ARTICLE

pubs.acs.org/IECR

Ion-Exchange Membrane Electrodialysis of Saline Water

and Its Numerical Analysis
Yoshinobu Tanaka*
IEM Research, 1-46-3 Kamiya, Ushiku-shi, Ibaraki 300-1216, Japan

ABSTRACT: A computer simulation program was developed for a continuous saline water electrodialysis process. A practical-scale
electrodialyzer was operated for concentrating seawater, and its performance was observed. The operating results of the
electrodialyzer were computed by using the operating conditions as input for the program. The computed data were generally
the same as the observed data. Thus, the program enables the semiquantitative discussion of the performance of a practical-scale
electrodialyzer. In addition, (1) the current density distribution; (2) the electric resistances of a membrane pair, a desalting cell, and a
concentrating cell; (3) the pressure drops in a desalting cell and a concentrating cell; and (4) the limiting current density of an
electrodialyzer are discussed.

1. INTRODUCTION calculated by computer simulation with the operating results of an

Ion-exchange membrane electrodialysis is a technique for electrodialyzer. In this investigation, a practical-scale electrodialy-
separating ionic species in a feed solution, and it is applied to zer was operated for seawater concentration under changing
saline water desalination.1
6 This technology is currently used in current density and solution temperature. The performance of
many fields such as drinking water treatment, wastewater treat- the electrodialyzer was computed using the electrodialysis pro-
ment, demineralization of amino acids, demineralization of whey, gram with the same conditions as applied to the electrodialysis
demineralization of sugar liquor, and treatment of organic operation used as input. The reasonability of the program is
substances. Electrodialysis is also applied to concentrate discussed by comparing the operating results of the electrodialyzer
seawater,7,8 and research on electrodialytic seawater concentra- with the calculated results.
tion has been carried out.9
11
In a salt-manufacturing process, the concentrated brine ob-
tained from an electrodialyzer is supplied to an evaporation 2. ELECTRODIALYSIS PROGRAM
process to produce edible salt. Currently, nearly 106 ton/year of The electrodialysis process considered in this investigation is a
edible salt is manufactured in Japan. The largest problem in continuous process for concentrating seawater.31 The principle of
seawater concentration is that the price of produced salt is higher the process is fundamentally the same as that of a continuous
than that of imported salt because of higher energy consumption. process for saline water desalination and has been investigated
To reduce energy consumption, homogeneous ion-exchange widely.32
35 However, in this work, the program is developed in the
membranes having excellent electrochemical properties have been following ways to describe the operating conditions more definitely:
synthesized. The mechanical strength of these membranes was (1) The relationship between solution temperature and
increased by cross-linking and reinforcement.12
14 Their perfor- electrodialyzer performance is clarified by evaluating
mance was tested by the long-term endurance operation of an the influence of temperature on the solution physical
electrodialyzer.15 A diagonal net spacer was incorporated into an properties and membrane characteristics.
electrodialyzer to mix a solution flowing in desalting cells.16 The (2) The electric current screening ratio of a spacer is defined
divalent ion permeability across the membranes was strongly and calculated.
suppressed to prevent CaSO4 scale precipitation.17
20 To prevent (3) The ionic concentration ratio in a concentrated solution
CaCO3 scale precipitation, hydrochloric acid was added to con- is calculated using empirical equations.
centrating cells.21 Small particles suspended in a feed solution were (4) The hydrodynamic diameters and pressure differences in
removed using sand filtration.22 However, extremely small parti- a desalting cell and a concentrating cell are calculated.
cles passed through the filter, entered into the electrodialyzer, and (5) A concentrated solution is circulated.
allowed microorganisms to breed at the membrane surface.23,24 Taking account of the above revisions, the electrodialysis
The deposits on the membrane were removed by stack disassem- program (compiled in section 7) is developed on the basis of
bling or washing with a chemical reagent.25
27 the following assumptions:
The electrodialysis process can be operated as a continuous, (1) Mass transport across the membrane pair is expressed by
batch, and feed-and-bleed process. In previous investigations,28
30 the overall mass-transport equation.
an electrodialysis program for these processes was developed to
analyze the performance of an electrodialyzer. The program Received: March 18, 2011
includes the model equations with ordinary principles such as Accepted: July 11, 2011
mass transport, mass balance, and energy consumption. To Revised: July 2, 2011
develop the program further, it is necessary to compare the data Published: July 11, 2011

r 2011 American Chemical Society 10765 dx.doi.org/10.1021/ie2005498 | Ind. Eng. Chem. Res. 2011, 50, 10765–10777
Industrial & Engineering Chemistry Research ARTICLE

Figure 1. Continuous process.

