 1996) based on
research work by Commissariat à l’Energie
2 Titania Membranes
Titania Membranes, Fig. 1 Molecular weight cutoff
curves for TiO2 porous membranes (solutes: sugars,
500 ppm) (Wildman et al. 1993)
Atomique (CEA). Colloidal sols with a diameter
of 15 nm, which showed an anatase phase and
which were stable up to 600  C, were coated on
porous alumina supports and fired at 500  C. Voigt
et al. (Puhlf€
urß et al. 2000) prepared polymeric
sols from a solution of Ti-isopropoxide in isopro-
pyl alcohol by the addition of a small amount of
water. NF membranes, which were prepared by
coating the polymeric sols on a TiO2 intermediate
layer (pore size 5 nm, prepared by colloidal TiO2
sols), followed by firing at 450  C, had an
MWCO of 480 and a pure water flux of 20 l/
(m2 h bar) and were applied to the separation of
electrolytes. Benfer et al. (2001) also developed
TiO2 NF membranes by the polymeric sol route.
Tetraethyl orthotitanate was partially hydrolyzed
at conditions where the molar ratio of water over
the alkoxide was less than 1, followed by the
addition of an acid or organic base to control the
viscosity of the polymeric sol solution, i.e., the
size of the polymeric network. They also pre-
pared zirconia porous membranes by the same
method. Filtration performance of TiO2 mem-
branes shows comparable water permeabilities
to those of polymeric NF membranes.
References
Benfer S, Popp U, Richter H, Siewert C, Tomandl G
(2001) Development and characterization of ceramic
nanofiltration membranes. Sep Purif Technol
22–23:231
Puhlf€
urß P, Voigt A, Weber R, Morbé M (2000) Micro-
porous TiO2 membranes with a cut off <500 Da. J
Membr Sci 174:123
Sarrade SJ, Rios GM, Carlès M (1996) Nanofiltration
membrane behavior in a supercritical medium. J
Membr Sci 114:81
Soria R, Cominottim S (1996) In: Proceedings of fourth
international conference on inorganic membranes,
p 194
Tsuru T, Hironaka D, Yoshioka T, Asaeda M. (2001)
Titania membranes for liquid phase separation: effect
of surface charge on flux. Sep Purif Technol 25: 307
Wildman DL, Peterson RA, Anderson MA, Hill CG
(1993) In: Proceedings of third international confer-
ence on inorganic membranes, p 111
Xu Q, Anderson M (1994) Sol–Gel Route to Synthesis of
Microporous Ceramic Membranes: Preparation and
Characterization of Microporous TiO2 and ZrO2
Xerogel. J Am Ceram Soc 77: 1939
A
Ammonia Decomposition
in Catalytic Membrane Reactors
Toshinori Tsuru
Department of Chemical Engineering, Hiroshima
University, Higashi-Hiroshima, Japan
Recently, NH3 has been proposed as a H2 carrier
in a promising solution that would bypass the
intractable issues related to H2 storage and deliv-
ery, since NH3 has a high hydrogen storage
capacity of 17.6 wt.% and can be easily stored
and transported in liquid form under mild condi-
tions. NH3 decomposes to H2, which produces
only H2O after combustion, and N2, which is
not a greenhouse gas; in other words, NH3 is a
COx-free H2 carrier. Another class of a hydrogen
carrier is an organic hydride such as cyclohexane
(CH) and methylcyclohexane (MCH). In dehy-
drogenation reaction, CH and MCH reversibly
produce benzene (BEN) and toluene (TOL),
based on the equilibrium reaction, respectively,
while BEN and TOL are re-hydrogenated into
CH and MCH, respectively. Methylcyclohexane-
toluene-hydrogen (MTH cycle) and
cyclohexane-benzene-hydrogen (CBH cycle)
need reversible and highly selective conversion
to sustainable use. Therefore, the advantages of
NH3 mentioned above make the NH3-mediated
hydrogen economy extremely attractive and
promising. Other H2 carriers, such as methanol,
dimethyl ether, etc., inevitably cause end-user
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1424-2
CO2 emissions, since they are carbonaceous com-
pounds and on-board CO2 capture is not feasible.
As shown in the following equations, another
advantage of NH3-energy systems is the low heat
of reaction. Approximately 30 kJ is required for
one mole of produced H2 in NH3 system, which is
lower than in MTH cycle (70 kJ) and steam
reforming of methane (SRM) (40 kJ).
