ARTICLE

pubs.acs.org/IECR

Ion-Exchange Membrane Electrodialysis for Saline Water Desalination

and Its Application to Seawater Concentration
Yoshinobu Tanaka
IEM Research, 1-46-3 Kamiya, Ushiku-shi, Ibaraki 300-1216, Japan

ABSTRACT: Membrane pair characteristics of commercially available ion-exchange membranes are measured by changing current
density and seawater temperature supplied to the electrodialyzer. The hydraulic permeabilities (leading parameter) for three types of
commercially available membranes are almost the same, and their averages are expressed by the empirical function of temperature.
Hydraulic osmosis is predominant at lower current density and electro-osmosis is predominant at larger current density. The
influence of temperature and salt concentration on the physical properties of saline water, such as solution density, specific
Downloaded by UNIV NACIONAL AUTONOMA MEXICO at 13:41:29:094 on June 04, 2019

conductance, and NaCl activity coefficient, is expressed by empirical equations. Ionic constituents in a concentrated solution are
expressed by empirical equations. Electric current screening ratio of a spacer is defined and calculated. Direct current electric
resistance of a membrane pair is calculated, and it is predominant over that of a desalting cell and a concentrating cell. It is necessary
to decrease electric resistance of an ion-exchange membrane for reducing energy consumption in a salt manufacturing process.
from https://pubs.acs.org/doi/10.1021/ie102386d.

1. INTRODUCTION
Industrial application of ion-exchange membranes started
from saline water desalination1 and the membranes are now
applied in many fields, such as drinking water treatment, waste-
water treatment, demineralization of amino acid, demineraliza-
tion of whey, demineralization of sugar liquor, treatment of
organic substances, etc. Among these applications, saline water
desalination is the most important fundamental technology, and
it is applied widely.2
11
Ion-exchange membranes have the functions of desalting and
of concentrating saline water. The targets (products) of both
functions are different from each other. However, the principles
of both functions are fundamentally the same. In the previous
investigation, a computer simulation program for evaluating the
performance of saline water desalination was developed.12
14
The overall mass-transport equation15 is the fundamental principle
in this program, and it was established from seawater concentra-
tion. The equation makes it possible to evaluate the membrane
pair characteristics, which are discussed initially in this article.
Furthermore, in order to improve the precision of the computer
simulation program, the following phenomena are also discussed:
(1) Relationship between temperature and the overall hy-
draulic permeability F (leading parameter),
(2) Influence of temperature and salt concentration on the
physical properties of saline water,
(3) Ionic constituent in a concentrated solution,
(4) Electric current screening ratio of a spacer, and
(5) Direct current electric resistance of an ion-exchange
membrane.
In Japan, there are no rock salt deposits and, because of its
climate, is not suitable to manufacture salt; thus, salt require-
ments have been largely met by imported salt. Only table salt has
been produced by a method in which seawater is introduced into
a salt field and then thickened by solar energy. However, this
method requires a wide area of land and is labor-intensive. In
addition, such conditions as wind, rain, and length of the dry
season raise the cost to rather higher levels, compared to the price
of imported salt.16 With the circumstances described above,
research on seawater concentration by means of ion-exchange
membranes has been progressed.17
20 In 1971, all salt field
methods were converted to ion-exchange membrane methods,
which presently enable the production of ∼1 000 000 tons of
edible salt per year. The largest problem in ion-exchange mem-
brane methods is that the cost is still higher, compared to the price
of imported salt. This problem has become more acute recently,
because of rising energy prices. Therefore, cost reduction is the
most important target in ion-exchange membrane technology. In
this manuscript, we discuss also the fundamental performance of
an electrodialyzer for seawater concentration, taking energy con-
sumption reduction into consideration.
2. EXPERIMENTAL SECTION
Three types of commercially available ion-exchange mem-
branes were integrated in the electrodialyzers: Aciplex K172/
A172 (Asahi Chemical Co.), Selemion CMR/ASR (Asahi Glass
Co.), and Neocepta CIMS/ACS3 (Tokuyama Corp.). Tables 1
and 221 respectively show electrodialyzer/ion-exchange mem-
brane specifications and electrodialysis conditions. Seawater was
supplied to the electrodialyzer, keeping a flow velocity of 5 cm/s
at the inlets of desalting cells. By passing an electric current, a
concentrated solution was extracted from concentrating cells.
After the electrolyte concentration of the concentrated solution
became constant, the solution was sampled, its volume velocity
was measured, and the concentrations of Naþ, Kþ, Mg2þ, Ca2þ,
Cl
, and SO42þ ions were analyzed. In seawater electrodialysis,
Received: November 26, 2010
Accepted: April 29, 2011
Revised: April 20, 2011
Published: April 29, 2011

r 2011 American Chemical Society 7494 dx.doi.org/10.1021/ie102386d | Ind. Eng. Chem. Res. 2011, 50, 7494–7503
Industrial & Engineering Chemistry Research ARTICLE

