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Abstract
Accurate prediction of concentration polarization (CP) phenomena is critical for properly designing reverse
osmosis (RO) processes because it enhances trans-membrane osmotic pressure and solute passage, as well as
surface fouling and scaling phenomena. The objective of this study was to compare available analytical CP models
to a more rigorous numerical CP model and experimental CP data. A numerical concentration polarization model
was developed to enable local description of permeate flux and solute rejection in crossflow reverse osmosis
separations. Predictions of channel averaged water flux and salt rejection by the developed numerical model, the
classical film theory model, and a recently proposed analytical model were compared to well-controlled laboratory
scale experimental data. At operating conditions relevant to practical RO applications, film theory and the numerical
model accurately predicted channel-averaged experimental permeate flux and salt rejection data, while the more
recent analytical model did not. Predictions of local concentration polarization, permeate flux, and solute rejection
by film theory and the numerical model also agreed well for realistic ranges of RO process operating conditions.
Keywords: Concentration polarization; Reverse osmosis; Film theory; Modeling; Membranes
1. Introduction
Concentration polarization (CP) is one of the
most important factors influencing the performance of membrane separation processes [1]. Prediction of solute concentration polarization is
crucial for designing reverse osmosis processes,
*Corresponding author.
0011-9164/06/$ See front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2005.05.017
112
between concentration polarization layer development and a locally varying permeate flux (in a
closed form analytical solution) by making use
of the retained solute concept [22]. This model
describes two dimensional convective-diffusive
solute transport without complex computational
effort, and hence, can be used to predict local concentration polarization and permeate flux in
spacer-free reverse osmosis flow channels. The
retained solute model appears an attractive alternative to film theory and is simpler than numerical
techniques, but it has not been subjected to
rigorous analysis or comparison to well-controlled
experimental data. A more rigorous numerical
convection-diffusion based concentration polarization model was developed for comparison with
the retained solute and film theory models. Predictions from all three models were compared to
experimentally-derived permeate flux and observed salt rejection data. The accuracy, limitations, and applicability of each model for RO
processes are discussed.
2. Theoretical
2.1. Analytical film theory (FT) model
A film theory approach to describe concentration polarization was developed by Michaels
and others [810]. Film theory simplifies a complex transport problem to a one-dimensional masstransfer problem by assuming axial solute convection near the membrane surface is negligible.
Integrating the one dimensional (transverse) convection-diffusion mass balance from the membrane surface out to a finite mass boundary (film)
layer thickness, , yields the relationship between
concentration polarization and permeate flux. The
result is
cw c p
v
= exp w
cb c p
D
(1)
( x)
h
= 1.475
x
x
2/3
1/ 3
umax h
(2)
D
1 3u D 2
k ( x) =
=
( x ) 1.475 2h x
1/ 3
D 2
= 0.538 w
x
113
D 2
k = 0.807 w
L
(4)
(5)
(3)
(6)
(7)
114
vw ( x ) C + D
C
=0
y
(8)
w yCdy = Ro cb vw ( x ) dx
0
(9)
vw ( x ) =
AF 0
(1 + 6F
X / Ns3 )
1/3
1/3
1/ 2
4
2
+
+
2
3
+
F
X
N
1
6
/
s )
(
(10a)
1/ 3
1/ 2
4
2
+
2
3
(1 + 6F X / Ns )
with F =
p 0
0
(10b)
1/ 3
and N s =
1 1 D 2 w
A 0 L
(10c)
p vw ( x ) / A + f os (1 Ro ) c0
f os
(11)
r2
r
v ( x, y ) = vw ( x ) 3 2 ;
h
2h
hvw ( x )
115
x +x
vw ( x )Wdx
(13)
Q ( x ) cb ( x ) = Q ( x + x ) cb ( x + x )
x +x
(12a)
(12b)
= Re w 1
vw ( x )Wcb ( x ) dx
(14)
where cb(x) and cb(x + x) are the bulk concentration at x and x + x, respectively. By solving
Eqs. (13) and (14) simultaneously, cb(x) is proved
constant and denoted as cb.