(2) The overall transport number, overall solute permeabil- with a constant electric current I as illustrated in Figure 1. An
ity, overall electro-osmotic permeability, and electric electrolyte solution (of concentration C0in) is supplied to the
resistance of an ion-exchange membrane pair are deter- inlets of desalting cells (De) at an average linear velocity of u0in.
mined from the overall hydraulic permeability (leading Electrolytes and solutions transfer from desalting cells to con-
parameter). centrating cells (Con) across an ion-exchange membrane pair
(3) The influence of the temperature on the performance of an with fluxes of JS and JV, respectively. The concentrated solution is
electrodialyzer is determined on the basis of the relationship circulated through the circulation tank equipped at the outside of
between temperature and overall hydraulic permeability. the electrodialyzer, with the solution velocity adjusted to u00in at
(4) Solution leakage and electric current leakage are assumed the inlets and u00out at the outlets of concentrating cells.
to be negligible. The salt concentration in the concentrated solution, C00 , is
(5) The frequency distribution of the solution velocity ratio maintained at a steady state in the flow system. In desalting cells,
in desalting cells is assumed to be a normal distribution. the electrolyte concentration decreases from C0in under an
(6) The current density i at a distance of x from the inlets of applied average current density of I/S and reaches an average
desalting cells is approximated by a quadratic equation. electrolyte concentration of C0out at the outlets of desalting
(7) The voltage difference between the electrodes at the cells. The change in the electrolyte concentration in desalting
entrance of desalting cells is assumed to be equal to the cells causes a change in current density along the flow pass
value at the exits. from iin at the inlets to iout at the outlets. The current density
(8) The limiting current density of the electrodialyzer is becomes i at a distance of x from the inlets of desalting cells. I/S,
defined as the average current density applied to the JS, JV, C0 , C00 , u0 , and u00 are the values of the corresponding
electrodialyzer when the current density reaches the limit quantities at a distance of pl from the inlets of desalting cells;
of an ion-exchange membrane at the outlet of the x = pl. Vin, Vout, and Vp are the voltage differences between the
desalting cell in which linear velocity and salt concentra- electrodes at the inlets (x = 0), outlets (x = l), and x = pl,
tion are the lowest. respectively, for the desalting cells.
(9) The salt concentration is assumed to be uniform in concen-
trating cells, and concentrated solutions are extracted from
the concentrating cells to the outside of the process. 4. ELECTRODIALYSIS PROGRAM
The limitations of the program are as follows: The performance of the electrodialyzer illustrated in Figure 1
(1) Saline water supplied to an electrodialyzer is a solution is computed according to the electrodialysis program presented
dissolving strong electrolytes. in Figures 2
4. The program consists of the following steps, as
(2) Empirical equations are developed on the basis of explained in the algorithm in section 7:
experiments using homogeneous ion-exchange mem- Figure 2 shows steps 1
3.
branes manufactured by Japanese companies.
Step 1. Simulation of the mass transport (sections
7.1
7.3)
3. ELECTRODIALYSIS PROCESS Step 2. Simulation of the current density distribution
An electrodialyzer (effective membrane area, S; flow-pass (section 7.7)
width, b; flow-pass length, l; flow-pass thickness, a) is operated Step 3. Simulation of the cell voltage (sections 7.5 and 7.8)
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Figure 2. Simulation of mass transport, current density distribution, and cell voltage (steps 1
3).

