Ict I Desalination and Water Reuse: "Sea To Sink To The Sea Again"

ICT I
Desalination and Water Reuse

J. Georgiadis, O. Coronell, L. Rakocevic,
P. Tontcheva, E. Morgenroth
sea to sink to the sea again
Desalination & Water Reuse
Institutions & PIs
U.C. Berkeley: R. Shen LLNL: O. Bakajin
Howard University: K. Jones Notre Dame: P. Bohn
University of Illinois: N. Aluru, D. Cahill, J. Economy, J.
Georgiadis, S. Granick, E. Luijten, B. Marias, J.
Moore, E. Morgenroth, M. Shannon
Massachusetts Institute of Technology: A. Mayes
Rutgers University: S. Prakash
University of Michigan: L. Raskin
Yale University: M. Elimelech
ICT-1: Organization & Objectives
Area I-A: Thermal Desalination and Liquid Discharge
Minimization
Reduce energy expenditure relative to RO
Minimize liquid discharge to less than 5% of total flux
Area I-B: Pressure-driven and Active Membranes
Increase flux 2-fold
Decrease fouling
Area I-C: Membrane Bioreactor Technology
Decrease sorptive, particle, and biofilm fouling
Link MBR with downstream processing (e.g. RO) for
water reuse
Reverse Osmosis Energy Use
Minimum
energy of
separation
John MacHarg and Randy Truby, West coast researchers seek to demonstrate SWRO affordability,
Desalination and Water Reuse, 14/3, 2004.
Energetics of Desalination
AP = t + AP
reject
+ AP
polar
+ AP
membrane
+ AP
viscous
+ AP
foul
Reverse Osmosis Cost
Shannon et al., Science and technology for water purification in
the coming decades, Nature, 452, 2008.
Area I-A: Thermal Desalination and Liquid
Discharge Minimization
Forward osmosis
Active membranes
NF/RO membranes
Antifouling membranes
Fouling mechanisms
Extracellular polymeric substances
0
1
2
3
4
5
6

k
W
h
/
m
3
MSF
MED-TVC
MED-LT
RO
FO-LT

Energy Requirements of Desalination
Technologies
Contribution from
Electrical Power
Adapted from: McGinnis, Elimelech, Energy Requirements of AmmoniaCarbon Dioxide
Forward Osmosis Desalination, Desalination, 207 (2007) 370-382.
RO FO
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0
0
5 0
1 0 0
1 5 0
2 0 0
2 5 0
3 0 0
3 5 0
4 0 0
4 5 0

t (atm)
R e c o v e r y ( % )
Seawater t
Minimizing Liquid Discharge
Forward Osmosis (FO)
R. McGinnis, D. Chen, O. Bakajin, M. Elimelech
Saline
Water
Draw
(NH
3
/CO
2
)
Product
Water
Brine
Membrane
Draw Solute
Recovery

Energy
Input
t
D,b

At
Theo

Water flux
t
F,b

At
eff

Convection
Porous
support
Active
layer
Challenge: Concentration Polarization in FO
Concentrative external CP
Feed
crossflow
Draw
crossflow
Diffusion
Dilutive Internal CP
Diffusion
) (
) (
, ,
eff W
m F m D W
A J
A J
t
t t
A =
=
Forward osmosis
Active membranes
NF/RO membranes
Fouling mechanisms
Active Transport Membranes
Active Transport - Nanocapillary Array Membranes
S. Prakash, J. Lucido, H. Fitzhenry, J. Wan, G. Mensing, J. Georgiadis, M. Shannon
NCAM
HEMA
Au- NCAM
Ion transport occurs across membranes and AC bias is
more effective than DC bias for manipulating ion flux.
0
40
80
120
160
0 25 50 75 100 125 150 175 200 225 250
Time (min.)
C
o
n
d
u
c
t
i
v
i
t
y

