J Porous Mater

DOI 10.1007/s10934-016-0226-8

Preparation of carbon molecular sieve membrane derived

from phenolic resin over macroporous clay-alumina based
support for hydrogen separation
Sanjukta Roy1 Rakhi Das1 Mahesh Kumar Gagrai1 Sandeep Sarkar1

Springer Science+Business Media New York 2016

Abstract An asymmetric carbon membrane was prepared

by coating alcoholic solution of industrial grade phenol
formaldehyde novolac resin (PFNR) directly over indigenously prepared macroporous clay-alumina based ceramic
support without using any microporous intermediate layer.
The initial three coatings of 40 wt% PFNR solution was
carried out using vacuum assisted dip coating method
followed by fourth coating of same solution by normal dip
coating method and final fifth coating of 60 wt% PFNR
solution also by normal dip coating method. After each
coating, the coated support was air dried in room temperature for 24 h and was subjected to pinhole test with
nitrogen gas, failing which the coating process was repeated. The finally coated support was carbonized at 780 C
in nitrogen atmosphere to obtain a layer of carbon molecular sieve membrane (CMSM) over the support. FESEM
and EDX analysis confirmed the formation of CMSM
membrane directly over the support. HK method of pore
size analysis revealed the presence of ultramicropores in
8A
in the prepared CMSM. Single gas
the range of 4A
permeation test through the CMSM showed that it exhibits
selectivities of 9.00, 14.28 and 10.21 for H2/N2, H2/CO2
and H2/CH4 systems respectively with H2 permeability of
27 9 10-9 mol.m-2.s-1.Pa-1.
Keywords Carbon molecular sieve  Hydrogen
separation  Clay-alumina  Phenol formaldehyde novolac
resin

& Sandeep Sarkar

sandeeep@cgcri.res.in; sandeepsarkar123@gmail.com
1

Ceramic Membrane Division, CSIR-Central Glass and

Ceramic Research Institute, Kolkata 700032, India

1 Introduction
Membrane systems are found to be advantageous over other
traditional separation methods due to their lower energy
consumption and lower environmental impact [1]. Considering the current trends in the membrane research field,
attempts are being made for the development of novel gas
separation membranes to overcome the limitations faced
with respect to permeability/selectivity trade-off relationship
with the commercially available membranes [2]. Polymeric
membranes have gained attention for gas separation purposes due to their process-ability and inherent permselectivity for different molecules but it is becoming increasingly
difficult to develop new polymeric membranes with high gas
selectivity without compromising its permeability [1]. In this
regard carbon molecular sieve membranes (CMSMs) have
been proved to be of much use. Since these materials are
known to have pores with dimensions that have close
resemblance to those of the diffusing species, minor variations in the atomic or molecular dimensions lead to a variation of diffusion rates for different gases [2]. Owing to
these characteristics, these membranes are termed to have
molecular sieving capabilities. A thin film of Carbon
Molecular Sieve (CMS) constitutes the Carbon Molecular
Sieve Membrane (CMSM) which enables a continuous
separation of gas mixtures [3]. CMSMs are known for their
unique characteristics such as good thermal and chemical
stability. They are more stable than polymeric membranes in
the presence of organic vapours at high temperatures,
organic solvents and non-oxidizing acid or base environments [4]. Consequently they have shown huge potential in
a variety of gas separation application fields that include
enrichment of nitrogen or oxygen from air, separation of
hydrogen from gasification gas, purification of natural gas,
recovery of hydrogen from hydrocarbons, separation of light

