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Electrodialysis

Ji Kratochvla, Petr Pnek, Roman Kodm, Dalimil nita


Introduction
Electrodialysis (ED) represents a modern progressive electromembrane separation technology
gaining recently an increasing attention in various branches of industry. Especially in the field
of brackish water desalination, which represents the largest application of this technology, the
ED is nowadays competitive to the conventional reverse osmosis process [1-4]. There can be
also increasing trend noted in application of ED within the waste water recovery and
desalination of process streams in the pharmaceutical and food industry. It is because the
electromembrane separation process doesnt endanger health and nutritious properties of the
final product e.g. by adding coagulants or regenerating agents. A demineralization of milk
whey can be mentioned as a representative example.

Fig. 1: Schema of the ED process with detail on one membrane pair and the spacer net, D
diluate compartments, K concentrate compartments, e1 and e2 electrode compartments,
AM and CM anion and cation selective membrane, respectively, (+) cation, (-) anion.
The electrodialyzer represents a typical plate-and-frame filter-press type device. The
main core of ED unit is membrane stack consisting of the planar plate anion (AM) and cation
(CM) selective membranes. The individual membranes are separated by electrochemically
inactive net-like spacers serving mainly as a mechanical support of the stack and determining
the space for the process solutions flow in between the membranes. Generally, there are two
independent hydraulic circuitries considered: a diluate stream (D) and concentrate stream (C),
supplying diluate and concentrate solutions into the diluate (DC) and concentrate
compartments (CC). A set of one AM and CM with corresponding compartments (DC and
CC) then represents a repeating motive of the ED unit often denoted as a membrane pair
(MP). For more detail, see the expanded scheme of the ED unit illustrated in Fig. 1. Beside
the two discussed hydraulic circuitries auxiliary hydraulic circuit is used to wash the electrode
compartments. The driving force of the separation process represents electric field imposed on
the membrane stack between two terminal electrodes. Cations move towards the cathode,
while anions towards the anode. However, the ions meet ion-selective membranes on this
way. Cations permeate across the CMs, otherwise they are rejected by AMs. On the contrary,
anions are allowed to cross through AMs, while CMs are not permeable for anions. By a
suitable combination of AMs and CMs in the membrane stack and electric field orientation, it
is possible to induce one-way transport of salt from diluate compartments into concentrate
compartments. The basic principles of this process are summarized in the literature [1-5]. If
ions have to be removed below a specific concentration level, the D is a product (e.g.
production of drinking and process water from brackish water or sea waters) and, on the
contrary, if ions are required to be concentrated above a specific level, the C is a product (e.g.
recovery of useful materials from effluents in metallurgy or salt production).
Theory
Material balance of ED unit
The single membrane pair has to fulfil a material balance of dissolved salts in the diluate
stream, see Eq.(1), and concentrate stream, see Eq.(2). First and second terms of these
equations represent mass inlet and outlet, respectively, and the third term corresponds to
transport of salt from D into C. Minus and plus sign indicate inlet and outlet, respectively.
Q
D,In
mp
c
D,In
Q
D,out
mp
c
D,out

I
Fz
= u
(1)
Q
C,In
mp
c
C,In
Q
C,out
mp
c
C,out
+
I
Fz
= u
(2)
Here Q is volumetric flow rate, where subscripts D and C corresponds to diluate and
concentrate, respectively, subscripts in and out indicate inlet and outlet, respectively,
superscript mp corresponds to one membrane pair, I symbolizes the electric current load and F
represents Faradays constant. The other parameters are related to a type of salt dissolved in
the process solution. In the case of brackish or sea water desalination, the real solution is often
substituted by equivalent solution of NaCl with same equivalent molar concentration. It is
possible because NaCl represents prevailing dissolved components in these waters. c in
Eqs. (1) and (2) thus denotes molar concentration of equivalent salt (NaCl) and z is charge
number of equivalent salt (number of electrons equivalent to transport of one molecule of
equivalent salt from D into C, note that for NaCl is z=1). An important process characteristic
is current efficiency of the electrodialysis (utilization of the electric current supplied for
transfer of equivalent salt from D into C). ranges in close interval from 0 to 1, where = 1
corresponds to a theoretical situation of ideally efficient process. Lower current efficiency can
be caused (a) primarily by by-pass (parasitic) current passing through the external hydraulic
circuitry, (b) by backward diffusion flux of salt from C into D due to high concentration
gradient, (c) and by migration flux due to the fact, that the membranes are not ideally
selective for cations or anions.
The ED unit plate-and-frame construction enables easy way to increase the capacity of
the unit simply by assembling more membrane pairs into the electrodialysis stack. The
electric current then passes in between the terminal anode and cathode through each MP in the
stack. The applied electric current therefore participate in the transport of salt from D into C
in each of MPs. The total amount of salt transported from D into C in the ED stack can be
obtained by multiplying the mass balance by number of membrane pairs N
mp
, see Eqs.(3) and
(4).
Q
D,In
c
D,In
Q
D,out
c
D,out