SRM reaction : CH4 þ 2H2 O $ CO2 þ 4H2
DH ¼ þ164:5 kJ=mol
MTH cycle : C7 H14 $ C7 H8 þ 3H2
DH ¼ þ204:6 kJ=mol
NH3 system : NH3 ! 0:5N2 þ 1:5H2
DH ¼ þ46 kJ=mol
Membrane reactors can be categorized based
on configuration of catalysts as packed type
membrane reactor, fluidized membrane reactor,
and catalytic membrane reactor. As shown in
Fig. 1, packed bed membrane reactors consist of
catalysts for reaction as well as membranes for
separation. Both catalyst particles and mem-
branes are packed into one unit, but reaction and
separation occur separately. On the other hand,
catalytic membranes have catalytic activity as
well as separation ability in one membrane. Zeo-
lite membranes such as ZSM-5 and TS-1 are
inherently catalytically active, while another
type of catalytic membrane is a silica hydrogen
separation membrane on catalytically active sup-
port which can be prepared using catalytically
active powders such as nickel oxides or
2 Ammonia Decomposition in Catalytic Membrane Reactors
Reactants retentate
packed catalyst
permeate
membrane
Packed Bed Membrane Reactor (PBMR)
Ammonia Decomposition in Catalytic Membrane Reactors, Fig. 1 Configuration of membrane reactors
COx-free H2
Ru catalyst
γ-Al2O3
α-Al2O3
¬
NH3 ¬ 1.5H2ˇ 0.5N2
NH3
Ammonia Decomposition in Catalytic Membrane Reactors, Fig. 2 Schematic diagram of the proposed bimodal
catalytic membrane reactor for COx-free H2 production via NH3 decomposition (Li et al. 2013)
impregnation of Ni-catalyst inside porous
a-alumina supports (Tsuru et al. 2004).
Membrane reactors combining a catalytic
reaction with the separation process into a single
unit offer an ideal device to produce H2 from NH3
efficiently, where enhanced NH3 conversion and
high-purity COx-free H2 can be simultaneously
obtained by applying a hydrogen separation
membrane. Ru is reported the most active catalyst
for ammonia decomposition and is supported on
porous carbon such as carbon nanotubes (CNT)
with supporting catalysts such as potassium (K).
To date, only a few studies have reported mem-
brane reactors for NH3 decomposition in a
packed bed Pd membrane reactor, and improved
NH3 conversion was obtained after H2 extraction.
Another class of membrane reactor is a cata-
lytic membrane reactor. Figure 2 shows a sche-
matic bimodal catalytic membrane reactor
(BCMR) (Li et al. 2013). This new type of mem-
brane reactor had a configuration that consisted of
a silica separation layer and a bimodal catalytic
Reactants retentate
catalytic
membrane permeate
Catalytic Membrane Reactor (CMR)
Silica membrane
Intermediate layer
Bimodal catalytic support layer
N2
support (Ru/g-Al2O3/a-Al2O3). The impregna-
tion of g-Al2O3 into an a-Al2O3 membrane sup-
port to form a bimodal support is expected to
effectively improve catalytic membrane reactor
performance, since the bimodal structure con-
tains both mesopores and macropores, which
results in improved catalytic activities by
mesopores and high gas diffusivity by
macropores.
Figure 3 shows an example of enhancement of
conversion for the BCMR performance for NH3
decomposition at 450  C. During the initial
250 min without sweep gas, a NH3 conversion
was 45 %. When N2 sweep gas was applied to the
permeate stream of the membrane reactor, NH3
conversion was significantly enhanced from 45 to
95 % after the selective H2 extraction. NH3
decomposition rate is strongly inhibited by the
presence of H2, particularly at a high pressure.
Therefore, the highly enhanced NH3 conversion
can be ascribed to the improved kinetics from H2
extraction in the BCMR.
Ammonia Decomposition in Catalytic Membrane Reactors 3

Ammonia
Decomposition
in Catalytic Membrane
Reactors, Fig. 3 Bimodal
catalytic membrane reactor
performance for NH3
decomposition at 450  C
(Li et al. 2013)

References membrane reactors for COx-free hydrogen production.