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J Porous Mater

alkenes/alkanes, removal of organic vapour or sour gas from

mixture [5], oxygen/nitrogen separation [6], etc. In general,
the carbon membranes used for gas separation are prepared
by coating a support media such as porous carbon, ceramic
or with a particular polymeric precursor followed by carbonization under controlled conditions. The preparation
process is one among the major obstacles in incorporating
these carbon membranes into actual industrial applications.
Usually the coating-carbonization cycle must be repeated
several times in order to attain a defect-free carbon membrane, which requires extended use of time, manpower and
raw materials. Considerable efforts are being made to prepare such a defect-free carbon membrane in a single casting
step. There are certain factors that need to be controlled and
optimized in order to produce a high efficiency carbon
membrane. The major factors that mainly dominate and
determine the microstructure and gas permeance characteristics are the polymeric precursor, membrane substrate,
membrane fabrication process and pyrolysis conditions.
Numerous polymeric precursors are being used for the
preparation of carbon membranes. It is preferred that the
polymer should have thermosetting property so that on
carbonization of the polymer layer the deposited layer of
CMSM is not deformed [7]. Damle et al. [8] coated porous
carbon supports with several thermosetting polymeric precursors such as polyacrylonitrile, polyfuryl acid, thermosetting phenolformaldehyde resin, cellulose, and
furfuryl alcoholphenolic resin to obtain a variety of carbon
membranes. The membranes were pyrolyzed at temperatures between 500 and 750 C under nitrogen atmosphere
and the coating-carbonization cycle was repeated several
times. Rao et al. [9] synthesized a carbon membrane by
coating polyvinylidene chloride latex over a macroporous
graphite sheet followed by carbonization at 1000 C under
nitrogen atmosphere. The coatingcarbonization process
was repeated five times. A carbon membrane using phenol
formaldehyde novolac resin was prepared by Wei et al. [10]
over a support with a similar composition (resin support)
which gave a separation factor of 28.22 for H2/CO2. A
similar approach for the synthesis of carbon molecular sieve
membrane was adopted by Zhang et al. where phenol
formaldehyde novolac resin along with some amount of
CMS was coated over the resin support (self carbon support)
and carbonized at 800 C [11].
Researchers generally have synthesized CMS membranes
over carbon supports with multiple cycles of coating and
carbonization. CMS can easily be prepared over the carbon
substrate both being made of carbon. These carbon substrates are prepared by pyrolysis at temperature lower than
1100 C [7] and are having less mechanical strength compared to substrates made of oxide ceramic (alumina, clay,
etc.) prepared at higher temperature ([1100 C). Literature
survey revealed that only a few works have been reported

123

regarding synthesis of CMS membrane over ceramic support. Kita et al. [12] prepared a carbon membrane by coating
a phenolic resin over porous alumina tubes. The coating and
pyrolysis was carried out several times which produced
carbon membranes having good separation factors for H2/
N2, O2/N2 and H2/CH4. Carbon membranes by coating
novolac phenolic resin over alumina supports in a single
casting step were prepared by Centeno et al. [13] which
showed a high selectivity for O2/N2. Kishore et al. [14]
synthesized nanofiltration carbon membrane by using phenolformaldehyde resin as a polymeric precursor. Tahri
et al. [15] used novolac phenolic resin along with carbon
black to prepare carbon ultrafiltration membrane, where the
casting-carbonization cycle was repeated to minimize surface defects. Similarly Ayadi et al. [16] prepared carbon
microfiltration membrane over graphite support using resol
type phenolic resin as binder with mineral coal powder.
Both the carbon microfiltration and ultrafiltration membranes were applied in treatment of textile industry effluent.
Tanco et al. [17] prepared CMS membranes from novolac
phenolic resin loaded with boehmite nanoparticles which
gave a good selectivity for H2/N2.
One of the significant practical problems that hinder the
development of carbon membrane technology and its
industrial application is the mechanical instability of these
carbon membranes due to their brittle nature [3]. Numerous
effective fundamental studies and practical techniques to
overcome this limitation have been studied and reported.
Nevertheless, there still remains a scope and requirement for
the exploration and development of newer methods in order
to simplify the membrane development process, reduce the
cost of production and improve the quality, performance and
reproducibility of these carbon membranes. A novel
approach to overcome these drawbacks has been tried by
synthesizing the CMS membrane over low-cost macroporous ceramic support instead of the carbon support. And
also the coating-carbonization cycle is carried out as minimum times as possible in a tubular support configuration.
This work proposes the preparation of carbon molecular
sieve membrane directly over indigenously prepared low-cost
clay-alumina based macroporous ceramic support without
providing any intermediate layer. Phenolformaldehyde
novolac resin (PFNR) was coated over the ceramic support
which is chosen due to its high carbon content and low cost.