(
S
)
0.00625 mM No bias
1 mM No bias
0.00625 mM DC bias
1 mM DC bias
0.00625 mM AC bias
1 mM AC bias
Slope: 0.045 0.001
Slope: -0.153 0.001
Slope: 0.106 0.002
Slope: -0.161 0.004 Slope: -0.231 0.008
Slope: -0.295 0.01
Forward osmosis
NF/RO membranes
Active membranes
Fouling mechanisms
Water flux in Nanochannels
L. Rakocevic, M. Suk, A. Raghunathan, N. Aluru, J. Georgiadis, M. Shannon
Water flux vs. P for
BNNT, CNT, and PMMA membrane
Flux enhancement
in CNT/BNNT
Water transport by collective hopping
events of single-file water molecules
Permeation coefficient, p
n
=k
0
by
reaction rate theory where k
0
is
equilibrium hopping rate
Density Functional Theory
Lengthscale O(A)
Molecular Dynamics
Timescale O(ns)
Lengthscale O(nm)
Coupled Poisson Nernst Planck
Timescale O(ms)
Lengthscale O(mm)
Ion mobility Diffusion
coefficient
Partial charges
The system

The material

Characterization of RO Membranes
O. Coronell, X. Zhang, D. Cahill, B. Marias
FT30 Reverse osmosis (RO)

Support Layer
(Polysulfone)
Selective barrier
(polyamide)
Membrane characterization
procedures are needed
~150 nm
Polyamide
(~100 nm)
NHCO
NH
2

CONH NHCO
CONH COOH
Pressurized feed
Amine group
Carboxylic group
Amide link
Functional groups in the active layer
Polysulfone
(50 m)
Polyamide
(~150 nm)
Ag
+
Ag
+

Ag
+
Ag
+
Ag
+

Ag
+

Ion probing Rutherford backscattering spectrometry (RBS)
RBS Detector
He
+
pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
I
o
n

p
r
o
b
e

c
o
n
c
e
n
t
r
a
t
i
o
n

(
M
)
0.0
0.1
0.2
0.3
0.4
0.5
R-COO
-

R-NH
3
+

1. Quantification of functional groups (FGs)
FT30 (RO) RBS data
pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
I
o
n

p
r
o
b
e

c
o
n
c
e
n
t
r
a
t
i
o
n

(
M
)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
w
1
= 0.2 ; pK
a,1
= 5.3
w
2
= 0.8 ; pK
a,2
= 9.0
Carboxylic
groups
[R-COO
-
]
MAX
=
0.435 M
2. Modeling of ionization behavior of FGs
FT30 (RO) RBS data
3. Location of FGs in the active layer
Polyamide
active layer
Polysulfone
support layer
Chlorine
FT30 (RO) Secondary ion mass spectrometry (SIMS) data
~150 nm

1. Elemental composition of active layer
2. Thickness and roughness of active layer
3. Quantification of functional groups (FGs)
4. Modeling of ionization behavior of FGs
5. Quantification of steric and valence effects
on counterions
6. Location of FGs in the active layer
Research achievements
Water Mobility in CNT Membranes
L. Rakocevic (UIUC), J. Georgiadis (UIUC), O. Bakajin (LLNL)
Thickness = 3 m
Porosity = 2 %
Hydrophobic material
Average pore size=1.6nm
Atomically smooth walls
Double walled
Carbon Nanotube
TEM image of CNT membrane
Holt et al. Science 2006
CNT Membrane Performance
MD: water diffusion coef. ~1.510
-5
cm
2
/s !
Bulk water diffusion coef. ~ 2.610
-5
cm
2
/s
Diffusion inside CNTs has not been measured before
Energy requirements (estimated): Reduced AP
membrane
40% reduction
relative to RO for seawater desalination
Experiment: Improved salt rejection and flux relative to commercial NF membranes
High water diffusion coefficient inside CNTs despite restricted space (~ nm)
Formasiero et al. PNAS 2008
Objectives
Verify high (restricted) water diffusivity
inside CNTs
Measure water dispersivity inside CNTs
Quantify water displacement statistics
inside CNTs
Advance unique experimental technique
(MRI) for probing mass transport inside
novel membranes