AIChE J 59:168–179
Li G, Kanezashi M, Tsuru T (2013) Highly enhanced Tsuru T, Yamaguchi K, Yoshioka T, Asaeda M (2004)
ammonia decomposition in bimodal catalytic silica Methane steam reforming by microporous catalytic
membrane reactors. AIChE J 50:2794
C
Chemical Vapor Deposition
Hiroki Nagasawa and Toshinori Tsuru
Department of Chemical Engineering, Hiroshima
University, Higashi-Hiroshima, Japan
Chemical vapor deposition (CVD) is a method
for depositing thin films of various materials
(Smith 1995). CVD process involves a series of
gas phase and surface reactions of volatile precur-
sors, which are induced by, for example, heat, light,
and/or plasma-discharge. CVD has been used
extensively in a number of industries such as semi-
conductor, electronics, and optics industries.
CVD techniques have also been utilized in the
fabrication of inorganic molecular sieve mem-
branes. Among the types of CVD technique, ther-
mal CVD has been most extensively studied since
Gavalas and coworkers first reported successful
synthesis of the hydrogen-selective silica mem-
branes in 1989 (Gavalas et al. 1989). There are
two types of reaction geometries available for
thermal CVD, as shown in Fig. 1: one-sided
CVD and counter-diffusion CVD (Nomura
et al. 1997; Nakao et al. 2000). For the case of
the one-sided CVD, all of the reactants are fed to
the same side of the porous substrate, and then,
the film-forming reactions occur at the surface of
the substrate. On the other hand, for the case of
the counter-diffusion CVD, the reactants are fed
to the opposite side of the substrate. The reactants
diffuse into the porous substrate and the reactions
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1425-1
take place at the location where the reactants
contact each other. Therefore, the deposition
occurs inside the pores and the pore size will be
decreased. The deposition continues until the
pore size becomes small enough to reduce diffu-
sion of the reactants. As a result, uniform pore
size can be obtained by using the counter-
diffusion CVD.
The hydrogen-selective silica membranes
reported by Gavalas et al. were prepared by
depositing a dense silica layer on the top of
Vycor glass membranes by the oxidation of SH4
at 450  C (Gavalas et al. 1989). The obtained
membranes were reported to have high H2/N2
selectivities as high as 3,000 but low H2
permeances of 2.1  10 8 mol/(m2 s Pa) at
450  C. Until then, a great deal of progress has
been made by several research groups. For exam-
ple, Gu and Oyama prepared a silica membrane
on the substrate with a graded g-alumina inter-
mediate layer by the thermal decomposition of
tetraethoxysilane (TEOS) at 600  C and reported
H2 permeance of 5.0  10 7 mol/(m2 s Pa) at
600  C, with H2/CH4 selectivity of 5,900
(Gu and Oyama 2007). Ohta et al. prepared silica
membranes on the g-alumina intermediate layer
by using oxidation of tetramethoxysilane
(TMOS), phenyltrimethoxysilane (PTMS), or
dimethoxydiphenylsilane (DMDPS) at 600  C
and reported that larger pores were formed
when the number of phenyl groups on the precur-
sor was increased (Ohta et al. 2008). The
DMDPS-derived membrane showed a high H2
2 Chemical Vapor Deposition
Chemical Vapor
Deposition,
Fig. 1 Schematic diagram
of (a) one-sided and (b)
counter-diffusion CVD
processes
permeance of the order of 10 6 mol/(m2 s Pa) at
300  C, with H2/SF6 selectivity of 6,800.
Plasma-enhanced CVD (PECVD) is another
type of CVD technique utilized for the membrane
fabrication. PECVD offers a low processing tem-
perature compared with thermal CVD due to the
high reactivity of plasma. Several research
groups reported the PECVD-derived membranes
prepared at room temperature by using several
kinds of precursors such as hexamethyldisiloxane
(HMDSO) (Roualdes et al. 2002; Tsuru
et al. 2011; Nagasawa et al. 2013), hexamethyl-
disilazane (HMDS) (Kafrouni et al. 2009), or bis
(dimethylamino)dimethylsilane (BDMADMS)
(Kafrouni et al. 2010). Typical PECVD-derived
membranes showed moderate selectivity (e.g.,
He/N2 selectivity of <10 at 25  C and ~30 at
150  C) with He permeance of the order of
10 8–10 7 mol/(m2 s Pa), probably because the
PECVD-derived layer remains to have high con-
tent of organofunctional groups which make the
structure more loose (Roualdes et al. 2002; Tsuru
et al. 2011; Nagasawa et al. 2013; Kafrouni
et al. 2009, 2010). Selectivity of PECVD-derived
membranes can be improved by 2-step PECVD
sequence, which involves HMDSO/Ar-PECVD
followed by HMDSO/O2-PECVD (Tsuru
et al. 2011; Nagasawa et al. 2013). Moreover,
the membrane prepared via 2-step PECVD
showed a good thermal stability, although the
membrane was fabricated at room temperature.