Table 1. Specifications of the Electrodialyzer and Membranes

manufacturer Asahi Chemical Co. Asahi Glass Co. Tokuyama Soda Co.
ion-exchange membrane Aciplex K172/A172 Selemion CMR/ASR Neocepta CIMS/ACS3
membrane area (dm2) 1.72 1.72 2.00
membrane pairs (pairs) 10 10 9
membrane thickness (mm) K172: 0.13
0.15 CMR: 0.11 CIMS: 0.14
0.17
A172: 0.11
0.13 ASR: 0.11 ACS3: 0.09
0.12
area electric resistance of the membrane (Ω cm2) K172: 1.9
2.2 CMR: 2.36 CIMS: 1.5
1.6
A172: 1.7
2.1 ASR: 1.80 ACS3: 1.5
2.0
transport number K172: >0.99 CMR: 0.94 CIMS: >0.98
A172: >0.99 ASR: 0.96 ACS3: >0.98
exchange capacity (mequiv/g dry memb) K172: 1.5
1.6 CMR: 3.7 CIMS: 2.2
2.5
A172: 1.8
1.9 ASR: 3.5 ACS3: 2.0
2.4
water content K172: 0.20
0.30 CMR: 0.34 CIMS: 0.30
0.35
A172: 0.24
0.25 ASR: 0.33 ACS3: 0.20
0.30
intensity (MPa) K172: 0.26
0.33 CMR: 0.2 CIMS: 0.3
0.4
A172: 0.22
0.30 ASR: 0.2 ACS3: 0.4
0.6

Table 2. Electrodialysis Conditions

temperature (°C) 25, 35, 50, 60
current density (A/dm2) 1.0, 3.0, 5.0, 7.0
solution velocity in a desalting cell (cm/s) 5

the electrolyte concentration (C) is given as

C ¼ CNa þ CK þ CMg þ CCa ¼ CCl þ CSO4

The cell voltage (Vcell) was measured from the voltage difference
observed with Pt electrodes included in the concentrating cells
that were integrated into both ends of the stack. The experiments
were repeated by the changing seawater temperature and current
density incrementally, via electrodialysis.

3. RESULTS AND DISCUSSION

3.1. Overall Mass-Transport Equation and Membrane Pair
Characteristics. Ion-exchange membrane electrodialysis is a
process for transporting ionic species across the membranes.
Ions and a solution in a desalting cell are transferred to a
concentrating cell across a cation- and anion-exchange mem-
brane under an applied electric current. Fluxes of ions (JS) and a
solution (JV) transported across a membrane pair are expressed
by the following overall mass-transport equation:15
JS ¼ C00 JV ¼ λi
μðC00
C0 Þ ¼ λi
μΔC
JV ¼ φi þ FðC00
C0 Þ ¼ φi þ FΔC
where i is the current density; C0 and C00 are the electrolyte
concentrations in a desalting and a concentrating cell, respec-
tively; the accents/superscripts 0 and 00 denote a desalting cell and
a concentrating cell, respectively; λ is the overall transport
number; μ is the overall solute permeability; φ is the overall
electro-osmotic permeability; and F is the overall hydraulic
permeability. These are membrane pair characteristics. The term
“overall” means that the coefficients express the contributions of
a cation- and anion-exchange membrane. It means also that the
coefficients express the contributions of many types of ions that
are dissolving in an electrolyte solution.
Figure 1. Plots of JS/i versus ΔC/i plot and JV/i versus ΔC/i. (Aciplex
K172/A172, 25 °C.)
Plots of JS/i and JV/i versus (C00
C0 )/i = ΔC/i yield straight
lines, such that λ, μ, φ, and F can be determined from the
intercepts and the gradients of the lines. Figure 1 gives repre-
sentative straight lines that were yielded in the experiment
described in section . All membrane pair characteristics measured
ð1Þ by changing the solution temperature are listed in Table 3.
In the previous investigation,15 we plotted λ (equiv C
1),
μ (cm s
1), and φ (cm3 C
1) against F (cm4 equiv
1 s
1), and
ð2Þ we found the following equations to be valid:
λ ¼ 9:208  10
6 þ 1:914  10
5 F ð3Þ
μ ¼ 2:005  10
4 F ð4Þ
φ ¼ 3:768  10
3 F0:2
1:019  10
2 F ð5Þ
Equations 3
5 are empirical equations that express the
approximated regularity between membrane pair characteristics
of commercially available ion-exchange membranes; they are not
influenced by current density i. These equations mean that F is
the leading parameter and represents all of the overall membrane
7495 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503
Industrial & Engineering Chemistry Research ARTICLE