Solute mass should be conserved within concentration polarization layer as well, that is,
vw ( x ) c ( x, y ) + D
c ( x, y )
y
= vw ( x ) c p ( x )
(15)
116
Fig. 1. The problem domain used in developing the numerical convection diffusion model for a laboratory scale crossflow
membrane filter without mesh feed spacer. Feed water flows from left to right along the channel length and some portion
of water flows through the membrane.
v ( x)
c ( x, y ) = cw ( x ) c p ( x ) exp w
y
D
(16)
+ c p ( x ) ; y ( x )
At steady state, axial and transverse input and
output should be balanced in the problem domain
within concentration polarization layer as shown
in Fig. 1, that is
( x )
u ( x, y ) c ( x, y ) y
0
at x
( x )
u ( x, y ) c ( x, y ) y
0
at x +x
= cb c p ( x )
x +x
vw ( x )dx
(17)
The integrations in Eq. (17) are solved numerically using the trapezoidal rule. The concentration profile starting from an arbitrary (initial)
wall concentration is solved for by Eq. (16). As
the transverse coordinate (y) increases, the concentration decreases due to solute back transport by
convection and diffusion. The extent of the CP
boundary layer thickness is defined as the position
when the concentration, calculated from Eq. (16),
equals the bulk concentration. Concentration
polarization layer thickness is defined as the
distance from that position to the channel wall.
Above the CP layer, all the concentrations are
equal to the bulk concentration.
Since the initial wall concentration is an
arbitrary value, an iteration process is required.
This is performed by solving Eqs. (12), (16) and
(17) simultaneously to obtain the salt concentration locally in the channel. Once the local salt
117
(18)
118
50 (1170) 94.1% 1.42 1.37 -3.5% 1.09 -23.2% 1.40 -1.4% 96.1% 1.70 1.72 1.2% 1.18 -30.6% 1.76 3.5% 97.1% 1.99 2.13 7.0% 1.35 -32.2% 2.17 9.0%
20 (1170) 95.9% 1.89 1.60 -15.3% 1.18 -37.6% 1.66 -12.2% 97.0% 2.17 2.12 -2.3% 1.33 -38.7% 2.19 0.9% 97.5% 2.54 2.73 7.5% 1.60 -37.0% 2.80 10.2%
10 (1170) 96.6% 2.43 1.73 -28.8% 1.22 -49.8% 1.80 -25.9% 96.9% 2.38 2.29 -3.8% 1.38 -42.0% 2.39 0.4% 97.3% 2.76 3.04 10.1% 1.71 -38.0% 3.13 13.4%
93.7% 1.48 1.41 -4.7% 1.10 -25.7% 1.44 -2.7% 96.0% 1.83 1.83 0.0% 1.23 -32.8% 1.87 2.2% 97.0% 2.23 2.30 3.1% 1.47 -34.1% 2.33 4.5%
CD % err
50 (590)
p = 1380 kPa
EX FT % err RS % err
95.9% 2.01 1.71 -14.9% 1.20 -40.3% 1.76 -12.4% 96.9% 2.39 2.32 -2.9% 1.42 -40.6% 2.39 0.0% 97.5% 2.87 3.07 7.0% 1.82 -36.6% 3.12 8.7%
Ri
20 (590)
CD % err
96.5% 2.57 1.86 -27.6% 1.25 -51.4% 1.96 -23.7% 97.0% 2.69 2.59 -3.7% 1.51 -43.9% 2.68 -0.4% 97.4% 3.21 3.53 10.0% 2.00 -37.7% 3.59 11.8%
p = 1035 kPa
EX FT % err RS % err
10 (590)
Ri
93.0% 1.62 1.54 -4.9% 1.15 -29.0% 1.57 -3.1% 95.4% 2.09 2.04 -2.4% 1.39 -33.5% 2.07 -1.0% 96.6% 2.72 2.67 -1.8% 1.82 -33.1% 2.67 -1.8%
% err
50 (290)
CD
95.7% 2.31 1.98 -14.3% 1.31 -43.3% 2.04 -11.7% 96.8% 2.97 2.85 -4.0% 1.76 -40.7% 2.89 -2.7% 97.5% 3.89 3.92 0.8% 2.51 -35.5% 3.88 -0.3%
p = 690 kPa
% err RS % err
20 (290)
EX FT
96.4% 2.91 2.27 -22.0% 1.39 -52.2% 2.34 -19.6% 96.9% 3.49 3.35 -4.0% 1.95 -44.1% 3.40 -2.6% 97.6% 4.68 4.89 4.5% 2.96 -36.8% 4.79 2.4%
Ri
10 (290)
c b (Re)
Table 1
Predicted and experimental CP moduli
120
28
24
RS model
Experiment
FT model
RS model
CD model
20
16
<
10 mol/m
<
20 mol/m
<
50 mol/m
Experiment,
FT model,
CD model
12
10 mol/m >
3
20 mol/m >
8
3
50 mol/m >
4
400
600
800
1000
1200
1400
1600
28
Experiment
FT model
RS model
CD model
24
<
10 mol/m
<
20 mol/m
<
50 mol/m
20
16
Experiment,
FT model,
CD model
12
10 mol/m >
20 mol/m >
50 mol/m >
4
400
600
800
1000
1200
1400
1600
28
Experiment
FT model
RS model
CD model
24
121
3
<
10 mol/m
<
20 mol/m
<
50 mol/m
1400
1600
20
16
Experiment,
FT model,
CD model
12
10 mol/m >
3
3
20 mol/m >
50 mol/m >
4
400
600
800
1000
1200
122
(a)
FT model
0.9
0.8
0.7
0.6
0.6
0.7
0.8
0.9
1.0
0.9
1.0
Experiment
1.0
(b)
CD model
0.9
0.8
0.7
0.6
0.6
0.7
0.8
Experiment
Fig. 3. The comparison between experimental and observed salt rejection (Ro) by (a) film theory (FT) model
and (b) numerical convection-diffusion (CD) model. The
experimental and simulation conditions are the same as
those for Fig. 2.