The 2-step PECVD-derived membrane showed
high He and H2 permeances of 5.2  10 7 and
2.4  10 7 mol/(m2 s Pa) at 400  C, respec-
tively, with He/N2 and H2/N2 permeance ratios
of 4,200 and 1,900, respectively (Tsuru
et al. 2011; Nagasawa et al. 2013).
References
Gavalas GR, Megiris CE, Nam CW (1989) Chem Eng Sci
44:1829–1835
Gu Y, Oyama ST (2007) High molecular permeance in a
poreless ceramic membrane. Adv Mater
19:1636–1640
Kafrouni W, Rouessac V, Julbe A, Durand J (2009) Syn-
thesis of PECVD a-SiCxNy:H membranes as molecu-
lar sieves for small gas separation. J Membr Sci
329:130–137
Kafrouni W, Rouessac V, Julbe A, Durand J (2010) Syn-
thesis and characterization of silicon carbonitride films
by plasma enhanced chemical vapor deposition
(PECVD) using bis(dimethylamino)dimethylsilane
(BDMADMS), as membrane for a small molecule
gas separation. Appl Surf Sci 257:1196–1203
Nagasawa H, Shigemoto H, Kanezashi M, Yoshioka T,
Tsuru T (2013) Characterization and gas permeation
properties of amorphous silica membranes prepared
Chemical Vapor Deposition
via plasma enhanced chemical vapor deposition.
J Membr Sci 441:45–53
Nakao S, Suzuki T, Sugawara T, Tsuru T, Kimura
S (2000) Preparation of microporous membranes by
TEOS/O3 CVD in the opposing reactants geometry.
Microporous Mesoporous Mater 37:145–152
Nomura M, Yamaguchi T, Nakao S (1997) Silicalite
membranes modified by counterdiffusion CVD tech-
nique. Ind Eng Chem Res 36:4217–4223
Ohta Y, Akamatsu K, Sugawara T, Nakao A, Miyoshi A,
Nakao S (2008) Development of pore size-controlled
3
silica membranes for gas separation by chemical vapor
deposition. J Membr Sci 315:93–99
Roualdes S, Sanchez J, Durand J (2002) Gas diffusion and
sorption properties of polysiloxane membranes pre-
pared by PECVD. J Membr Sci 198:299–310
Smith DL (1995) Thin-Film Deposition: Principles and
Practice, McGraw-Hill, Inc.,
Tsuru T, Shigemoto H, Kanezashi M, Yoshioka T (2011)
2-step plasma-enhanced CVD for low-temperature
fabrication of silica membranes with gas-separation
performance. Chem Commun 47:8070–8072
H
Hybrid Silica Membranes
Toshinori Tsuru
Department of Chemical Engineering, Hiroshima
University, Higashi-Hiroshima, Japan
A great deal of attention has been paid to silica
membranes, which can accomplish separation
tasks even under harsh conditions due to their
high-separation performance, chemical inertness,
and thermal stability (de Vos and Verweij 1998;
Tsuru 2008). Two strategies have been proposed
to prepare amorphous molecular sieving silica
membranes: the sol–gel process and the chemical
vapor deposition (CVD) method.
Tetraethoxysilane (TEOS), which is a common
Si precursor, has been widely adopted in both
approaches, and the resultant membranes have
been extensively investigated for gas separation,
pervaporation, and membrane reaction. However,
traditional TEOS-derived silica membranes suffer
from poor hydrothermal stability, which greatly
hampers their practical application. Inspired by
the distinctive features of organic–inorganic
hybrid silica materials with respect to flexibility,
hydrothermal stability, and tunable pore sizes,
researchers have concentrated on the preparation
of hybrid silica membranes with improved hydro-
thermal stability and controlled pore sizes, using
organoalkoxysilanes instead of TEOS.
Organic/inorganic hybrid membranes can be
prepared either by the post-modification of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1426-2
hydrophilic ceramic membranes (Tsuru
et al. 2004) or by the in-situ preparation using
hydrophobic sols. In post-modification, hydro-
philic porous membranes, the pore surface of
which is covered with hydrophilic hydroxyl
groups such as -SiOH, were modified with silane
coupling agents such as trimethylchlorosilane in
either a gas or a liquid phase, to convert the
hydroxyl groups to a trimethylated surface. How-
ever, this method has several disadvantages;
post-modification always reduces the effective
pore sizes, leading to a decrease in flux. More-
over, it is difficult to modify membrane pores to
less than several nanometers since the silane cou-
pling agents cannot enter such small pores (Tsuru
et al. 2004).