Table 3. Membrane Pair Characteristics

ion-exchange membrane temperature (°C) λ ( 106 equiv C
1) μ ( 106 cm s
1) φ ( 103 cm3 C
1) F ( 102 cm4 equiv
1 s
1)

Aciplex K172/A172 25 9.724 1.434 1.403 1.218

35 9.736 1.289 1.370 1.626
50 9.972 4.515 1.542 1.996
60 9.692 2.123 1.405 2.765
Selemion CMR/ASR 25 9.389 1.482 1.409 1.116
35 9.422 2.421 1.501 1.377
50 9.475 3.614 1.563 1.937
60 9.583 5.103 1.621 2.380
Neocepta CIMS/ACS3 25 9.349
1.055 1.004 1.254
35 9.373
1.679 1.067 1.538
50 9.459
1.239 1.067 1.835
60 9.547
0.561 1.405 2.059

Figure 2. Relationship between temperature (T) and the overall

hydraulic permeability (F).
characteristics. λ, μ, and φ are determined by setting the value
of F. In order to discuss the relationship between temperature T
and the membrane pair characteristics, F is plotted against T,
based on the data given in Table 3, as shown in Figure 2. F is the
independent parameter, and each membrane must have its own F
value. However, Figure 2 shows that the F value of each
commercially available membrane is almost the same and can
be expressed by the following empirical function of T (°C):
F ¼ 3:421  10
3 þ 3:333  10
4 T R ¼ 0:9364 ð6Þ
where R is the correlation coefficient.
3.2. Electromigration, Diffusion, Electro-Osmosis and Hy-
draulic Osmosis. Parameters λi and μΔC in eq 1 stand for the
electromigration and solute diffusion, respectively. Parameters
φi and FΔC correspond to the electro-osmosis and hydraulic
osmosis, respectively. These parameters are computed from
Table 3 and are shown in Figures 3 and 4 (Aciplex K172/
A172), Figures 5 and 6 (Selemion CMR/ASR), and Figures 7
and 8 (Neocepta CIMS/ACS3). The plots indicate that (i) μΔC
Figure 3. Electromigration (λi) and solute diffusion (μΔC) for Aciplex
K172/A172.
is negligible, compared to λi, and (ii) FΔC is predominant at
lower i and φi is predominant at larger i.
3.3. Influence of Temperature and Salt Concentration on
the Physical Properties of Saline Water. In order to evaluate
the performance of an electrodialyzer that was operated by changing
the solution temperature and current density as described in section ,
it is necessary to make clear the influence of temperature T (°C) and
electrolyte concentration C3 (g salt/kg solution) on the density D,
specific electric conductance (k), and electrolyte (NaCl) activity
coefficient (γ) of a solution. These relationships are determined as
follows. Density D is determined using22


D kg=dm3 ¼ 1:001
1:101  10
4 T
3:356
 10
6 T 2 þ ð7:881
1:368 ð7Þ
 10
2 T þ 8:978  10
5 T 2 Þ
 10
4 C3

7496 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503

Industrial & Engineering Chemistry Research ARTICLE

Figure 6. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for

Selemion CMR/ASR.
Figure 4. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for
Aciplex K172/A172.

Figure 7. Electromigration (λi) and solute diffusion (μΔC) for Neo-

cepta CIMS/ACS3.