Figure 3 shows step 4. • average linear velocities at the inlets of desalting and
concentrating cells, u0in and u00in, respectively;
Step 4. Simulation of the NaCl concentration and energy
• current density, I/S
consumption (sections 7.4 and 7.10)
• flow-pass thicknesses in desalting and concentrating
Figure 4 shows step 5.
cells, a0 and a00 , respectively;
Step 5. Simulation of the limiting current density (section • flow-pass widths in desalting and concentrating cells, b0
7.11) and b00 , respectively;
Computation of the electrodialysis program is performed by • flow-pass lengths in desalting and concentrating cells, l0
substituting the following inputs and control keys in Figures 2
4: and l00 , respectively;
Inputs • standard deviation of the normal distribution of solution
• temperature of the feed solution, T; velocity ratio in desalting cells, σ = 0.1;
• salt concentration at the inlets of desalting cells, C0in; • and so on.
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Figure 4. Simulation of limiting current density (step 5). Superscript #

indicates the lowest value in an electrodialyzer.

Figure 3. Simulation of the NaCl concentration in a concentrated of u0in. The desalted seawater was extracted to the outside of the
solution and energy consumption (step 4). process. Seawater was supplied to the concentrating cells at an
average linear velocity at the inlets of the concentrating cells of u00in and
Control Keys circulated through the concentrated solution circulating tank. The
• average salt concentration in desalting cells at x = pl, C*; pH of the concentrated seawater was adjusted to less than 5.8 by
• position at which the current density becomes I/S in an adding sulfulic acid to prevent CaCO3 precipitation on the anion-
electrodialyzer, p*; and exchange membranes. The anode chamber was supplied with sea-
• salt concentration at the outlet of the desalting cell0 at water (desalted seawater) in which sodium thiosulfate had been
#*
which linear velocity becomes the lowest in a stack, Cout , added to remove Cl2 generated at the anode. To avoid deterioration
In the computation, if the algorithm reaches a decision point of the membrane due to Cl2, the washing chamber was incorporated
(diamond symbol), it is adjusted by changing control keys to realize between the anode chamber and the membrane stack. Seawater was
the equations given at the decision points. Then, it loops back to an also supplied to the cathode chamber into which hydrochloric acid
earlier portion in the algorithm. The trial-and-error calculation had been added to maintain pH 2.0 to prevent Mg(OH)2 precipita-
repeats until all equations are satisfied. The computation finished tion on the cathode. Next, an electric current was passed between
within 10 min to obtain one group of plots in the figures. electrodes as the stack voltage was observed. After steady state was
achieved, the cell voltage was measured with Pt electrodes inserted
into the concentrating cells integrated at both ends of the stack. The
5. ELECTRODIALYSIS EXPERIMENTS solutions were sampled at the inlets of the desalting cells and the
In the electrodialysis experiments, 45 or 90 pairs of ion- outlets of the desalting and concentrating cells to analyze the con-
exchange membranes, Aciplex K172/A172 or Aciplex K182/ centrations of Na+, K+, Mg2+, Ca2+, and SO42
ions. In seawater
A182 (Asahi Chemical Co.), were integrated in an electrodialyzer electrodialysis, the electrolyte concentration C is given as C = CNa +
(effective membrane area, 48.5 dm2 = 50 cm width  97 cm CK + CMg + CCa = CCl + CSO4. Tables 1 and 236 list the specifications
length; distance between the membranes, 0.05 cm). An electro- of the electrodialyzer and electrodialysis conditions, respectively.
dialysis system was formed as illustrated in Figure 5. In this
system, the temperature of sand-filtered seawater was controlled 6. RESULTS AND DISCUSSION
to T ( 0.3 °C by a temperature controller and supplied to the
seawater feeding tank. It was further supplied to the electrodia- 6.1. Calculated Values versus Observed Values. The ob-
lyzer at an average linear velocity at the inlets of the desalting cells served experimental values, Xobs, were plotted versus the values
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Table 2. Electrodialysis Conditions

temperature (°C) 20, 30, 40
current density (A/dm2) 1.0, 2.0, 3.0, 4.0
linear velocity (cm/s)
desalting cells 5
concentrating cells 0.5
solution flow system
desalting cells one-pass flow
concentrating cells circulation flow

Figure 5. Electrodialysis system.