In-situ preparation of hydrophobic silica
membranes was reported in sol–gel processing.
Two typical kinds of organoalkoxysilanes have
been used as Si precursors to prepare silica mem-
branes via a sol–gel process. One is a bridged
alkoxide, that is, a di-silicon alkoxide with a
bridged group between the two silicon atoms,
such as 1, 2-bis(triethoxysilyl)ethane(BTESE)
(CH3CH2O)3Si CH2CH2Si(OCH2CH3)3 and bis
(triethoxysilyl)methane (BTESM)
(CH3CH2O)3SiCH2Si(OCH2CH3)3 (Kanezashi
et al. 2009; Castricum et al. 2008a, b). Castricum
and coworkers (2008a; Castricum et al. 2008b)
first reported on the BTESE-derived silica mem-
brane and applied it to pervaporation dehydration
of solvents of 95 wt% n-butanol-5 wt% water in
an attempt to increase hydrothermal stability. The
2 Hybrid Silica Membranes
membrane was stable after 1.5 years, even though
the test temperature was as high as 150  C, while
TEOS-derived silica membrane completely lost its
separation ability within weeks at a much lower
temperature of 95  C. The excellent hydrothermal
stability endowed by the organic–inorganic struc-
tures appears to be very promising for practical
application. The formation of a looser structure
and improved hydrothermal stability was due to
the presence of a Si–C–C–Si minimum unit in the
silica networks.
Another typical kind of organoalkoxysilane is
a mono-silicon alkoxide with a pendant group,
such as methyltriethoxysilane (MTES),
(trifluoropropyl)triethoxysilane (TFPTES),
ethylenetriethoxysilane (ETES), or
3-methacryloxypropyltrimethoxysilane (MPS)
(Raman and Brinker 1995; de Vos et al. 1999;
Tsuru et al. 2011). Without burning out organic
pendant groups, hybrid hydrophobic silica mem-
branes could be obtained via the sol–gel process,
which was first reported by de Vos et al. using
TEOS and MTES as co-precursors (de Vos
et al. 1999). The hybrid membranes prepared
via this route also showed good hydrothermal
stability and have been used for both gas separa-
tion and pervaporation. Considerable research on
silica membranes prepared by mono-silicon alk-
oxides with pendant groups has led to a great deal
of progress in understanding both the sol–gel
process and the membrane characteristics.
References
Castricum HL, Sah A, Kreiter R, Blank DHA, Vente JF,
ten Elshof JE (2008a) Hybrid ceramic nanosieves:
stabilizing nanopores with organic links. Chem
Commun 11037–1105. DOI: 10.1039/B718082A
Castricum HL, Kreiter R, van Veen HM, Blank DHA,
Vente JF, ten Elshof JE (2008b) High-performance
hybrid pervaporation membranes with superior hydro-
thermal and acid stability. J Membr Sci 324:111
de Vos RM, Verweij H (1998) High-selectivity, high flux
silica membranes for gas separation. Science 279:1710
de Vos RM, Maier WF, Verweij H (1999) Hydrophobic
silica membranes for gas separation. J Membr Sci
158:277
Kanezashi M, Yada K, Yoshioka T, Tsuru T (2009)
Design of silica networks for development of highly
permeable hydrogen separation membranes with
hydrothermal stability. J Am Chem Soc 131:414
Raman NK, Brinker CJ (1995) Organic “template”
approach to molecular sieving silica membranes.
J Membr Sci 105:273
Tsuru T (2008) Nano/subnano-tuning of porous ceramic
membranes for molecular separation. J Sol–gel Sci
Technol 46:349
Tsuru T, Kondo H, Yoshioka T, Asaeda M (2004) Perme-
ation of nonaqueous solution through organic/inor-
ganic hybrid nanoporous membranes. AIChE
J 50:1080–1087
Tsuru T, Nakasuji T, Oka M, Kanezashi M, Yoshioka
T (2011) Preparation of hydrophobic nanoporous
methylated SiO2 membranes and application to
nanofiltration of hexane solutions. J Membr Sci
384:149–156
C
Chiral Drug Separation by
Membranes
Keiji Sakaki
National Institute of Advanced Industrial Science
and Technology (AIST), Research Institute for
Sustainable Chemistry, Tsukuba, Ibaraki, Japan
An enantiomer is one of two stereoisomers that
are mirror images of each other and
non-superposable. This feature of an enantiomer
is called “chirality.”