IN
mp
Fz
= u
(3)
Q
C,In
c
C,In
Q
C,out
c
C,out
+
IN
mp
Fz
= u
(4)
Generally, the total inlet and outlet volumetric flow rates are equal and after rearranging
the material balances then obtain form of Eqs. (5) and (6), where Q
D
and Q
C
corresponds to
total volumetric flow rate through diluate and concentrate compartments, respectively.
(c
D,In
c
D,out
) = +
IN
mp
Q
D
Fz

(5)
(c
C,In
c
C,out
) =
IN
mp
Q
C
Fz

(6)
An important characteristic of the electrodialysis process is degree of desalination
representing a measure of inlet solution desalination. It is traditionally defined by Eq.(7).
= _1
c
D,out
c
D,In
_ 1uu | % ]
(7)
A combination of Eqs. (7) and (5) provides an expression for degree of desalination in a
form of Eq.(8).
=
IN
mp
c
D,In
Q
D
Fz
1uu | % ]
(8)
The maximum theoretical degree of desalination for given current load is then given by
Eq.(9).

max
=
IN
mp
c
D,In
Q
D
Fz
1uu | % ]
(9)
The dependence of current efficiency on the current load can be calculated from the
outlet concentration of the salt in D according to Eq.(10). This equation results from
combination of Eqs. (7) and (9).
=

max
=
Q
D
Fz
IN
mp
(c
D,In
c
D,out
)
(10)
Faradays law
The electric current is applied in to the system via electrochemical reactions represented by
water electrolysis. At the surface of the terminal anode oxygen is formed, while hydrogen is
produced at the terminal cathode. The electrodes are washed by sodium sulphate solution in
the electrode chambers, which form a different hydraulic circuitry separated from the diluate
and concentrate streams. Faradays law representing a fundamental relationship of
electrochemistry can then be applied for the calculation of amount of gasses evolved during
the entire electrodialysis process. The Faradys law is given by Eq.(11).
m
i
=I
N
i
t
Fn

(11)
Here m represents weight of the developed i-th gas, I is electric current, M is a molecular mass
and t denotes operational time of the electrodialysis. Finally, n corresponds to number of
electrons exchange during the individual electrode reaction.
Goals of the laboratory work
1. Perform experimental parametrical studies with the pilot plant electrodialysis unit.
Vary stepwise total voltage U from 0 to 50 V under several different values of
volumetric flow rates Q. Q is identical for diluate and concentrate streams. Record the
values of U, I, specific conductivity of inlet and outlet solutions and temperature.
2. Compute the values of the inlet and outlet solutions concentration using linear
interpolation of empirical data of electric conductivity in dependence on temperature
and molar concentration.
3. Read the volume of produced oxygen and hydrogen and compute the charge passed
through the device (by means of Faradays law) and compare this value with real total
charge provided by the electric current source.
4. Make following plots:
- dependence of U on I for various Q.
- dependence of desalination degree on current load for various volumetric flow
rates. Add to this plot the dependence of the maximum theoretical desalination
degree
max
obtained under a condition of = 1 for the same values of I and Q.
- dependence of desalination degree on the electric energy input defined by
P = *I [+ for various Q.
- dependence of the efficiency of electrodialysis process on the current load for
different I and Q.
Experimental part
Description of the pilot plant ED unit
The photography of the electrodialyzer and the supporting fixtures can be seen in Fig. 2 and
corresponding schema in Fig. 3.

Fig. 2: Photography of the pilot plant electrodialysis unit installed in ICT Prague, (A)
membrane stack, (V2 through V5) rotameters for diluate and concentrate streams, (V1 and
V6) rotameters for electrode solutions, (B) and (C) cylindrical reservoirs for gasses
produced at the electrodes, (D, E,F, G) conductometers (diluate inlet (D), concentrate inlet
(E), diluate outlet (F) and concentrate outlet (G)).