Table 1. Specifications of the Electrodialyzer

ion-exchange membrane Aciplex K172/A172, Aciplex K182/
A182
thickness of the membrane (mm) 0.08
0.10 (K172, K182)
0.09
0.11 (A172, A182)
electric resistance of the membrane 1.9
2.2 (K172), 1.7
2.1 (A172)
(Ω cm2) 1.5
1.8 (K182), 1.4
1.7 (A182)
number of membrane pairs in the 45 (K172/A172), 90 (K182/A182)
stack (pair)
effective membrane area 48.5 dm2 (50 cm width  97 cm
length)
distance between the membranes 0.5
(mm)
fastening frame stainless steel plate fastened with
bolts and nuts Figure 6. Ion flux across a membrane pair.
gasket (desalting and concentrating synthetic rubber (0.5 mm thick)
cells)
spacer polyethylene net (diagonalnet)
anode titanium (3 mm thick) + platinum
(3 μm thick)
cathode stainless steel (SUS316, 3 mm thick)

calculated by means of simulations, Xcal, taking temperature T and

current density I/S as parameters. The results are shown in Figure 6
(JS), Figure 7 (JV), Figure 8 (η, ηNaCl), Figure 9 (C0out), Figure 10
(C00 ), Figure 11 (C00 NaCl), Figure 12 (θ), Figure 13 (Vcell), and
Figure 14 (ENaCl). Compared with the Xcal = Xobs line plotted in the
figures, the observed values are seen to be generally equivalent to the
calculated ones. However, there are some cases where considerable
deviations arise. The deviations are estimated to be due to (1) errors
in the assumptions and empirical equations applied in the computer
program and/or (2) errors in the electrodialysis experiments.
Inspecting the assumptions described in section 2, one can see
that the computed results cannot be exactly the same as the
experimental results. However, the deviations do not eliminate
the usefulness of the program because the performance of a
practical-scale electrodialyzer can be discussed semiquantita-
tively based on this program.
6.2. Current Density Distribution. Figure 15 shows distribu-
tions of the current density i taking the average current density Figure 7. Solution flux across a membrane pair.

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Figure 10. Electrolyte concentration in a concentrated solution.

Figure 8. Current efficiency.

Figure 11. NaCl concentration in a concentrated solution.

Figure 9. Electrolyte concentration in a desalted solution.

energy consumption in a seawater concentration process, it is

I/S as a parameter. Current density increased at the inlets (x/l = 0) necessary to reduce the electric resistances of the ion-exchange
of the desalting cells and decreased at the outlets (x/l = 1) of the membranes.
desalting cells. The current density changes in Figure 15 are rather 6.4. Pressure Differences in a Desalting Cell and a Con-
small. This is because the salt concentration in the feed solution, centrating Cell. Figure 18 shows the pressure drops in a
namely, seawater, is high. If dilute saline water were supplied to an desalting cell (ΔP0 ) and a concentrating cell (ΔP00 ).
electrodialyzer, the current density change would be greater. 6.5. Limiting Current Density. Limiting current density,
i becomes equivalent to I/S at x = pl, and p is plotted against (I/S)lim, is plotted against current density, I/S, in Figure 19.
I/S in Figure 16. It should be noticed that (I/S)lim was computed using the
6.3. Electric Resistances of a Membrane Pair, a Desalting standard deviation of the normal distribution of the solution
Cell, and a Concentrating Cell. The electric resistances of a velocity ratio, σ = 0.1. The actual limiting current density of the
membrane pair (rmemb), a solution in a desalting cell (r0 ), and a electrodialyzer can be estimated from the intersection of the
solution in a concentrating cell (r00 ) were calculated at x = pl (I/S)lim and I/S = (I/S)lim lines in the figure and is approximately
(Figure 17). rmemb is greater than r0 and r00 . To decrease the 9 A/dm2 in this electrodialyzer.
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Figure 12. NaCl purity in a concentrated solution.

Figure 14. Energy consumption.

Note that eq 1 involves two equations. The first expresses the

material conservation law for the concentrating compartment,
and its general form is
00 00 00 00 00 00
Cin uin þ JS S ¼ Cout uout ¼ Cout ðuin þ JV SÞ ðaÞ
Equation 1 is obtained by setting = C00in C00out
= C in eq a. The 00

second part presents the ion transfer into this compartment.39

Equation 2 is one of the Kedem
Katchalsky equations.40

The electrolyte concentration in concentrating cells, C00 , is

obtained from eqs 1 and 2 as38
1  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 
C00 ¼ A2 þ 4FB
A ð3Þ
2F