NaCl activity coefficient (γ) is determined from the expression24

Figure 5. Electromigration (λi) and solute diffusion (μΔC) for Sele-
mion CMR/ASR.
Specific electric conductance k (S/cm) is determined using the
expression23
k ðS=cmÞ ¼ ð0:9383 þ 3:463  10
2 TÞ
 10
3 C3
ð1:655 þ 3:863  10
2 TÞ
ð8Þ
 10
6 C3 2
ð1:344 þ 3:160  10
2 TÞ
 10
9 C3 3
γ ¼ 0:5927 þ 0:4355C3
0:5
7:201  10
5 C3 þ 3:503  10
6 C3 2
 
in the range from normal temperature to 70°C
ð9Þ
Electrolyte concentration C3 (g salt/kg solution) is calculated
from the electrolyte concentration C (equiv salt/cm3 solution),
according the following steps:
C1 ðequiv salt=dm3 solutionÞ
¼ C ðequiv salt=cm3 solutionÞ  103 ð10Þ

7497 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503

Industrial & Engineering Chemistry Research ARTICLE

Figure 8. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for Neo- Figure 10. Relationship between rNa and rK.
cepta CIMS/ACS3.
and
B ¼ 1:001
1:101  10
4 T
3:356  10
6 T 2 ð15Þ
Solving eq 13 yields
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
B2 þ 4AC2
B
C3 ¼ ð16Þ
2A

3.4. Ionic Constituent in a Concentrated Solution. In

an electrodialysis process for concentrating seawater, the perme-
ability of divalent ions across the membranes is strongly sup-
pressed for preventing CaSO4 scale precipitation in concentrating
cells.25
28 The membranes being discussed in this investigation
are given such low permeability of the divalent ions. In order to
evaluate NaCl concentration in a concentrated solution (the output
of an electrodialysis process) and energy consumption to produce
one ton of NaCl in an electrodialysis process, it is necessary to
discuss the ionic constituents in the concentrated solutions.
Figure 9 gives the equivalent ratio of Naþ ions to total ions rNa
in the concentrated solution for three types of membrane pairs
integrated in the electrodialyzer. Averaging these data, rNa is
expressed by the following empirical function of i (expressed in
units of A/dm2) and T (given in Celsius).
Figure 9. Relationship between i and rNa. r Na ¼ 0:9584
4:269  10
3 T þ ð0:7983 þ 9:824
ð17Þ
C2 ðg salt=dm3 solutionÞ ¼ 57:87C1 ð11Þ  10
2 TÞ  10
2 i0:5
8
3
C3 ðg salt=kg solutionÞ ¼
C2
ð12Þ >
> 0:4421 ð25°CÞ
D >
< 0:5100 ð35°CÞ
R ¼
From eqs 7 and 12, > 0:5906 ð50°CÞ
>
>
C2 : 0:6017 ð60°CÞ
C3 ¼ ð13Þ
AC3 þ B Figures 10
12 show rNa versus rK, rMg, and rCa. These plots
where are expressed by the following equations, which do not include
A ¼ ð7:881
1:368  10
2 T þ 8:978  10
5 T 2 Þ  10
4 i and T.
ð14Þ rK ¼ 1:905  10
2 þ 8:838  10
3 r Na R ¼ 0:2440 ð18Þ

7498 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503

Industrial & Engineering Chemistry Research ARTICLE

Figure 11. Relationship between rNa and rMg. Figure 13. Relationship between i and rCl.

3.5. Electric Current Screening Ratio of a Spacer. Spacers

are integrated in desalting and concentrating cells to maintain the
distance between the membranes and increase the limiting
current density due to solution disturbance.29
34 However, the
spacers partially screen an electric current and increase the local
current density. In order to discuss energy consumption of an
electrodialyzer, it is necessary to evaluate the electric current
screening ratio of a spacer. The structure of the diagonal net
spacer incorporated in the electrodialyzer is illustrated in
Figure 14, which shows that the rods arranging in two directions
are piled upon each other. The solution supplied to the cell flows
along two watercourses (channels); therefore, solution stagna-
tion is prevented, because the solution stream fans out and
solution mixing is promoted between the two watercourses.
The electric current screening ratio ε of the diagonal net spacer
in Figure 14 is represented by the following equation:

electric current screening area of an unit net mesh

ε ¼
total area of an unit net mesh
ða=2Þ  r  2
¼
r 2 sin R
Figure 12. Relationship between rNa and rCa. a
¼
r sin R
ð23Þ
r Mg ¼ 0:7405
0:7668r Na R ¼ 0:9959 ð19Þ
where a is the flow-pass thickness in the cell, d the diameter of the
rCa ¼ 0:2460
0:2482r Na R ¼ 0:9654 ð20Þ spacer rod (d = a/2), r the distance between the rods, and R the
crossing angle of the rods. The numeral “2” means that two
screening parts are taken into account in the four screening parts
The relationship between i and rCl is exhibited in Figure 13, that surround the unit net mesh.
and it is approximated by eq 21, Substituting the specifications of the diagonal net spacer
r Cl ¼ 0:9929 þ 1:947  10
3 i R ¼ 0:3703 ð21Þ incorporated with the electrodialyzer (a = 0.075 cm (d =
0.0375 cm), r = 0.3 cm, sin R = sin 60° = 0.8660) to eq 23, ε
in which T is not included. The relationship between rCl and rSO4
is calculated to be equal to 0.2887.
is given by eq 22: 3.6. Electric Resistance of a Desalting Cell, a Concentrat-
r SO4 ¼ 1
rCl ð22Þ ing Cell, and an Ion-Exchange Membrane Pair. When the

7499 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503

Industrial & Engineering Chemistry Research ARTICLE

Figure 14. Structure of a diagonal net spacer.

electrolyte concentration C (equiv salt/cm3 solution) and the

electrolyte activity coefficient γ in a desalting cell and in a
concentrating cell respectively become (C0 , γ0 ) and (C00 , γ00 )
at an applied current density i, the cell voltage Vcell is given by the
following equation:35
Vcell ¼ ðrmemb þ r 0 þ r 00 Þi
   00 00 
RT γ C
þ 2ðtK þ tA
1Þ ln 0 0
F γC Figure 15. Electric resistance of a desalting cell, a concentrating cell,
0 00 and an ion-exchange membrane pair for Aciplex K172/A172.
¼ ðrmemb þ r þ r Þi þ Vmemb ð24Þ
in which
tK þ tA
1 ¼ λF ð25Þ
γ is computed using eq 9, and λ is listed in Table 3. Vmemb is the
membrane potential.
Direct current electric resistance of an ion-exchange mem-
brane pair (rmemb = rK þ rA) is introduced from eqs 24 and 25 as
follows:
 00 00 

1 γ C
rmemb ¼ Vcell
2λRT ln 0 0
ðr 0 þ r 00 Þ
i γC
ð26Þ
1
¼ ðVcell
Vmemb Þ
ðr 0 þ r 00 Þ
i
r0 and r00 represent the electric resistance of a desalting cell and a
concentrating cell:
a0
r0 ¼ ð27Þ
ð1
ε0 Þk0