2 Materials and methods

2.1 Materials
Alpha alumina (a-Al2O3) of 99 % purity, with a mean
particle size of 7 microns was purchased from Hindalco
Industries Ltd., India. Methocel was purchased from Dow

J Porous Mater

Chemicals, USA and clay (Kaolinite) with a mean particle

size of 10 microns was supplied locally, Kolkata, India.
The polymer precursor phenol formaldehyde novolac resin
(PFNR) (industrial grade) was purchased from local sources and ethanol from Merck, Germany. Purified nitrogen
(99.995 % purity), hydrogen (99.95 % purity), carbon
dioxide (99.95 % purity) and methane (99.95 % purity)
was supplied by Linde India, India.
2.2 Preparation of low cost clay-alumina based
macroporous ceramic support
Initially 60 wt% alumina and 40 wt% clay were dry mixed
in a sigma mixture (Brabender, Germany) for around
30 min. To this mixture methocel (organic binder) was
added (4 wt% of total clay-alumina mixture weight) and
mixed further. Finally water was added (22.5 wt% of total
clay-alumina mixture weight) to obtain an extrudable
ceramic paste. This ceramic paste was then extruded by a
single screw extruder (Brabender, Germany) with the aid of
an extrusion die. The green tubes with dimensions of
10 mm/7 mm (OD/ID) obtained were dried for 7 days at
room temperature. The dried tubes were sintered at
1350 C for 90 min as per the firing schedule shown in
Fig. 1 to obtain 8 mm/6 mm (OD/ID) macroporous ceramic support. The tubes were cut into lengths of 70 mm
each and were ultrasonicated to remove dust particles
present. Finally, the tube ends were glaze sealed prior to
CMSM preparation. The pore size and porosity of the
obtained ceramic support were found to be 0.57 lm and
27 % respectively. The addition of clay to alumina in the
ceramic paste provides dual advantage of reducing the cost
and lowering the sintering temperature [18].
2.3 Selection of polymeric precursor for the CMS
membrane
The precursor of the CMSMs plays a key role in governing
the structure and gas separation performance along with the

Fig. 1 Firing schedule for pyrolysis of green ceramic support

production cost of the CMSMs to a great degree [19].

Carbon membranes can be obtained by the carbonization or
pyrolysis of various carbon containing materials such as
thermosetting resin, graphite, coal, pitch and plants, under
inert atmosphere or vacuum [20]. Lately, numerous synthetic precursors, of which are mainly polymers such as
polyimide and derivatives, polyacrylonitrile (PAN), phenolic resin, polyfurfuryl alcohol (PFA), polyvinylidene
chlorideacrylate terpolymer (PVDCAC), phenol
formaldehyde, cellulose and others, have been used to form
carbon membranes [19]. Among these phenolic resins
being very popular and inexpensive polymers, find their
applicability in manufacturing of everyday commodity to
high technology materials [3]. Phenolic resins show
promising scope in application as precursor for CMSM due
to some of its properties such as:
(1)
(2)
(3)

The pyrolysis of phenolic resins produces carbon

films with molecular sieve properties [13].
They provide a high carbon yield after carbonization [3].
They are low cost polymers with a wide range of
applications in different fields [13].

Considering these features along with its easy availability, phenolformaldehyde novolac resin (PFNR) of
industrial grade has been chosen as the precursor for
preparation of CMSM in the present study (Fig. 2).
2.4 Preparation of CMS membrane over ceramic
support with PFNR precursor
Low cost industrial grade PFNR was used for coating the
macroporous ceramic support without any further pre-treatment. A 40 wt% coating solution of PFNR having viscosity
0.0346 Pa.s was prepared by dissolving PFNR in ethanol and
continuously stirring for 3 h in the temperature range of
4050 C in an Erlenmeyer flask with screw cap to avoid
loss of alcohol by evaporation. A 60 wt% coating solution of
PFNR having viscosity 0.3678 Pa.s was also prepared by
similar method. Both the polymeric solutions were degassed
in a vacuum system to remove gas bubbles present if any.
The PFNR solution was coated directly over the macroporous ceramic support, without any intermediate coating, by
inverted siphon technique. The coating process, as elaborated