A ¼ ϕðI=SÞ þ μ
FC0 ð4Þ

B ¼ λðI=SÞ þ μC0 ð5Þ

In a practical-scale electrodialyzer, solution leakage and electric
current leakage are usually generated to greater or lesser degrees.
However, in the above equation, the influence of both leakages is
not taken into account.
Figure 13. Cell voltage. 7.2. Membrane Characteristics. The membrane-pair char-
acteristics λ (equiv C
1), μ (cm s
1), and ϕ (cm3 C
1) and the
7. ALGORITHM membrane-pair alternating-current electric resistance ralter
The algorithm is compiled in this section. It is explained in (Ω cm2) (where 2ralter = rK + rA) are expressed by the following
detail in the textbook by Tanaka.37 functions of F (cm4 equiv
1 s
1)38
7.1. Mass Transport. The ion flux, JS, and volume flux, JV, λ ¼ 9:208  10
6 þ 1:914  10
5 F ð6Þ
transported across a membrane pair are expressed by the
following overall mass-transport equation38
μ ¼ 2:005  10
4 F ð7Þ
00 00 0
JS ¼ C JV ¼ λðI=SÞ
μðC
C Þ ð1Þ
ϕ ¼ 3:768  10
3 F0:2
1:019  10
2 F ð8Þ
00 0
JV ¼ ϕðI=SÞ þ FðC
C Þ ð2Þ
2ralter ¼ rK þ rA ¼ 1:2323F
1=3 ð9Þ
in which λ is the overall transport number, μ is the overall solute
permeability, ϕ is the overall electro-osmotic permeability, and F F is the leading parameter representing the other membrane-pair
is the overall hydraulic permeability. characteristics. Each membrane must have its own F value.
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Figure 17. Electric resistances of a membrane pair and a solution in a

Figure 15. Current density distributions. desalting cell and a concentrating cell.

concentration C (g of salt/kg of solution)

d ¼ 1:001
1:101  10
4 T
3:356  10
6 T 2
þ ð7:881
1:368  10
2 T þ 8:978
 10
5 T 2 Þ  10
4 C ð11Þ

k ¼ ð0:9383 þ 3:463  10
2 TÞ  10
3 C

ð1:655 þ 3:863  10
2 TÞ  10
6 C2

ð1:344 þ 3:160  10
2 TÞ  10
9 C3 ð12Þ

γ ¼ 0:5927 þ 0:4355C
0:5
7:201  10
5 C

þ 3:503  10
6 C2 ð13Þ

Equation 13 holds in the range from normal temperature to
70 °C.
7.4. Ionic Constituents in a Concentrated Solution41. In the
electrodialysis of seawater, the equivalent ratio of Na+ ions to
total ions, rNa, in the concentrated solution is expressed as the
following function of current density (I/S) (A/dm2) and T (°C)

Figure 16. p values at which i becomes equal to I/S. rNa ¼ 0:9584
4:269  10
3 T
However, the F values of various commercially available mem- þ ð0:7983 þ 9:824  10
2 TÞ  10
2 ðI=SÞ0:5
branes have been found to be nearly the same, and they can be ð14Þ
expressed by the following empirical function of temperature
T (°C)41 The relationships between rNa and rK, rMg, and rCa are

F ¼ 3:421  10
3 þ 3:333  10
4 T ð10Þ rK ¼ 1:905  10
2 þ 8:838  10
3 rNa ð15Þ

This equation reveals the relationship between temperature and rMg ¼ 0:7405
0:7668rNa ð16Þ
membrane characteristics.
7.3. Relationship between Temperature and Electrolyte rCa ¼ 0:2460
0:2482rNa ð17Þ
Concentration of an Electrolyte Solution and Its Physical
Properties. Density d (kg/dm3) can be obtained from ref 42; The relationship between (I/S) and rCl is approximated by the
specific electric conductance k (S/cm), from ref 43; and electro- equation
lyte (NaCl) activation coefficient γ, from ref 44. They are given by
the following functions of temperature T (°C) and electrolyte rCl ¼ 0:9929 þ 1:947  10
3 ðI=SÞ ð18Þ

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Figure 20. Structure of a diagonal net spacer.