a00
r 00 ¼ ð28Þ
ð1
ε00 Þk00
in which k is computed using eq 8, ε = 0.2887 (eq 23), and
a = 0.075 cm.
The parameters rmemb, r0 , and r00 are computed by substituting
experimental data and electrodialyzer specifications into eqs 26
28.
Figures 15
17 represent i vs r0 , r00 , and rmemb for the three ion-
exchange membranes, showing that rmemb is predominant over
r0 and r00 . rmemb is influenced by concentration polarization, so
it must increase with current density. On the other hand, rmemb is
influenced by ion concentration in the membrane, which is
equivalent to ion concentration in the solution passing through
the membrane and it is equal to the value in the concentrating cell
(C00 ) at steady state. So, rmemb must decrease with increasing
current density. Inspecting Figures 15
17, the influence of
concentration polarization is assumed to be minor and rmemb
7500
Figure 16. Electric resistance of a desalting cell, a concentrating cell,
and an ion-exchange membrane pair for Selemion CMR/ASR.
decreases with increasing current density, because of the
increased concentration in the membrane.
3.7. Concentration of a Concentrated Solution and En-
ergy Consumption in an Electrodialysis Process for Sea-
water Concentration. In order to enhance the performance of
the electrodialyzer, one is expected to increase the NaCl con-
centration in a concentrated solution (C00NaCl (g NaCl/L)) and
decrease the energy consumption necessary to produce one ton
of NaCl (ENaCl (kWh/(t NaCl))). The current technical target
for strengthening the competitive position of an electrodialysis
system in the salt market is assumed to be C00NaCl > 200 g NaCl/L
dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503
Industrial & Engineering Chemistry Research
Figure 17. Electric resistance of a desalting cell, a concentrating cell,
and an ion-exchange membrane pair for Neocepta CIMS/ACS3.
Figure 18. Relationship between the NaCl concentration in a concen-
trated solution (C00NaCl) and the energy consumption necessary to
produce one ton of NaCl (ENaCl) for Aciplex K172/A172.
and ENaCl < 120 kWh/(t NaCl).36 Figures 18
20 give the relation-
ship between CNaCl and ENaCl obtained in electrodialysis experi-
ments in section . Comparing the experimental data with the target
indicates that a reduction in energy consumption is desirable.
Figures 18
20 are combined and are shown in Figure 21.
ENaCl can be expressed as a function of cell voltage (Vcell),
electric current (I), and NaCl output (PNaCl) as follows:
Vcell I
ENaCl ¼
PNaCl
ARTICLE
Figure 19. Relationship between NaCl concentration in a concentrated
solution (C00NaCl) and the energy consumption necessary to produce one
ton of NaCl (ENaCl) for Selemion CMR/ASR.
Figure 20. Relationship between NaCl concentration in a concentrated
solution (C00NaCl) and the energy consumption necessary to produce one
ton of NaCl (ENaCl) for Neocepta CIMS/ACS3.
Vcell is given by eq 24, including the ohmic term and membrane
potential term. With regard to the electric resistances in the
ohmic term, rmemb, r0 , and r00 are evaluated in Figures 15
17,
which reveal that rmemb is predominant over r0 and r00 . Consider-
ing that the membrane potential term in eq 24 is inevitable in the
electrodialysis process, energy consumption is estimated to be
reduced with reductions in rmemb. However, this situation is
accompanied by a decrease in C00 (C00NaCl), because of the increase
in F.
The policy that can be applied to decrease the electric
ð29Þ
resistance of the membrane is assumed to be (1) decrease the
7501 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503
Industrial & Engineering Chemistry Research ARTICLE

’ ACKNOWLEDGMENT
We are grateful to Mr. M. Akiyama (Sea Water Science
Research Laboratory, Japan Tobacco & Salt Public Corporation)
for offering the experimental data obtained by electrodialysis. We
thank Mr. G. Takahashi and Miss A. Shinohara (Department of
Chemistry, School of Hygienic Science, Kitasato University) for
assistance in the fundamental investigation.