The heart of the device represents membrane stack consisting of 192 membrane pairs. Active
area of one membrane is of 0.32 x 0.64 m
2
. Both sides, left and right, are bordered by
electrode compartments equipped with platinized titanium terminal electrodes washed by
Na
2
SO
4
solution. Volumetric flow rate of the electrode solutions is controlled by rotameters
V1 and V6. There are two transparent plastic columns, where hydrogen and oxygen from
water electrolysis are accumulated. There are four rotameters V2 through V5 controlling
volumetric flow rate of concentrate and diluate solutions. NaCl solution with equal
concentration is used for both concentrate and diluate. The set of four conductometers are
used for measuring the electrical conductivity of diluate and concentrate inlet and outlet.

Fig. 3: Scheme of the pilot plant electrodialysis unit, V valves, H reservoirs, B and C
storage columns for gasses, C conductometer
Measurement with ED pilot plant unit
Values of the voltage and volumetric flow rate, which will be measured, are written in the
protocol which you obtain in the laboratory.
1. Set the volumetric flow rate of diluate (V2), concentrate (V3) and electrode solutions
(V1, V6) only WHEN THE ELECTRICAL SOURCE IS SWITCHED OFF and
voltage and passing current are equalled to zero.
2. After the assistant control and under his supervision the current source is switched on and
required voltage is set.
3. After each change of the voltage record three times every 5th minute the values of
electric conductivity, temperature, voltage and electric current to the protocol until the
steady state is reached (approx. 5 min).
4. After the measurements, reduce the voltage to zero and switch off the current source.
5. Change the values of volumetric flow rates and repeat the steps from 2 to 4.
6. Finally, set the voltage to zero and switch off the current source and call the assistant
who switch off the whole device.
7. Determine the volume of oxygen produced using graduated cylinder.
Summary
1. Assistant control
2. Switch on the pumps
3. Set the first value of volumetric flow rate
4. Switch on the electrical source
5. Set the voltage
6. 5 min to the steady state, read and write the first set of values of the measured quantities
7. Reset the voltage
8. After 5 min. read and write the second set of values of the measured quantities
9. Repeat the step 7 and 8
10. Increase the voltage to the next measured value and repeat the steps from 5 to 9
11. Decrease the voltage to zero
12. Set the second value of volumetric flow rate, repeat the steps from 3 to 11
13. Decrease the voltage to zero and switch off the source
14. Switch off the pumps
15. Determine the volume of oxygen using cylinder
Safety
Keep on mind that it is worked with electrical conductive solutions under relatively high
values of current and voltage. According to EU regulation the safety DC current is
I < 10 mA and safety DC voltage is U < 25-60 V.
Manipulate only with valves mentioned within this instruction (V1 V6).
A short speech about the safety will take place right before the work starts. Please listen
carefully and ask immediately if you need.
References
1. Strathmann H, Giorno L, Drioli E (2006) An introduction to membrane science and
technology, Institute on Membrane Technology, CNR-ITM, Italy
2. Baker R W (2004) Membrane Technology and Applications, 2nd ed., John Wiley & Sons,
ISBN 0-470-85445-6
3. Baker et al. (1991) Membrane separation systems, Noyes Data corp., USA, ISBN 0-8155-
1270-8
4. Strathmann H: Electrodialysis, a mature technology with a multitude of new applications
(2010) Desalination 264(3):268-288
5. Tanaka Y (2007) Ion exchange membranes fundamentals and applications, 1st ed.,
Elsevier, Amsterdam
Symbols
c

molar concentration of equivalent salt [mol m
-3
]
F Faradays constant, 96,485 C mol
-1

I electric current [A]
m weight [kg]
M molecular mass [kg mol
-1
]
n number of electrons exchange in the electrode reaction
N
mp
number of membrane pairs, 192 pairs
Q volumetric flow rate [m
3
s
-1
]
Q
el
electrical source charge [C]
Q
mt
mass transport charge
Q
i
oxygen respectively hydrogen production charge
t time [s]
U total voltage [V]
I

volumetric flow rate [m


3
s
-1
]
z charge number of equivalent salt
degree of desalination [%]
electrodialysis process efficiency

Subscripts and superscripts
D

diluate
C concentrate
in inlet
out outlet
mp membrane pair
max maximum theoretical value
Questions
1. What was the aim of this laboratory work? Which quantities were measured and which
were set?
2. Under which conditions the electric source could be switched on?
3. Check the results and estimate and afterwards compute the desalination degree and
maximum theoretical desalination degree when volumetric flow rate is 5,000 dm
3
h
-1
and
applied voltage is 50 V. Assume the corresponding dependences to be linear if it is
necessary.