because the solution stream fans out and solution mixing is

promoted between the two channels.
The electric current screening ratio, ε, of the diagonal net
spacer in Figure 20 is represented by the equation41
Figure 18. Pressure drops in a desalting cell and a concentrating cell. ε ¼ ðelectric current screening area of a unit meshÞ=ðtotal area of a unit meshÞ
2rða=2Þ a
¼ ¼ ð20Þ
r 2 sin R r sin R
in which a is the flow-pass thickness of the cell, d = a/2 is the
diameter of the spacer rod, r is the distance between the two rods,
and R is the crossing angle of the two rods. The numeral 2 means
that two screening parts are taken into account in four screening
parts surrounding the unit net mesh.
The electric resistances of a desalting cell (r0 ) and a concen-
trating cell (r00 ) are given as
a0
r0 ¼ ð21Þ
ð1
ε0 Þk0

a00
r 00 ¼ ð22Þ
ð1
ε00 Þk00

7.6. Hydrodynamic Diameters and Pressure Differences in

a Desalting and a Concentrating Cell. The hydrodynamic
diameter, dH, of a desalting or concentrating cell incorporated
with a diagonal net spacer is expressed as45,46
d=2
Figure 19. Limiting current density. 8
4π
dH ¼  r ð23Þ
4 1 d=2 1
in which T is not included. rCl and rSO4 are related through þ þ 2π 1

b d=2 b r
rSO4 ¼ 1
rCl ð19Þ where d/2 is the radius of the spacer rods (d/2 = a/4), r is the
distance between two spacer rods or mesh size, and b is the flow-
pass width of the cell.
7.5. Electric Current Screening Ratio of a Spacer and
Assuming the flow pattern in the cell to be laminar, the
Electric Resistances of a Desalting Cell and a Concentrating
Cell. Spacers partially screen the electric current and increase the pressure difference between the inlet and the outlet of the cell is46
local current density. To discuss the energy consumption of an 32μlu
electrodialyzer, it is necessary to evaluate the electric current ΔP ¼ ð24Þ
dH 2
screening ratio of a spacer. The structure of the diagonal net
spacer incorporated in the electrodialyzer of this work is illu- in which l is the flow-pass length in the cell. The viscosity
strated in Figure 20, which shows that rods arranged in two coefficient of the solution, μ (g cm
1s
1), can be obtained from
directions are stacked on each other. The solution supplied to the ref 43 and is given by the following function of temperature T
cell flows along two channels, so solution stagnation is prevented (°C) and electrolyte concentration C (g of salt/kg of solution) of
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the solution 7.8. Cell Voltage. The cell voltage, Vcell, is given by the

2
4 equation49,50
μ ¼ 1:200  10
1:224  10 T
þ ð2:107  10
5
1:529  10
7 TÞC Vcell ¼ VΩ, in þ Vmemb, in ¼ VΩ, out þ Vmemb, out ð35Þ
þ ð
1:392  10
8 þ 1:123  10
10 TÞC2
þ ð5:819  10
10
6:769  10
12 TÞC3 ð25Þ The ohmic potential, VΩ,in, and membrane potential, Vmemb,in, at
the inlets of desalting cells in eq 35 are given as
7.7. Current Density Distribution. Solution velocities in 0