’ NOMENCLATURE
a = flow-pass thickness in a cell (cm)
C = electrolyte concentration (equiv cm
3)
d = diameter of a spacer rod (cm)
D = solution density (kg dm
3)
ENaCl = energy consumption to produce one ton of NaCl (kWh/t
NaCl)
F = Faraday constant (C equiv
1)
i = current density (A cm
2)
I = electric current (A)
JS = flux of ions across a membrane pair (equiv cm
2 s
1)
JV = flux of a solution across a membrane pair (cm3 cm
2 s
1)
r = electric resistance (Ω cm2)
R = correlation coefficient
Figure 21. Relationship between the NaCl concentration in a concen- r = distance between spacer rods (cm)
trated solution (C00NaCl) and the energy consumption necessary to ri = concentration ratio of ion i to total ions in a concentrated
produce one ton of NaCl (ENaCl) for all three ion-exchange membranes. solution (equiv equiv
1)
t = transport number of ions in a membrane
thickness of the membrane and (2) form a double-layered T = temperature (°C)
Vcell = cell voltage (V pair
1)
membrane consisting of a fine porous thinner functional layer
and porous reinforced layer. Another approach to be discussed is Greek Letters
(3) apply an electrodialysis process in which the optimal operat- R = crossing angle of spacer rods (degrees)
ing condition is applied. γ = activity coefficient of electrolyte (NaCl)
ε = electric current screening ratio of a spacer
k = specific electric resistance (S cm
1)
4. CONCLUSION λ = overall transport number of a membrane pair (equiv C
1)
Electrodialysis was performed using an electrodialyzer inte- μ = overall solute permeability of a membrane pair (cm s
1)
grated with commercially available ion-exchange membranes, ΔC = C00
C0 (equiv cm
3)
and the overall membrane pair characteristics (λ, μ, φ, and F) of F = overall hydraulic permeability of a membrane pair (cm4
commercially available membranes are measured. equiv
1 s
1)
In order to improve the computer simulation program devel- φ = overall electro-osmotic permeability of a membrane pair
oped in the previous investigation,12
14 the following phenom- (cm3 A
1 s
1)
ena are discussed:
Subscripts
(1) Relationship between temperature and the overall hy-
A = anion exchange membrane
draulic permeability F (leading parameter),
K = cation exchange membrane
(2) Influence of temperature and salt concentration on the
physical properties of saline water, Superscripts/Accents
(3) Ionic constituent in a concentrated solution, 0
= desalting cell
(4) Electric current screening ratio of a spacer, and 00
= concentrating cell
(5) Direct electric current resistance of an ion exchange
membrane.
This manuscript is one of the series describing the computer ’ REFERENCES
simulation of the electrodialysis process. The computing techni- (1) Reahl, E. R. Half a century of desalination with electrodialysis;
que developed here must contribute to developing the computer Ionics Technical Paper, Ionics, Watertown, MA, 2004. (Ionics was
program in the next version. purchased by General Electric in 2005.)
Energy consumption and salt concentration in concentrating (2) Parsi, E. J. Large electrodialysis stack development. Desalination
1976, 19, 139–151.
cells for seawater concentration are measured, and they are
(3) Kusakiri, K.; Kawamata, F.; Matsumoto, N.; Saeki, H.; Terada, Y.
compared to the technical target for strengthening the compe- Electrodialysis plant at Hatsushima. Desalination 1977, 21, 45–50.
titive position of an electrodialysis system in the salt market. In (4) Katz, W. E. The electrodialysis reversal (EDR) process. Desali-
order to improve the performance of the seawater concentration nation 1979, 28, 31–40.
process, it is necessary to decrease the electric resistance of ion- (5) Kuroda, O.; Takahashi, S.; Wakamatsu, K.; Itoh, S.; Kubota, S.;
exchange membranes. Kikuchi, K.; Eguchi, Y.; Ikenaga, Y.; Sohma, N.; Nishinori, K. An