Chirality is a very important key word in phar-
maceutical industry, because more than half of
pharmaceutically active ingredients are chiral
(Sekhon 2010). In chiral drugs, one enantiomer
shows desirable bioactivity, but the other enan-
tiomer frequently does the less bioactivity or
sometimes toxic side effects. Therefore, world-
wide sales of single-enantiomer drugs have been
growing (Maier et al. 2001; Li and Haynie 2007).
There are some techniques to prepare single-
enantiomer drugs in pharmaceutical industry.
One is chemical synthesis using chiral building
blocks as starting materials. Another is asymmet-
ric synthesis using enantioselective catalysts like
chiral organocatalysts or biocatalysts. Optical
resolution of enantiomers in a racemate is another
important technique in chiral drug industry. The
method of optical resolution can be applied to not
only final racemic drugs but also racemic inter-
mediates appeared in preparation steps.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1428-3
We already have some techniques to separate
one enantiomer from the other isomer: preferen-
tial crystallization, chiral chromatography,
enantioselective extraction, enzymatic kinetic
resolution, membrane separation, and so
on. Among these techniques, membrane-based
method has some advantages such as low energy
demand, continuous operation, and easy scale-up.
The important factor of membrane-based
enantioselective separation is the way how to
give the function of chirality recognition to mem-
branes. In a supported liquid membrane, a liquid
containing enantioselective carriers is impreg-
nated into a porous support membrane (see the
topic “▶ Supported liquid membrane for
enantioselective separation”). In enantioselective
solid membranes, chirality recognition exists in
main polymer chain, chiral polymer branch,
doped chiral selector, or cavity formed by molec-
ular imprinting (see the topic
“▶ Enantioselective transport of amino acids by
membrane operations”).
Although the industrial application of
membrane-based chiral separation has been very
few until now, one successful example exists in
chiral drug production. Diltiazem is a calcium
channel blocker used for hypertension and angina
treatment, and a lipase-immobilized membrane
reactor was applied to the enantiomeric separa-
tion of chiral intermediate of this drug (Lopez and
Matson 1997). In the separation process,
a biphasic membrane system is used. Figure 1
shows the concept of enantiomeric separation in
2 Chiral Drug Separation by Membranes
Chiral Drug Separation
by Membranes,
Fig. 1 Concept of (R), (S)-isomers (ester)
enantiomeric separation in
a biphasic enzyme
membrane reactor
a biphasic membrane reactor using enzyme
immobilized on the membrane surface. The
immobilized enzyme on a membrane hydrolyzes
preferentially one isomer ester in the organic feed
phase, and the produced acid is extracted into the
aqueous phase. In this system, reaction and sep-
aration occur simultaneously in/on membranes.
Membrane technology has a potential to
improve the application of enzymatic reactions
to the industrial scale production of chiral drugs.
The recent progress of enzymatic membrane
reactors was reviewed elsewhere (Rios
et al. 2004).
The most important factor for successful opti-
cal resolution of enantiomers in a racemate is the
design of a chiral selector fitting for the separa-
tion, because many drugs have complicated steric
structures. One of the measures devised to deal
with this problem is the implementation of com-
binatorial strategies (Maier et al. 2001). Large
Organic phase (shell side)
(R)-isomer (ester)
Lipase-immobilized UF membrane
(S)-isomer (acid)
Aqueous Phase (lumen side)
libraries of potential selectors are generated, and
the systems with desirable properties are
extracted from the libraries.
References
Li B, Haynie DT (2007) Chiral drug separation. In: Ency-
clopedia of chemical processing. Taylor & Francis
Online, pp 449–458
Lopez JL, Matson JL (1997) A multiphase/extractive
enzyme membrane reactor for production of diltiazem
chiral intermediate. J Membr Sci 125:189–211
Maier NM, Franco P, Lindner W (2001) Separation of
enantiomers: needs, challenges, perspectives.
J Chromatogr A 906:3–33
Rios GM, Belleville MP, Paolucci D, Sanchez J (2004)
Progress in enzymatic membrane reactors – a review.