Gradient G is applied for time

Diffusion-Weighted MRI (1)
Free water
Bound water
Bound water
20 30 40 50 60 70
G
o |
0 0
Gx = A
Free water
wait for a short time A.
Bound water
Bound water
x k x x
x
A +
0 0
Bound water
Bound water Free water
G
-20 -30 -40 -50 -60 -70
Gradient G is applied for time
o o | x Gk Gx
s
A = A
0 1
Diffusion causes phase incoherence and
therefore MRI signal loss
The diffusion-weighted q-space (displacement space) gives
a signal E
(q) such that:

Example: 1-D Fickian diffusion

MRI signal:

Displacement-Weighted MRI
dR R q i R P q S ) 2 exp( ) , ( ) ( - A =
}
t
Propagator function
Probability that a
spin will displace
amount R (R = r r)
during time
Accumulated phase term,
where q = 1/(2) g
(g is the gradient amplitude)
) exp( ) ( bD q S =
Experimental setup and current
progress
2% 20 % void fraction
3 m 100 m-thick layers
with aligned carbon nanotubes
Experimental setup
LLNL current membrane fabrication improvements
Current Progress
Sample with water
Sample with water +
CNT membrane parts
) exp( ) ( bD b S =
Forward osmosis
Active membranes
NF/RO membranes

Fouling mechanisms
PAN-g-PEO as an Additive for UF
Fouling Resistance
Doctor Blade
Coagulation Bath
Casting Solution
Heat Treatment
Bath
Casting
Solution

Doctor
Blade
Coagulation
B ath

Heat
Treatment
graft copolymer added
to casting solution
segregate & self-organize
at membrane surfaces
PEO brush
layer on
surface and
inside pores
Fouling
resistance
Asatekin, Kang, Elimelech, and Mayes: J.Membr.Sci. 298 (2007) 136-146.
Kang, Asatekin, Mays, and Elimelech: J.Membr.Sci. 296 (2007) 42-50.
Increased clean
water flux with
increased comb
content

After fouling with
BSA - complete
flux recovery with
20% comb content
Fouling Reversibility (with BSA)
Gray: Recovered flux after
BSA fouling/water flushing
White: Pure water
Average AFM results are not
consistent with observed fouling
reversibility
-8
-6
-4
-2
0
2
4
F
/
R

(
m
N
/
m
)
PAN (P0-0)
P50-5
P50-10
P50-20
Carboxylate-modified latex
particle as model foulant
Membrane
Attractive interaction
Repulsive interaction
Comb content
0%
5%
10%
20%
Incomplete flux recovery with 10% comb content
Average AFM results suggest repulsive interactions
PAN
-12 -10 -8 -6 -4 -2 0
0
15
30
45
60
F
r
e
q
u
e
n
c
y

(
%
)
F/R (mN/m)
PAN (P0-0)
Incomplete fouling reversibility due
to heterogeneous comb distribution
PAN 5%
-12 -10 -8 -6 -4 -2 0 2 4
0
15
30
45
60
F
r
e
q
u
e
n
c
y

(
%
)
F/R (mN/m)
P50-5
Comb content
PAN 5% 10%
-1 0 1 2 3
0
15
30
45
60
F
r
e
q
u
e
n
c
y

(
%
)
F/R (mN/m)
P50-10
Comb content
PAN 5% 10% 20%
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0
15
30
45
60
F
r
e
q
u
e
n
c
y

(
%
)
F/R (mN/m)
P50-20
Comb content

10 100
-1.0
-0.5
0.0
0.5

NaCl alone
NaCl + CaCl
2
F
/
R

(
m
N
/
m
)
Ionic Strength (mM)
Fouling resistance
due to steric interactions
Interaction forces are
independent of ionic
strength
Electrostatic forces
cannot explain
observed effects
Steric interactions
Promising results using model foulants but in
MBR fouling mechanisms are more complex
Model foulants
Proteins (BSA)
Polysaccharide (alginate)
Natural organic matter (humic
acid)

