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Desalination and Water Treatment
Desalination and Water Treatment
To cite this article: Albert S. Kim & Sung Woo Kim (2013) Performance analysis of forward osmosis processes from the
integral equation theory, Desalination and Water Treatment, 51:25-27, 5289-5297, DOI: 10.1080/19443994.2013.768757
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Desalination and Water Treatment 51 (2013) 5289–5297
www.deswater.com July
doi: 10.1080/19443994.2013.768757
b
Department of Chemical Engineering, College of Engineering, Kyung Hee University, Gyeonggi-do 446-701,
Korea
Email: albertsk@hawaii.edu
c
Department of Physics and Astronomy, Dickinson College, Carlisle, PA 17013, USA
Received 15 June 2012; Accepted 24 September 2012
ABSTRACT
7th Aseanian Membrane Society Conference (AMS7), 4–7 July 2012, Busan, Korea
After Loeb [43] studied energy production from side, which results in interfacial concentrations of
concentrated brines using PRO, Lee et al. [29] devel- C2(<C1) and C4(>C5), that is, ECP. In the porous sub-
oped the PRO theory as an alternative approach of strate, the salt diffusion is hindered by the solid part
solution-diffusion model: active membrane layer faces of the substrate, which plays an impeding role of geo-
seawater and porous substrate faces fresh water. Loeb metrical obstacles to diffusing molecules. Taking
et al. [30] switched the membrane and substrate sides, detoured routes, molecules spend more time in the
facing to low and high concentrations, respectively, porous media (than bulk spaces) so that effective dif-
and called this configuration, “osmosis” mode. In con- fusivity decreases. As a consequence, the concentra-
trast to Lee et al. [29]’s PRO mode, we in this study tion at the membrane–substrate interface, C3, is
called Loeb et al. [30]’s osmosis mode FO mode. Sche- noticeably higher than C4 of substrate–fresh water
matic of concentration profiles of PRO and FO modes interface. The net concentration gradient across the
are shown in Fig. 1. top active layer is then proportional to C2-C3, which is
When concentration polarization occurs across the smaller than the overall concentration difference, C1-
FO membrane as well as the porous substrate, it is C5 (between bulk phases of seawater and fresh water).
often called internal concentration polarization (ICP) Through the membrane active layer, the water and
as opposed to the external concentration polarization solute fluxes were written as [29]
(ECP) which often occurs in conventional pressure-
driven membrane processes such as RO. In PRO of Jw ¼ APeff ¼ AðP2 P3 Þ ð1Þ
the concentrative ICP, the active layer faces the higher
concentration solution; and in FO of the dilutive ICP, and
the active layer faces the lower concentration solution
[44]. Js ¼ BðC2 C3 Þ ð2Þ
In the PRO mode of Fig. 1, the osmosis phenom-
ena drives water to flow from low salt concentration where Peff is the effective osmotic pressure (i.e. net
(fresh water) to high salt concentration (seawater) driving force of solvent flux), Pi is osmotic pressure
A.S. Kim and S.W. Kim / Desalination and Water Treatment 51 (2013) 5289–5297 5291
of concentration Ci (i = 15), and A and B are perme- where P2 ¼ PðC02 Þ and P4 ¼ PðC04 Þ in Fig. 1. Mathe-
abilities of water and solute, respectively. In a steady matically, Jw in the numerator of Eq. (4) is switched
state, the solute mass flux in the porous region is to + Jw in the denominator of Eq. (7), that is, from PRO
to FO mode. As stated previously, Loeb et al. [30]
@C
Js ¼ Ds Jw C ð3Þ recognized that the osmotic pressure varies in a non-
s @x linear manner with respect to salt concentration, but
where Ds is the solute diffusivity, and and s are Eq. (7) presumes the validity of van’t Hoff’s equation
porosity and (diffusive) tortuosity of the porous sub- in the FO mode processes.
strate [45]. Lee et al. [29] developed an analytic repre- Tan and Ng [31] investigated impacts of concen-
sentation of a steady-state permeate flux: tration polarization on flux behavior by taking into
account the non-linear diffusion coefficient and
B þ AP2 Jw osmotic pressure, which were represented as a power
Jw ¼ K1 ln ð4Þ series and a quadratic function of solute concentra-
B þ AP4
tion, respectively. OLI software (Steam Analyzer, OLI
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where K was defined as “a measure of the resistance Systems, Inc. New Jersey, USA) was used to calculate
to salt transport in the porous substrate”: D and P as functions of C, and expansion coeffi-
cients were obtained by fitting simulation data from
ds commercial software. Although Ng [31]’s modified
K¼ ð5Þ theory begins with generalized Fick’s law of concen-
Ds
tration-dependent diffusivity, the mass balance equa-
Physically, K1 ¼ Ds =ds s has the same dimension of tion was not rigorously solved to derive an analytic
Jw and therefore can be regarded as a (conventional) solution for the permeate flux. Instead, k ¼ ds s=
mass transfer coefficient. During derivation of Eq. (4), was proposed as analogous to K of Lee et al. [29]’s
C3 and P3 were eliminated using the continuous original theory and arbitrarily expressed to include
boundary condition of the salt concentration at the the non-linear impacts. Any fundamental relationship
membrane–substrate interface (at x = 0). Lee et al. [29] between P, D, and K⁄ was not obtained as they were
specifically assumed quantified using fitting parameters of OLI simulation
results.