J Membr Sci 242:189–196
Sekhon BS (2010) Enantioseparation of chiral drugs – an
overview. Int J PharmTech Res 2:1584–1594
M
Magnetically Responsive
Membranes
S. Ranil Wickramasinghe1 and Xianghong Qian2
1
Ralph E Martin Department of Chemical
Engineering, University of Arkansas,
Fayetteville, AR, USA
2
Department of Biomedical Engineering,
University of Arkansas, Fayetteville, AR, USA
Synonyms
Environmentally responsive membranes;
Multifunctional responsive membranes; Respon-
sive membranes; Smart membranes; Stimuli-
responsive membranes
Introduction
Responsive membranes represent a new class of
advanced membranes that respond to an external
stimulus (Bhattacharyya et al. 2012; Wandera
et al. 2010). They are a subset of multifunctional
membranes where the membrane performs more
than one function simultaneously. The develop-
ment of responsive membranes has been inspired
by biological membranes such as skin and epi-
thelial tissue. The barrier properties of biological
membranes can be modulated by environmental
conditions such as temperature, humidity, pres-
ence of a specific ion, etc. Responsive
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1431-1
membranes mimic this behavior allowing for
modulation of membrane performance by envi-
ronmental conditions. In general, in the case of
porous membranes, responsive behavior is
imparted by grafting responsive polymer layers
onto the membrane surface. For nonporous mem-
branes the responsive groups are often part of the
membrane polymer (Husson 2012).
Stimuli-responsive membranes make use of
the interplay between membrane structure and
changes in polymer conformation, polarity, and
reactivity (Darvishmanesh et al. 2015). Respon-
sive behavior occurs in two steps: an environ-
mental trigger causes a conformational and/or
property transition at the microscopic level
which is then amplified to a macroscopically
measurable change in membrane performance.
Responsive behavior is a result of changes in
polymer chain conformation and/or property.
Changes in polymer chain conformation and
property are due to variations in protonation or
deprotonation, hydrophilicity/hydrophobicity,
charge density and distribution, solvation free
energy, etc. The conformational change is driven
thermodynamically to minimize the Gibbs free
energy of the polymer/solvent system
(Du et al. 2010).
Types of Stimuli
Responsive behavior may be categorized
according to the type of stimulus used to elicit
2 Magnetically Responsive Membranes
Magnetically Responsive Membranes, Fig. 1 Types
of stimuli (Reprinted from Current Opinion in Chemical
Engineering, vol number: 8, Siavash Darvishmanesh,
polymer conformational and/or property changes
(Darvishmanesh et al. 2015). Figure 1
(Darvishmanesh et al. 2015) gives a schematic
representation of the three types of stimuli: direct,
indirect, and field induced. Direct stimulation is
specific. The responsive groups on the membrane
respond to a specific chemical or biological cue.
For example, pH-responsive groups respond to
changes in pH (H+ ion concentration) (Himstedt
et al. 2013a; Gugliuzza 2013; Wee et al. 2013).
A carboxylic group (e.g., acrylic acid) at pH
below its pKa is protonated leading to its
decreased hydration and de-swelling effect. The
polymer network swells when the pH exceeds its
pKa as the carboxylic groups become
deprotonated and repel each other. Thus mem-
brane permeability can be adjusted. In the case of
pH-responsive groups, a number of different
Xianghong Qian, S Ranil Wickramasinghe, Responsive
membranes for advanced separations, 98–104, 2015, with
permission from Elsevier)
weak base and acid groups respond to a specific
chemical cue, H+ ions in solution.
Solution ionic strength is another example of a
direct stimulus and can affect the degree of poly-
mer swelling in a number of ways. The presence
of salt ion and its type and concentration affect
charge interactions in the membrane/solution
system. It affects the degree of swelling for
pH-responsive membranes. Salt ions can cause
charge screening thus limiting the amount of
swelling. Strong acid and base groups such as
quaternary amines are insensitive to solution pH
but respond to changes in ionic strength (Husson
2012). In addition poly (zwitterion)-based multi-
layer membranes have also been shown to
respond to solution ionic strength (de Grooth
et al. 2014). However unlike weak polyelectro-
lytes such as weak acids and weak bases, increas-
ing ionic strength leads to an increase in swelling.
Magnetically Responsive Membranes
Biologically inspired responsive groups
include (i) antigen-responsive membranes
(Zhang et al. 2007; Lu et al. 2003), (ii) redox/
thiol-responsive groups (Wong et al. 2008;
Cerritelli et al. 2007; Ghosh et al. 2009), (iii)
enzyme-responsive membranes (Ulijn 2006),
and (iv) glucose-responsive membranes (Chu
et al. 2004). In these cases a chemical or biolog-
ical cue directly interacts with a specific chemical
groups on the membrane surface. Thus they are
much more specific than the pH and ionic
strength-responsive group describe above.