Fouling in MBR dominated by
(EPS)
Microbial flocs
Biofilm growth
Floc fragments Colloidal EPS Soluble EPS
Shear forces
Bacteria/archaea
EPS
Microbial floc
Membrane
Biofilm Growth
Organic
substrate
Organic
substrate
10 mM 30 mM 30 mM+Ca 100 mM
0
300
600
900
1200

C
e
l
l
s

A
d
h
e
r
e
d

(
m
m
-
2
)

PAN/PAN-g-PEO
Commercial PAN
No E. coli Adhesion on
PAN/PAN-g-PEO!
No attachment of E. coli cells on
PAN-g-PEO membrane during
static (1 h batch) adhesion test
Commercial membrane
exhibited increased cell
attachment as the ionic strength
was increased
PAN-g-PEO UF membranes resistant
against bacterial attachment
1 h
10 100
0
25
50
75
90
100
PAN/PAN-g-PEO with NaCl With 1 mM Ca
Commercial PAN with NaCl With 1 mM Ca
R
e
m
o
v
a
l

(
%
)
Ionic strength (mM)
Percent removal of E. coli cells
from the membrane at 150 cm/s
cross flow velocity
Clean water rinsing can remove previously
attached E. coli from PAN-g-PEO membrane
Forward osmosis
Active membranes
NF/RO membranes
Fouling mechanisms
Relevance of MBR to Advanced
Wastewater Reuse
Disinfection
(UV )
Wastewater
MBR
using MF or UF
RO
Water
suitable
for reuse
MBR: Microbial production and degradation of foulants (e.g., soluble
extracellular polymeric substances - proteins, polysaccharides)

RO: Fouling in RO (ICT1-B) is directly related to effectiveness of MBR
treatment (ICT1-C)

Disinfection: ICT III
Wastewater
Effects of long-term operation of MBR
Comparing short (hours) and long-term
(weeks) fouling in anaerobic MBR
Petia Tontcheva

Mixing and mechanical shear in MBR affects
the microbial ecology
Floc structure
Amount and characteristics of
extracellular polymeric substances (EPS)
Membrane fouling
Shear forces
Bacteria/archaea
EPS
Microbial floc
Membrane
Biofilm Growth
Organic
substrate
Organic
substrate
Short and long-term fouling in
anaerobic membrane bioreactors

Petia Tontcheva (UIUC)
PIs: Morgenroth (UIUC), Raskin (Michigan), Anne M. Mayes (MIT)

Background: Antifouling NF (PVDF-g-POEM)
Membranes
Dead-end filtration of activated sludge from MBR
PVDF-g-POEM NF: no flux loss over 16 h filtration
PVDF base: 55% irreversible flux loss after 4 h

0 12
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4

N
o
r
m
a
l
i
z
e
d

f
l
u
x
Time (hours)
PVDF base (-,-)
PVDF-g-POEM (,)
Volatile suspended solids
(VSS): ~1800 mg/L
Asatekin, Menniti, Kang, Elimelech, Morgenroth, Mayes: J.Membr.Sci. 285 (2006) 81-89.
How will the antifouling membranes perform in long-term
experiments?
Time of cross-flow cell operation (d)
0 5 10 15 20 25 30 35
F
l
u
x

(
L
/
m
2
h
)
0
20
40
60
80
100
120
Clean water flux of new membrane
Flux with anaerobic biomass
Clean water flux after fouling
Long-term (30d) operation of PAN/PAN-g-PEO in
anaerobic MBR
Reduced flux due to cake
layer formation