P2 P3 C2 C3
¼ ð6Þ
P2 P4 C2 C4
3. Theory
which implies that the osmotic pressure is linearly Fundamental theories for FO/PRO phenomena
proportional to concentration, that is, the van’t Hoff can provide in-depth physical understanding of the
equation: P = CRT where R is the universal gas con- solvent/solute transport and suggest essential oper-
stant and T is the absolute temperature. In recent ating parameters to optimize the processes in terms
papers that adopted Eq. (4) for theoretical improve- of water flux. To the best of our knowledge, the
ment, it is often disregarded that Lee et al. [29]’s PRO state-of-the-art theoretical developments are primar-
theory is fundamentally limited by van’t Hoff’s equa- ily based on Lee et al. [29]’s and Loeb et al. [30]’s
tion for estimating osmotic pressure. Loeb et al. [30] work, which presumed the validity of van’t Hoff’s
indicated that Eq. (6) is “not-always-precise”. If so, linear osmotic pressure generating constant diffusion
accurate prediction of osmotic pressure in very high coefficient. As stated previously, non-linear behav-
concentration is a crucial step to analyze PRO/FO iors of osmotic pressure were investigated using
performance in terms of Jw, as the osmotic pressure commercial software (Steam Analyzer, OLI Systems,
gradient is proportional to diffusion coefficient: Inc. New Jersey, USA) [27,31]. Although the simula-
D / oP/oC. tion results provide a method to analyze how water
Loeb et al. [30] investigated the efficiency of the flux changes with solute species and concentrations,
osmosis-based power generation by positioning the the effects of inter-molecular interactions on osmotic
low concentration solution on the active layer side of pressure have not been scrutinized. In this work, we
the membrane (i.e. switching from PRO mode to FO combined the random mixture theory and OZ inte-
mode) and derived the water flux equation: gral equation to calculate the radial distribution
function (RDF) and the second virial coefficient of
B þ AP2
Jw ¼ K1 ln ð7Þ the osmotic pressure.
B þ AP4 þ Jw
5292 A.S. Kim and S.W. Kim / Desalination and Water Treatment 51 (2013) 5289–5297
3.1. Osmotic pressure and diffusion coefficient that inorganic species in high concentrations of PRO
and/or FO processes are inert and have similar physi-
Generalized Fick’s law for diffusive flux Jdiff can
cochemical properties. This leads to a simple approxi-
be represented as
mation: gij(r) ’ g(r), which converts Eq. (13) to the
original form of
D0 @P @C
Jdiff ¼ ¼ DðCÞ ð8Þ Z
RT @x @x P 2PC2 1
dUðrÞ 3
¼C gðrÞ r dr ð14Þ
RT 3RT 0 dr
where D(C) is the generalized (concentration-depen-
dent) diffusion coefficient
where U(r) is the mean potential of the mixture:
@ PðCÞ X
DðCÞ ¼ D0 ð9Þ UðrÞ ¼ xi xj Uij ðrÞ ð15Þ
@C RT
i;j
and D0 is that of dilute solution. In high concentra- The second virial coefficient is
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DðCÞ ¼ D0 ð1 þ 2b2 CÞ ð11Þ In this random mixture theory, similar species are
transformed into a single ideal species interacting
At low concentrations (b2C << 1), the osmotic pressure with the mean potential U(r) and drifting with effec-
and diffusion coefficient converge to the van’t Hoff tive diffusivity D0 of Eq. (19).
equation (CRT) and constant Do, respectively. When
multiple solute species are present in solution, the
total molar concentration is 3.2. Pair potentials
X Specific form of the pair potential between mole-
C¼ Ci ¼ C1 þ C2 þ ð12Þ cule i and j consists of Coulombic (C) and Lennard–
i
Jones (LJ) potentials:
and Ci = xiC where xi is a mole fraction of species i. In
liquid-state statistical physics, the osmotic pressure is Ui;j ðrÞ ¼ UijC þ UijLJ ð20Þ
represented as
Z z i z j e2
P 2P X 1
dUij ðrÞ 3 UijC ðrÞ ¼ ð21Þ
¼C Ci Cj gij ðrÞ r dr ð13Þ r
RT 3RT i;j 0 dr
rij 12 rij 6
where Uij and gij (r) are the potential energy and RDF UijLJ ¼ 4ij ð22Þ
r r
of molecular species i and j, respectively. We assume
A.S. Kim and S.W. Kim / Desalination and Water Treatment 51 (2013) 5289–5297 5293
where e is the elementary electric charge, zi is the 3.3. Integral equation theory
valence of species i, and ij and rij are LJ parameters
With necessary LJ parameters known, the second
having dimensions of energy and distance, respec-
virial coefficient b2 needs to be calculated using princi-
tively. For interaction between two molecules of dif-
ples of statistical mechanics. Molecular dynamics and
ferent species (i.e. i – j), LJ parameters, ij and rij, are
Monte Carlo simulations are standard techniques to
calculated as geometric and arithmetic means, respec-
investigate physical and chemical properties of spe-
tively, of those of species i and j:
cific materials in various phases including liquids.