7502 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503

Industrial & Engineering Chemistry Research ARTICLE

electrodialysis sea water desalination system powered by photovoltaic (27) Mizutani,Y.; Yamane,R.; Sata, T.; Izuo, T. Permselectivity treat-
cells. Desalination 1987, 65, 161–169. ment of a cation-exchange membrane. Jpn. Patent No. S56-42083, 1971.
(6) Harries, R. C.; Elyanow, D.; Heshka, D. N.; Fischer, K. L. (28) Mihara, K.; Misumi, T.; Yamauchi, H.; Ishida, Y. Production of
Desalination of brackish groundwater for a prairie community using a cation-exchange membrane having excellent specific permselectivity
electrodialysis reversal. Desalination 1991, 84, 109–121. between cations. Jpn. Patent No. S47-3081, 1972.
(7) Kawahara, T. Construction and operation experience of a large- (29) Berfort, G.; Guter, G. A. An experimental study of electro-
scale electrodialysis water desalination plant. Desalination 1994, 96, dialysis hydrodynamics. Desalination 1972, 10, 221–262.
341–348. (30) Matsuzaki, H.; Kuroda, O.; Takahashi, S. Effect of spacer on
(8) Allison, R. P. Electrodialysis reversal in water reuse applications. electric resistance in an Electrodialyzer. Kagaku Kogaku 1981, 7, 465–468.
Desalination 1995, 103, 11–18. (31) Miyoshi, H.; Fukumoto, T.; Kataoka, T. A consideration on
(9) Ryabtsev, A. D.; Kotsupalo, N. P.; Titarenko, V. I.; Igumenov., flow distribution in an ion exchange compartment with spacer. Desalina-
I. K.; Gelfond, N. V.; Fedotova, N. E.; Morozova, N. B.; Shipachev, V. A.; tion 1982, 42, 47–55.
Tibilov, A. S. Development of a two-stage electrodialysis set-up for (32) Feron, P.; Solt, G. S. The influence of separators on hydro-
economical desalination of sea-type artesian and surface waters. Desali- dynamics and mass transfer in narrow cells: Flow visualization. Desalina-
nation 2001, 137, 207–214. tion 1991, 84, 137–152.
(10) Larchet, C.; Eigenberger, G.; Tskhay, A.; Tastanov, K.; Nikonen- (33) Zimmerer, C. C.; Kotte, V. Effects of spacer geometry on
ko, V. Application of electromembrane technology for providing drinking pressure drop, mass transfer, mixing behavior, and residence time
water for the population of the Aral region. Desalination 2002, 149, distribution. Desalination 1996, 104, 139–134.
383–387. (34) Tsiakis, P.; Papageorgiou, L. G. Optimal design of an electro-
(11) Walha, K.; Amar, R. B.; Firdaous, L; Quemeneur, F.; Jaouen, P. dialysis brackish water desalination plant. Desalination 2005, 173, 173–186.
Brackish groundwater treatment by nanofiltration, reverse osmosis and (35) Tanaka, Y. Mass transport and energy consumption in ion-
electrodialysis in Tunisia: Performance and cost comparison. Desalina- exchange membrane electrodialysis of seawater. J. Membr. Sci. 2003,
tion 2007, 207, 95–106. 215, 265–279.
(12) Tanaka, Y. A computer simulation of continuous ion exchange (36) Fujita, T. Current challenges of salt production technology.
membrane electrodialysis for desalination of saline water. Desalination Bull. Soc. Sea Water Sci. Jpn. 2009, 63, 15–20.
2009, 249, 809–821.
(13) Tanaka, Y. A computer simulation of batch ion exchange
membrane electrodialysis for desalination of saline water. Desalination
2009, 249, 1039–1047.
(14) Tanaka, Y. A computer simulation of feed and bleed ion
exchange membrane electrodialysis for desalination of saline water.
Desalination 2010, 254, 99–107.
(15) Tanaka, Y. Irreversible thermodynamics and overall mass
transport in ion-exchange membrane electrodialysis. J. Membr. Sci.
2006, 281, 517–531.
(16) Tsunoda, Y. Electrodialysis for producing brine concentrates
from sea water. Proc. First Int. Symp. Water Desalination, Washington, DC
1965, 325–339.
(17) Kaho, M.; Watanabe, T.; Azechi, S.; Akiyama, M.; Nagatsuka,
S.; Fujimoto, Y. Long-tem concentration test by unit cell-type electro-
dialytic apparatus of practical use. Bull. Soc. Sea Water Sci. Jpn. 1969,
23, 3–20.
(18) Watanabe, T.; Azechi, S.; Tanaka, Y.; Nagatsuka, S.; Yigi, N.
Effects of the concentration and temperature of feed solution and
current density on the characteristics of electrodialytic concentration.
Bull. Soc. Sea Water Sci. Jpn. 1970, 24, 104–128.
(19) Azechi, S.; Fujimoto, Y.; Yuyama, T.; Itami, Y. Studies on
electrodialytic equipment with ion exchange membrane on the improve-
ment of the filter press-type concentrator. Bull. Soc. Sea Water Sci. Jpn.
1973, 26, 244–264.
(20) Watanabe, T.; Hiroi, I.; Azechi, S.; Tanaka, Y.; Fujimoto, Y.
Concentration process by ion-exchange membrane method. Bull. Soc.
Sea Water Sci. Jpn. 1980, 34, 61–90.
(21) Akiyama, M. Ion Exchange Membrane Electrodialysis for Con-
centrating Seawater: Influence of Temperature and Current Density on the
Performance of an Electrodialyzer, Technical Report, Sea Water Science
Research Laboratory, Japan Tobacco & Salt Public Corp., 1994.
(22) Sato, K.; Mastuo, T. Seawater Handbook. Soc. Sea Water Sci.
Jpn. 1974, 110.
(23) Akiyama, M. Technical Report, Sea Water Science Research
Laboratory, Japan Tobacco & Salt Public Corp., 1992.
(24) Harned, H. S.; Owen, B. B. Physical Chemistry of Electrolyte
Solutions; Reinhold Publishing Corporation: New York,1998; p 726.
(25) Hani, H.; Nishihara, H.; Oda, Y. Anion-exchange membrane
having permselectivity between anions. Jpn. Patent No. S36-15258, 1961.
(26) Mihara, K.; Misumi, T.; Yamauchi, H.; Ishida, Y. Anion-
exchange membrane having excellent specific permeability between
anions. Jpn. Patent No. S45-19980, S45-30693, 1970.

7503 dx.doi.org/10.1021/ie102386d |Ind. Eng. Chem. Res. 2011, 50, 7494–7503