Fig. 2 Chemical structure of repeated unit in PFNR

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J Porous Mater

in Table 1, involving both vacuum assisted dip coating and

normal dip coating methods along with different concentration of coating solution, was explored with an aim of producing a defect free CMSM over the ceramic support.
Vacuum assisted dip coating method was adopted in the
initial three coatings for the aid of developing a good
anchorage between the macroporous ceramic substrate and
the coated layer. Also precursor solution of lower concentration was used for the initial four coatings in order to
achieve good grip between the substrate and the coated layer.
Solution of low concentration penetrates into the irregularities of the macroporous substrate surface thus providing a
better rooting of the coated layer. A final fifth layer of thicker
precursor solution was coated to provide sufficient residual
carbon after pyrolysis for the formation of a dense carbon
membrane. After each coating process the coated tube was
air dried at room temperature for 24 h followed by pinhole
test with nitrogen gas. The coating process was repeated until
the membrane was found to be pinhole free. The finally
coated tube was carbonized in nitrogen atmosphere at
780 C following the firing schedule as shown in Fig. 3. The

Table 1 Coating process for

preparation of CMS membrane

coated tube was placed inside a horizontal alumina tube

chamber equipped with microprocessor controlled heating
elements. A gas feed system was connected to the alumina
tube chamber inlet. A flow rate of 40 cm3/min of N2 gas was
maintained throughout the pyrolysis process.
2.5 Characterization techniques
Thermogravimetric Analysis (TGA) and Differential
Thermal Analysis (DTA) of PFNR were performed using
TGA/DTA analyzer (NETZSCH, Germany). The temperature of the analyzer was risen at 10 C/min from room
temperature to 900 C in nitrogen atmosphere. The surface
morphology and cross-sectional images of the PFNR/ceramic composite CMS membrane was characterized using
Field Emission Scanning Electron microscope (FESEM),
(Zeiss, Oberkochen, Germany) and the elements present
were examined by adopting EDX analysis (Zeiss Supra
35VP, Germany). The average pore size and porosity was
determined by mercury intrusion porosimetry (Quantachrome Poremaster, Quantachrome).

Parameters
Coating cycles

PFNR soln. conc. (wt%)

Method

Pin hole test

1st coating

40

Vacuum assisted dip coating

Failed

2nd coating

40

Vacuum assisted dip coating

Failed

3rd coating

40

Vacuum assisted dip coating

Failed

4th coating

40

Normal dip coating

Pin hole free

5th coating

60

Normal dip coating

Pyrolysis at 780 C

780 C

0.5 C/min

380 C

120
min

2 C/min

0.5 C/min

180 C

90
min

0.5 C/min

30 C
Room
Temp.

60
min

Fig. 3 Firing schedule for pyrolysis of coated ceramic support

123

25 C
Room
Temp.

J Porous Mater

2.6 Gas permeation test

Fig. 4 Setup for measuring single gas permeation through CMS

membrane

The selectivity and permeability of single gas was studied

for the CMSM prepared. The single gas permeation studies
), CO2
were conducted for the following gases: H2 (2.89 A

(3.3 A), N2 (3.64 A) and CH4 (3.8 A). The selectivity (a)
was measured for the H2:N2, H2:CO2 and H2: CH4 systems.
The inlet pressure for the gases was kept at 15.92 psi
(109764.54 Pa) and the outlet pressure was atmospheric
pressure. The experiment was carried out at room temperature of 27 C. The schematic single gas permeation set
up has been illustrated in Fig. 4. The pure gases from the
cylinders passing through a pressure controller entered the
tube side of the membrane module where a dead-end flow
was maintained by closing the valve on the other side. The

Fig. 5 TGA/DTA curve for

precursor (PFNR)

Fig. 6 FESEM micrographs of prepared CMSM: a surface view b cross section view

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Fig. 7 EDX elemental mapping
of the CMSM a cross-section
view b top surface view

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J Porous Mater
0.0005

a
3.0
Upper Bound

2.5
0.0003

Log10 (H2/N2)

Pore volume,cc//g

0.0004

0.0002

2.0

1.5
Present Work

1.0

0.0001

0.5
0.0000

10

0.0

Pore Diameter,

Fig. 8 Pore size distribution of the supported CMSM by HK method

b
Table 2 Permeation rates and selectivity of pure gases through the
prepared CMSM