Indirect stimulation, like direct stimulation,
involves mass transfer to the responsive groups.
However unlike direct stimulation, changes in
polymer conformation/property occur due to
changes in the thermodynamic environment and
not to a specific interaction with a chemical or
biological cue. Most temperature-responsive
polymers display a lower critical solution tem-
perature (LCST). A common example is poly
(N-isopropylacrylamide) (PNIPAM). PNIPAM
is a hydrogel that is water soluble when the tem-
perature is below its LCST. Above its LCST, the
polymer becomes hydrophobic and will phase
separate. When PNIPAM chains are attached to
a membrane surface, the grafted polymer layers
swell and de-swell when the local temperature
fluctuates below or above the LCST. Previous
studies have shown that conformational
switching can lead to the release of adsorbed
foulants (Wandera et al. 2011, 2012; Tomer
et al. 2009). The LCST of thermo-responsive
polymers is strongly affected by the salt ion, its
type, and concentration. An increase in concen-
tration will lead to a decrease in LCST. The
actual decrease in ionic strength depends on the
specific ion present in solution. Recent studies
suggest that modulation of LCST by solution
ionic strength could be used to develop high-
performance ligands for applications such as
membrane-based hydrophobic interaction chro-
matography (Wu et al. 2014; Himstedt
et al. 2013b).
Ultrasound represents another method of indi-
rect stimulation. Ultrasound-responsive mem-
branes have been reported for biomedical
applications such as controlled drug release. To
3
date most responses to ultrasound waves lead to
irreversible cleavage of weak bonds in the poly-
mer structure. Consequently, unlike the other
responsive mechanisms described here,
ultrasound-responsive membranes tend to
undergo irreversible transformations
(Li et al. 2010; Zhang et al. 2009). Development
of reversible ultrasound-responsive polymers that
undergo reversible transformations could be an
area of future development.
Field-induced responsive behavior is funda-
mentally different to the direct and indirect
responses as no mass transfer is required. Three
types of external field, electric, magnetic, and
electromagnetic waves, have been considered in
the past. Electric field-responsive membranes
shrink, swell, or twist in response to an external
electric field due to the interaction of charged
species with the external field. These changes in
polymer confirmation can be used to control sol-
ute permeation through the membranes. In addi-
tion development of fouling-resistant membranes
based on desorption of adsorbed solutes due to
changes in polymer conformation induced by
changes in an external electric field has been
described (Wandera et al. 2010).
Magnetic field-responsive groups such as
magnetic nanoparticles are usually physically
entrapped within the membrane structure or
immobilized onto the membrane surface.
Changes in an external magnetic field can cause
movement and/or heating of these magnetically
responsive groups. Recent studies indicate that
movement of magnetically responsive polymer
chains attached to the membrane surface can
suppress concentration polarization during
nanofiltration (Himstedt et al. 2011; Yang
et al. 2013). In addition magnetically responsive
polymer chains attached to the inside pore sur-
face of microfiltration membranes can be used to
modulate membrane permeability by applying an
external magnetic field (Himstedt et al. 2012).
Electromagnetic radiation such as UV, IR,
etc. has been used to trigger structural transfor-
mations of functional species such as azo groups
(Ishihara et al. 1984; Ishihara and Shinohara
1984; Kinoshita et al. 1986). For example,
photo-responsive polyethersulfone (PES)
4 Magnetically Responsive Membranes
membranes were prepared from blending PES
with azobenzene(Azo) and b-cyclodextrin
(b-CD). The water permeability of the mem-
branes was tested under light irradiation at
450 and 365 nm, respectively. At 450 nm, the
membrane pores close and water flux decreases
due to the complex formation between Azo and
b-CD. By changing irradiation wavelength to
365 nm, the membrane pores open due to com-
plex dissociation between Azo and b-CD, and the
membranes show higher permeability.
Outlook
Though very much in its infancy, development of
responsive membranes offers numerous opportu-
nities for designing high-performance mem-
branes for future separations needs. It is likely
that more complicated responsive mechanisms
that involve a cascade of stimuli-response inter-
actions will be developed analogous to biological
membranes. It is also likely that computational
simulations will provide valuable guidance when
developing the appropriate nanostructures for
these advanced membranes.
References
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(2004) Control of pore size and permeability of a
glucose-responsive gating membrane for insulin deliv-
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(2015) Responsive membranes for advanced separa-
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