desalting cells vary between the cells, which gives rise to a VΩ, in ¼ ðrin þ rmemb, in þ r 00 Þiin ð36Þ
solution velocity distribution. We assume here that the fre-
quency, Yj, of the solution velocity ratio ξ of group j defined by  
RT γ00 C00
ub
u Vmemb, in ¼ 2ðtK þ tA
1Þ ln 0 0 ð37Þ
ξ¼ ð26Þ F γin Cin
u
These potentials at the outlets of desalting cells in eq 35 are given
where u is the average linear velocity in every desalting cell and ub by averaging the values for N cell pairs integrated in an electro-
is the linear velocity in each desalting cell, is approximated by the dialyzer
normal distribution. Here, the standard deviation of the normal ! 
distribution of ξ is defined as σ. jmax jmax
∑ ∑
0
00 1
Assuming the existence of this solution velocity distribution, VΩ, out ¼ Yj rout, j þ Yj rmemb, out, j þ r N
the electrolyte concentration decreases along flow passes in j¼0 j¼0 N
desalting cells and gives rise to an electric resistance distribution ð38Þ
and a current density distribution. We assume here that the
current density i at a distance of x from the inlet of a desalting cell
is approximated by    jmax
RT γ00 C00
∑
1
   2 Vmemb, out ¼ 2ðtK þ tA
1Þ ln 0
x x F N j ¼ 0 γout, j C0out, j
i ¼ a1 þ a2 þ a2 ð27Þ
l l ð39Þ
To determine the coefficients a1, a2, and a3 in eq 27, the following
three simultaneous equations are set up47,48 in which Yj is the number of desalting cells in group j and
subscript j denotes group j in the normal distribution within the
Vin ¼ Vout ð28Þ range of ξj
Δξj < ξj < ξj + Δξj.
7.9. Direct Electric Resistance of an Ion-Exchange Mem-
Vin ¼ Vp ð29Þ brane Pair. rmemb,in in eq 36 and rmemb,out in eq 38 are
membrane-pair direct-current electric resistance at the inlet
ζinout ¼ ζinp ð30Þ and outlet, respectively, of a desalting cell and are evaluated as
follows:50 The alternating-current electric resistance of an ion-
ζinout is introduced from eq 28 and expressed as exchange membrane, ralter, given in eq 9 is equivalent to the
electric resistance measured by the conventional method, but it is
R1 þ R2 p þ R3 p2 iout calculated from the overall hydraulic permeability F in this
ζinout ¼ ¼ ζout ¼ ð31Þ
β1 þ β2 p þ β3 p2 I=S investigation. To measure the direct-current electric resistance
of an ion-exchange membrane, the membrane is set in a
As shown in eq 31, it equals the outlet current density non- two-cell apparatus, and a low-concentration NaCl solution
uniformity coefficient ζout. ζinp is introduced from eq 29 and [specific conductivity k0 (S/cm)] is supplied to both cells. The
expressed as direct-current electric resistance of the membrane, rdire* (Ω cm2),
is measured at 25 °C by passing a direct current. The rela-
γ1 þ γ2 p þ γ3 p2
ζinp ¼ ¼ ζout ð32Þ tionship between k0 and rdire*/ralter is given by the empirical
ð2p
3p2 ÞðI=SÞ equation

It is also equal to ζout. 

!
r
We determined a1, a2, and a3 from the inlet current density log dire ¼ 0:3380 þ 0:6386k0 þ 0:2961ðlog k0 Þ2
nonuniformity coefficient ζin, outlet current density nonunifor- ralter
mity coefficient ζout, inlet current density iin, and outlet current
ð40Þ
density iout

ζin ¼
iin
¼
a1
ð33Þ A low-concentration NaCl solution (specific conductivity k0 )
I=S I=S is supplied to the desalting side, and a high-concentration
solution (specific conductivity k00 ) is supplied to the concentrat-
ing side of the above apparatus. The direct-current electric
iout a1 þ a2 þ a3
ζout ¼ ¼ ð34Þ resistance of the membrane, rdire, is measured at 25 °C by passing
I=S I=S a direct current and subtracting the effect of membrane potential.
10774 dx.doi.org/10.1021/ie2005498 |Ind. Eng. Chem. Res. 2011, 50, 10765–10777
Industrial & Engineering Chemistry Research ARTICLE

The empirical relationship between k00 /k0 and rdire/r*dire is as its limiting current density, (I/S)lim, introduced from eqs 34
 00  and 50, which is expressed by51
rdire k
¼ 1:000
0:1359 ð41Þ  

rdire k0 I ilim ðm1 þ m2 u#out Þ 0 # n1 þ n2 u#out
¼ ¼ Cout ð51Þ
The direct electric current of a membrane pair, rmemb, is S lim ζout ζout
0
estimated by multiplying eq 40 by eq 41 #
in which Cout is C0out at u = u#out.