(19)
( cb + C )
vw ( cb + Cw ) + D
= vwc p
y
y =0
(20)
Here Cw is the excess concentration at the membrane surface. Since the bulk concentration (cb)
is constant, the derivative is zero.
Rearranging the left hand side of Eq. (20) and
applying the definition of retained solute, i.e.,
Eq. (8), yields
C
vw cb + vwC + D
= vw c p
y y = 0
(21a)
or
C
vw C + D
= vw c p vwcb
y y = 0
(21b)
123
124
Table 2
Simulation conditions for the comparison of FT and CD models
#
Re
p, kPa
cb, mol/m3
30
10
11
38
912
50
191
912
50
380
912
50
1910
912
50
191
576
50
191
1580
50
191
2930
50
191
912
10
191
912
100
191
912
500
191
912
1000
1.0
(a)
(b)
25
FT model
FT model (m/s)
0.9
20
15
10
0.8
0.7
5
0
10
15
20
25
30
0.6
0.6
0.7
0.8
0.9
1.0
CD model
CD model (m/s)
Fig. 4. The comparison between the film theory (FT) and the numerical convection-diffusion (CD) model predictions for
(a) channel averaged permeate flux and (b) observed salt rejection. Constant simulation conditions employed were temperature, water permeability, and salt rejection of 298 K, 1.121011 mPa1s1, and 97%. Table 2 summarizes the simulation conditions that were varied. Crossflow hydrodynamics were varied within the laminar range (Re < 2100).
cw ( x )
v ( x )
= 1 Ri + Ri exp w
cb ( x )
k ( x )
(22)
12
11
CP modulus (cw/cb)
10
9
125
p
FT model CD model
576 kPa
912 kPa
1580 kPa
2930 kPa
8
7
6
5
4
3
2
1
0.0
0.2
0.4
0.6
0.8
1.0
x/L
Fig. 5. Prediction of local CP moduli depending on different applied pressures using the film theory (FT) and the numerical convection-diffusion (CD) models. Constant simulation conditions employed were temperature, water permeability,
and salt rejection of 298 K, 1.121011 mPa1s1, and 97%. Simulation conditions employed were combinations #2, 5, 6,
and 7 in Table 2. Crossflow hydrodynamics were varied within the laminar range (Re < 2100).
126
CP modulus (cw/cb)
Re FT model CD model
38
190
380
1900
1
0.0
0.2
0.4
0.6
0.8
1.0
x/L
Fig. 6. Predicted local CP moduli depending on different crossflow Reynolds numbers using the film theory (FT) and the
numerical convectiondiffusion (CD) models. Constant simulation conditions employed were temperature, water permeability, and salt rejection of 298 K, 1.121011 mPa1s1, and 97%. Simulation conditions employed were conditions 14
in Table 2.
model were compared to experimental RO separation performance data. The three models allowed
the prediction of local solute concentration polarization, permeate water flux, and permeate salt concentration given inputs of operating parameters,
filter geometry, and membrane properties. Predictions by film theory and the numerical convectiondiffusion model compared favorably to experimental data and to each other, providing accurate and consistent predictions of observed water
flux and salt rejection. An important result of this
study is the validation of film theory as a simple
and reliable indicator of concentration polarization
phenomena in reverse osmosis separations, particularly for mechanistic studies of fouling and
scaling conducted in laboratory scale crossflow
membrane filters. Further, the use of film theory
based concentration polarization models in real
RO processes appears justified given the specific
operating conditions of high crossflow and low
flux used in most practical applications.
Acknowlegements
The research described above was performed
while Dr. Suhan Kim was a postdoctoral fellow
at University of California, Riverside. Partial
financial support for this work was obtained
through a post-doctoral fellowship from the Korea
Science and Engineering Foundation (KOSEF) for
Dr. Kim. Additional support was obtained from
the California Department of Water Resources
through the Desalination Research Innovation
Partnership (DRIP), which is managed by the
Metropolitan Water District of Southern California.
Symbols
A
C
cb
cp
cw
p
w
127
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