Complete recovery of flux
after clean water flushing
VSS: ~ 11, 000 mg/L
PES-V PES-O PVDF PAN-g-PEO/PAN
I
r
r
e
v
e
r
s
i
b
l
e

r
e
s
i
s
t
a
n
c
e

(
1
0
-
1
2
m
)
-1
0
1
2
3
4
5
Short-term (5 hrs)
Long-term (13 d)
Long-term (30 d)
The PAN/PAN-g-PEO membranes did not exhibit
irreversible fouling
Membrane surface analysis by XPS
No indication of inorganic fouling (no Ca, Mg, ... detected)
Increasing quantities of organic foulants on PES-O membranes during the long-
term tests
c
le
a
n
m
e
m
b
ra
n
e
S
h
o
rt-te
rm
L
o
n
g
-te
rm
A
t
o
m
i
c

r
a
t
i
o
0
20
40
60
80
100
120
(C+N)/S
O/S
PES-O membrane
Functional group identification by ATR-
FTIR
Wavenumbers (cm
-1
)
1000 1500 2000 2500 3000 3500
A
b
s
o
r
b
a
n
c
e
0.00
0.02
0.04
0.06
0.08
0.10
Long-term (13 d)
Short-term
O-H
N-H
C-H
COOH
Amide I
C-O
Amide II
Irreversible foulants: proteins, carbohydrates, and humic acids
PES-O Membrane
Shear
High Shear
Low Shear
S
o
l
u
b
l
e

E
P
S

High shear
results in
Smaller
microbial flocs
Less floc
associated EPS
Less soluble
EPS

Influences microbial physiology to reduce
microbial foulant (= EPS) production in MBR
Low shear
High shear
EPS from high shear MBR is stickier
Continuous high shear produces
less EPS in MBR - but EPS is
stickier

How to best operate MBR?
Mixing/shear main
contribution to energy input
Reduced fouling potential for
high shear operation
Variable shear can release
floc associated EPS and
result in fouling

Membrane
CML
COO
-
C
O
O-
C
O
O
-
EPS
- O
O
C
F
3 m carboxylate modified latex particle
Membrane
CML
COO
-
C
O
O-
C
O
O
-
EPS
- O
O
C
F
3 m carboxylate modified latex particle
Extracellular polymeric
substances (EPS) extracted
from microbial flocs
Vision for integrated MBR for
wastewater reuse
Wastewater
NF based MBR
Integrated application
of sorptive, ion
exchange, catalytic
media
Water
suitable
for reuse
Wastewater
Single unit system without the need
for downstream processing

Increase membrane rejection (NF
instead of UF or MF membrane)
Integrate alternative removal
mechanisms with biological process
ICT 1 Path forward
Fundamental Science
Multiscale computational framework
to explain RO and active membrane
systems
Computational and experimental
techniques to understand
electrokinetic transport in single
nanopores
Novel optical, spectroscopic, AFM,
and RBS techniques to understand
transport in membrane systems

Membrane materials
Improve robustness of novel
UF/NF/RO membranes (e.g. RSA,
CNT, PAN-g-PEO, etc.)
Develop appropriate membrane for
forward osmosis desalination
Long-term fouling and cleaning with
novel fouling resistance membrane
Biological processes
Link microbial ecology to fouling in MBR
Mechanisms and characterization of microbial
EPS production and degradation
Microbial mechanisms of cell attachment and
biofilm formation
Removal of micropollutants (w/ SIEMENS)
Microbial conversion
Integrate sorptive or catalytic media with
microbial processes

System integration
Demonstrate active membrane desalination
Complete pilot FO system
Apply magnetic resonance imaging (MRI) and
computational fluid dynamics (CFD) to reduce
cake formation in MBR (w/ SIEMENS)
Compare of aerobic and anaerobic MBR (w/
SIEMENS)
Shear
Bacteria/archaea
EPS
Microbial floc
Membrane
Shear
Bacteria/archaea
EPS
Microbial floc
Membrane
Biofilm Growth Biofilm Growth
CNT-membrane

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