-9

System

H2

27 9 10

H2/N2

N2

3 9 10-9

H2/CO2

14.28

H2/CH4

10.21

-10

CO2

19 9 10

CH4

265 9 10-11

Upper Bound

Selectivity (a)

Log10 (H2/N2)

Permeation rate
(P) (mol.m-2.s-1.Pa-1)

3.0

2.5

Gas

Log10 P(H2), Barrer

9.00

2.0

1.5
Present Work

1.0

0.5

permeate gas flowed from the module to a soap bubble flow

meter where the flow rate was measured. The permeation
rate (P) was calculated using Eq. 1 [11]. The ratio of the
permeation rate or permeability of two gases at same inlet
pressure gave the selectivity.

c
2.5

Upper Bound

Where V is the volume of gas permeation in unit time, Dp

is the pressure difference in the membrane side, A corresponds to the area of the membrane tube, patm is the
atmospheric pressure, p0 is considered to be 101325 Pa and
T0 is 273 K, T is the ambient temperature.

Log10 P(H2), Barrer

2.0

Log10 (H2/CH4)

VT0 patm
P
ADpTp0

0.0

1.5

Present Work
1.0

0.5

3 Results and discussion

3.1 TGA/DTA analysis

0.0
1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Log10 P(H2), Barrer

The TGA/DTA analysis of PFNR precursor solution was

carried out to determine the pyrolysis schedule (Fig. 5). The
TGA analysis revealed that first noticeable weight loss starts
at around 170 C where nearly 14 % mass change occurs,
which was due to loss of excess solvent. Further substantial
weight loss, about 40 %, was observed from 380 C which

Fig. 9 Gas separation performance analysis of the prepared CMSM

on Robesons plot for a H2/N2, b H2/CO2 and c H2/CH4 systems

accounted for the release of hydrocarbons. Consequently two

dwells in the pyrolysis schedule, one at 180 C for 60 min
and another at 380 C for 90 min were maintained to avoid

123

J Porous Mater

hasty release of residual solvent and hydrocarbons, which

may result in uneven contraction and damage to carbon
matrix, causing micro-cracks or defects. A slow rise in
temperature (0.5 C/min) was maintained throughout for the
aid of slow heating. The final pyrolysis temperature was set
at 780 C where the rate of weight loss was found to be
considerably low. The soaking time at that temperature was
kept 2 h for proper carbonization which is important for
obtaining the final CMSM structure. Also the TGA analysis
revealed that the residual weight after carbonization was
about 45 %. Thus, not less than 40 wt% PFNR precursor
solution was used for membrane preparation to get a substantial amount of residual carbon after pyrolysis.
3.2 FESEM and EDX analysis
Field Emission Scanning Electron Microscopy was used to
study the surface and cross-sectional morphology of the
CMSM prepared. Figure 6a shows the surface morphology
of the membrane where a homogeneous top layer is seen
and Fig. 6b shows the cross-section. From the cross-sectional view, the formation of dense carbon membrane
directly over the macroporous support can be seen.
As evident from the EDX elemental mapping of the
membrane cross-section (Fig. 7a), the top layer shows peak
for carbon and the support shows peak for aluminum, silicon and oxygen. Further, EDX elemental mapping of the
membrane surface confirms the formation of a homogeneous top carbon layer.
Table 3 Experimental data
points close to the present
empirical upper bound for H2/
N2 separation

Table 4 Experimental data

points close to the present
empirical upper bound for H2/
CO2 separation

123

3.3 Pore size distribution analysis of CMS

membrane
The pore size distribution analysis of the supported CMS
membrane by HK method revealed the presence of pores in
(Fig. 8).
the size range of 48 A
3.4 Single gas permeation
The gas permeance of the prepared CMSM was measured
for gases with different kinematic diameters namely H2,
CO2, N2 and CH4 as discussed in Sect. 2.6. Permeation rate
of the different gases through the membrane along with the
selectivities obtained for H2:N2, H2:CO2 and H2: CH4
systems are summarized in Table 2. Considering the high
permeation rate of the gases, the selectivities are acceptable. The gas permeation rates through the membrane are
correlated with the kinetic diameter of the gas molecules
and decrease with increase in molecular size of gas, except
for carbon dioxide. Such low permeation rates of carbon
dioxide have also been reported elsewhere [7, 11].
3.5 Analysis of the prepared CMS membrane
by Robesons plot
The gas separation performance of the prepared CMS
membrane was analyzed on Robesons plot which relates the
permeability-selectivity trade-off relationship to an upper
bound relationship where the log of the separation factor

Material

P (H2), barrers

a (H2/N2)

References

Polybenzoxazinone imide (PBOI-2-Cu?)