! ! In eq 51, u#out is nearly equal to u#in for commercially available
rdire rdire membranes. Substituting u#in = u#out in eq 51 leads to
rmemb ¼ rK þ rA ¼  2ralter ¼ 2rdire ð42Þ
ralter rdire  
I m1 þ m2 u#in  0 # n1 þ n2 u#in
¼ Cout ð52Þ
rmemb is calculated by substituting ralter expressed in eq 9 into S lim ζout
0
eq 42. in which Cin# is C0in at u = u#in, which is given by
7.10. NaCl Concentration in a Concentrated Solution
and Energy Consumption. The concentration of ion i, C00i u#in ¼ u#in ð1
3σÞ ð53Þ
(equiv/cm3), in a concentrated solution is calculated from
ionic concentration ratio of ion i, ri (cf. section 7.4), and the where σ is the standard deviation of the normal distribution of
concentration of electrolyte, C00 (equiv/cm3) (cf. eq 3), using the the solution velocity ratio defined by eq 26.0
#
equation The relationship between (I/S)lim and Cout is also introduced
as
00
Ci ¼ ri C00 ð43Þ    
I a # 0 0
#Þ
¼ u ðC
Cout ð54Þ
The concentrations of NaCl, C00NaCl, and electrolyte, C00 , in a S lim λl in in
concentrated solution; the NaCl purity, θ, of the concentrated Setting eq 52 equal to eq 54 gives
solution; the electrolyte output, JS, and the NaCl output, PNaCl,
are given by49,50  0
n1 þ n2 u#in
#
Cout
00 00
CNaCl ðg=cm3 Þ ¼ 58:443CNa ðequiv=cm3 Þ ð44Þ Z1 ¼ # ð55Þ
C0in
C0out
  !
C00 ðg=cm3 Þ ¼ 57:84C00 ðequiv=cm3 Þ ð45Þ aζout u#in
Z2 ¼ ð56Þ
λl m1 þ m2 u#in
00
CNaCl ðg=cm3 Þ
θ¼ ð46Þ
C00 ðg=cm3 Þ Z1 ¼ Z2 ð57Þ
The limiting current density of the electrodialyzer, (I/S)lim, is
JS ½kg=ðm2 hÞ ¼ ½C00 ðkg=m3 Þ½JV ðm=hÞ ð47Þ computed
0
#*
by a0 trial-and-error calculation by substituting control
#
key
0
Cout for Cout in eq 55 to realize Z1 = Z2 (eq
0
57) to determine
# #
Cout. (I/S)lim is calculated by substituting Cout into eq 52.
PNaCl ½kg=ðm2 hÞ ¼ fJS ½kg=ðm2 hÞgθ ð48Þ
8. CONCLUSIONS
The energy consumption to produce one ton of NaCl, ENaCl, is
expressed using Vcell by the equation Data computed with the electrodialysis program described in
this work are generally equivalent to the data observed in
Vcell I electrodialyzer operation, but some deviations are found be-
ENaCl ¼ ð49Þ tween the two data sets. The deviations do not eliminate the
PNaCl
usefulness of the program because the program enables the
performance of a practical-scale electrodialyzer to be discussed
7.11. Limiting Current Density. The limiting current density
semiquantitatively.
of a cation-exchange membrane is less than that of an anion-
exchange membrane, because the mobility of the counterions in
solution for a cation-exchange membrane is less than that for an
’ AUTHOR INFORMATION
anion-exchange membrane. Therefore, the limiting current den- Corresponding Author
sity of an ion-exchange membrane integrated in an electrodialy- *E-mail: [email protected].
zer, ilim, is given by the following empirical equation established
for a cation-exchange membrane51
’ ACKNOWLEDGMENT
0
n1 þ n2 uout
ilim ¼ ðm1 þ m2 uout ÞCout ð50Þ We are grateful to Mr. Masao Akiyama, Sea Water Science
Research Laboratory, Japan Tobacco & Salt Public Corporation,
When the current density reaches the limit of a cation-exchange for offering the experimental data and Ms. Noriko Nakai, Central
membrane, ilim, at the outlet of the desalting cell in which the Research Institute, Japan Tobacco & Salt Public Corporation, for
linear velocity is the lowest among the uoutvalues, that is, u#out, the assistance in the experimental work. We thank Mr. Goro
average current density applied to the electrodialyzer is defined Takahashi and Miss Aki Shinohara, Department of Chemistry,
10775 dx.doi.org/10.1021/ie2005498 |Ind. Eng. Chem. Res. 2011, 50, 10765–10777
Industrial & Engineering Chemistry Research ARTICLE

00
School of Hygienic Science, Kitasato University, for assistance in = concentrating cell
the fundamental investigation. # = lowest
* = control key
’ NOMENCLATURE
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