Integral equation theory for the random mixture, on
pffiffiffiffiffiffiffiffi 1
ij ¼ ii jj and rij ¼ ðrii þ rjj Þ ð23Þ the other hand, provides a convenient and fast
2 method to calculate b2 and investigate properties of
Ensuring the global charge neutrality, represented as the high concentration solution.
Ck zk ¼ 0, one can nullify the average influence of If the fluid is uniform and isotropic, the OZ–rela-
k tion is
Coulombic potential:
Z
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and and
"P #16 Z
xi xj ij r12
¼ P
r
i;j ij
ð27Þ
b
CðkÞ ¼ cðrÞexpði~
k ~
rÞdr ð31Þ
i;j xi xj ij rij
6
Table 1
LJ parameters for Na+ and Cl (denoted as 1 and 2, respectively) obtained from molecular dynamics force fields and
mean values calculated using Eqs. (26) and (27). Units of e’s and r’s are cal/mol and Å, respectively
X-PLOR CHARMM Smith-94 OPLS GROMACS AMBER
ij rij ij rij ij rij ij rij ij rij ij rij
11 100.0 2.730 46.9 2.430 100.1 2.350 2.8 3.330 14.8 2.575 2.8 3.328
22 150.0 4.276 150.0 4.045 129.9 4.400 117.8 4.417 106.4 4.448 100.0 4.401
12 122.5 3.503 83.9 3.237 114.0 3.375 18.2 3.874 39.6 3.384 16.6 3.865
mean 77.1 4.075 59.6 3.916 57.2 4.222 36.2 4.364 34.2 4.366 31.3 4.344
A.S. Kim and S.W. Kim / Desalination and Water Treatment 51 (2013) 5289–5297 5295
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Fig. 3. Comparison of (a) osmotic pressure and (b) osmotic pressure ratio with respect to van’t Hoff’s equation as
functions of NaCl concentration.
and r = 3.916Å), and gives the second highest b2 higher osmotic pressures than one predicted using
(=0.02671 lit/mol) followed by that of CHARMM van’t Hoff’s equation. X-PLOR predicted higher osmo-
(b2 = 0.02230 lit/mol). g(r) shapes of CHARMM and tic pressure than that of OLI, which is similar to those
Smith-94 can be compared in terms of their peak posi- of Smith and CHARMM. As expected, OPLS, GRO-
tions and heights. Because values of Smith and MACS, and AMBER provide lower osmotic pressure
CHARMM are similar, larger r (=4.222 Å) of Smith-94 than those of other force fields. Fig. 3(b) shows ratios
than that of CHARMM ( r=3.916Å) seems to contribute of osmotic pressures to that of van’t Hoff’s equation.
to higher second virial coefficient than that of Slopes of straight lines in Fig. 3(b) represent b2 values
CHARMM. Comparing , r , and b2 values of X-PLOR, of the force fields. Interestingly, osmotic pressure ratio
Smith-94 and CHAMRR, one can conclude that b2 pri- predicted using Stream Analyser (SA) software from
marily increases with , followed by r . Conversely OLI is smaller than 1.0, in other words, pOLI(C) 6 RTC
saying, when draw solutes for the FO processes are for C . 1.6. For higher concentrations (3 M < C < 5 M),
sought, ones with higher and then larger r will SA, Smith-94, and CHARMM give similar values, spe-
surely increase the osmotic pressure and its gradient cifically indicating that the osmotic pressure increases
(i.e. P and oP/oC) and therefore enhance water flux. about 20% from van’t Hoff’s equation near C = 4 M.
4.2. Osmotic pressure 4.3. Diffusion coefficient and permeate flux: implications
Fig. 3 shows osmotic pressure curves predicted In this section, we qualitatively discuss effects of
using the six force fields, OLI software, and van’t p(C) and D(C) on water flux in FO. Comparing Eqs.
Hoff’s equation. In Fig. 3(a), calculation results show (10) and (11), one can notice that the slopes of
Table 2
The second virial coefficient b2 and b2RT at T = 298.5 K
X-PLOR Smith-94 CHARMM OPLS GROMACS AMBER
Acknowledgments
This research was supported by Kyung Hee Uni-
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