3.7

960

[22]

Polyimide (1,1-6FDA-DIA)

31.4

165

[23]

Polyimide (NTDA-BAPHFDS(H))

52

141

[24]

Poly (amide-imide) (3a)

72

103

[25]

PIM-7

860

20.5

[26]

PIM-1

1300

14.1

[26]

Poly (trimethylsilylpropyne-co-phenylpropyne) (95/5)

20,400

2.5

[27]

Present work

80,634.60

9.0

Material

P (H2), Barrers

a (H2/CO2)

References

Liquid crystalline polyester (HBA/HNA 30/70)

0.0545

100.9

[28]

Polyaniline (redoped)
Polyimide (1,1-6FDA-DIA)

1.753
31.4

Poly (trimethylsilylpropyne)

13,900

0.495

[30]

Poly (trimethylsilylpropyne)

16,200

0.489

[31]

Poly (trimethylsilylpropyne-co-phenylpropyne) (95/5)

20,400

0.538

[27]

Poly (trimethylsilylpropyne)

23,300

0.53

[27]

Present work

80,634.60

23.1
8.05

14.28

[29]
[23]

J Porous Mater
Table 5 Experimental data
points close to the present
empirical upper bound for H2/
CH4 separation

P (H2), barrers

Material

a (H2/CH4)

References

Sulfonated polyimide [DAPHFDS(H)]

52

325

[24]

Polyimide (6FDA-mMPD)

106

121

[32]

Polyimide (6FDA-DDBT)

156

78.8

[33]

Hyflon AD60X

187

61.7

[34]

Teflon AF-2400

3300

5.5

[35]

Poly (trimethylsilylpropyne)

17,000

1.13

[36]

Poly (trimethylsilylpropyne-co-phenylpropyne)(95/5)

20,400

0.953

[27]

Poly (trimethylsilylpropyne)

23,200

0.995

[27]

Present work

80,634.60

10.21

versus the log of the higher permeability gas yields a limit for
achieving the desired result of a high separation factor
combined with a high permeability [21]. The performance of
the prepared CMS membrane was found to cross the upper
bound for all the H2/N2, H2/CO2 and H2/CH4 systems
(Fig. 9a, b, c). The key data points for construction of the
upper bound for the H2/N2, H2/CO2 and H2/CH4 systems are
tabulated in Tables 3, 4 and 5 respectively.

4 Conclusion
This study details the method of preparation of carbon
molecular sieve membrane directly over indigenously
prepared low cost clay-alumina based ceramic substrate.
Use of industrial grade phenol formaldehyde novolac resin
as precursor material and elimination of an intermediate
layer further lowers the cost of membrane preparation. The
coating process adopted in this work involved both vacuum
assisted as well as dip coating techniques, which resulted in
good anchorage between the carbon layer and the substrate.
Carbonization was carried out only once, after the final
coating. Sufficient number of dwells as required in the
firing schedule and a slow rise of temperature resulted in
the formation of a homogeneous carbon molecular sieve
membrane over the macroporous ceramic substrate. The
CMSM formed had selectivities of 9.00, 14.28 and 10.21
for H2/N2, H2/CO2 and H2/CH4 systems respectively with
H2 permeability of 27 9 10-9 mol.m-2.s-1.Pa-1.
Acknowledgement The work has been jointly funded by CSIR 12th
five year plan project (Project No.CSC0115 & ESC 0104) and
DST, GoI, project No. GAP0341. The authors thank Dr. Anshu
Nanoti, Mr. Swapnil Divekar and Mrs. Pushpa Gupta, CSIR-Indian
Institute of Petroleum, Dehradun248 005, India for their kind help
and valuable suggestions during the study.

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