Separation Science and Technology

ISSN: 0149-6395 (Print) 1520-5754 (Online) Journal homepage: http://www.tandfonline.com/loi/lsst20

Transport phenomena in the electrodeionization

of cesium from AMP-PAN

Ch. Mahendra, P. M. Satya Sai, C. Anand Babu & K. K. Rajan

To cite this article: Ch. Mahendra, P. M. Satya Sai, C. Anand Babu & K. K. Rajan (2017)
Transport phenomena in the electrodeionization of cesium from AMP-PAN, Separation Science and
Technology, 52:8, 1468-1476, DOI: 10.1080/01496395.2017.1290109

To link to this article: http://dx.doi.org/10.1080/01496395.2017.1290109

Accepted author version posted online: 14

Feb 2017.
Published online: 14 Feb 2017.

Submit your article to this journal

Article views: 34

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lsst20

Download by: [Visvesvaraya Technological University - VTu] Date: 10 August 2017, At: 23:19
 SEPARATION SCIENCE AND TECHNOLOGY
2017, VOL. 52, NO. 8, 1468–1476
http://dx.doi.org/10.1080/01496395.2017.1290109

Transport phenomena in the electrodeionization of cesium from AMP-PAN

Ch. Mahendraa, P. M. Satya Saib, C. Anand Babuc, and K. K. Rajana
a
Fast Reactor Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, India; bWaste Immobilization Plant, Bhabha Atomic
Research Centre, Kalpakkam, India; cSri Venkateswara College of Engineering, Chennai, India

ABSTRACT ARTICLE HISTORY

Electrodeionization (EDI) of cesium from cesium-sorbed ammonium molybdophosphate-polyacry- Received 8 June 2016
lonitrile (AMP-PAN) was investigated by passing eluant through the packed bed of ion-exchange Accepted 30 January 2017
resin in an electrodialysis cell. The deionized cesium from the packed bed was recovered in KEYWORDS
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

catholyte by migration and in the eluant by convection. Recovery percentage of Cs by migration AMP-PAN; cesium;
increased while the recovery by convection decreased with increase in current density from 20 to convection; migration;
40 mA/cm2. Increased eluant concentration resulted in low migration percentage of cesium. recovery
Increased catholyte concentration had a negligible effect on total recovery. Apparent diffusion
coefficients evaluated using the Nernst–Plank relation increased with increase in current density
and catholyte concentration while a decreasing trend was observed with increase in eluant
concentration.

Introduction at the electrodes. Thus EDI reduces the usage of

Electrodeionization (EDI) process is a combined
technique of electrodialysis and ion exchange used
for the treatment of dilute heavy/transition metals.
It has proven to be a successful method for the
production of ultrapure water[1,2] since its first
application for the treatment of dilute radioactive
waste by Glueckauf.[3]
In conventional EDI, dilute metal solutions are
treated by injecting continuously through a packed
bed of ion-exchange resins inserted between two
electrode compartments, separated by ion-selective
membranes. Metal cations are sorbed by the resins,
and are transported to the cathode compartment
under the action of the applied electrical field. EDI
minimizes the amount of chemicals needed for the
regeneration of the resins as in conventional ion
exchange and minimizes the usage of ion exchange
resins.
EDI has been successfully applied for the treat-
ment of many industrial effluents containing metal
ions like Ni2+,[4–10] Co2+,[11–14] Cr6+,[15] Cs+,[16,17]
and Cu2+.[18–22] In these studies, the metal ions
sorbed by the ion-exchange resins are regenerated
by the protons generated at the bipolar interface
between the ion-exchange resins and membranes
and also by secondary water dissociation reactions
acids to regenerate the ion-exchange resins.
Ammonium molybdophosphate-polyacrylonitrile
(AMP-PAN) was reported to be having high affinity
for Cs from nuclear acidic waste.[23–26] Owing to its
high affinity for cesium, column regeneration of
AMP-PAN to obtain Cs in pure form is a multistep
process.
In our previous studies,[27,28] we have investi-
gated an electrodialysis ion exchange (EDIX) system
for recovery of Cs from AMP-PAN in limited opera-
tions. The regeneration of AMP-PAN was studied
by passing ammonium salt solution as anolyte from
which ammonium ions migrate toward the cathode
on application of an electric field. The ammonium
ions, while passing through the middle compart-
ment, replace the sorbed Cs+ on the resin and the
released Cs+ ions migrate to the cathode compart-
ment, where it is recovered and concentrated. In
these studies, various parameters affecting the pro-
cess were studied. Maximum recovery of 40%
cesium could be achieved for a loading capacity of
31.25 mg/g of resin, with a current density of 20
mA/cm2 and an eluant concentration of 10000 ppm
for an operating time of 30 h.
To reduce the operating time and increase the
percentage of recovered cesium, another approach
for regeneration or recovery of Cs from AMP-PAN

CONTACT Ch. Mahendra mahendra.ch6@gmail.com Fast Reactor Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102,
India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2017 Taylor & Francis
 SEPARATION SCIENCE AND TECHNOLOGY 1469

was investigated in the present study. The eluant is Table 3. Properties of AMI-7000.
passed directly through the packed bed instead of Technical specification AMI-7001S
passing as an anolyte, as was done in our previous Functionality Strong base anion exchange membrane
polymer structure Gel polystyrene cross linked with
studies. Two different streams are generated in the divinylbenzene
process, one by convection of eluant through the Functional group Quaternary ammonium
Standard thickness (mils) 20 ± 1
middle compartment and another by migration of Total exchange capacity 1.0 ± 0.1
cesium into the catholyte. The stream generated by (meq/g)
Water permeability(ml/hr/ft2) <20
migration will be very low in ammonium and easy @5psi
for processing. The effect of various parameters on Mullen burst test strength >80
(psi)
the total recovery as well as recovery by migration is Thermal stability (C°) 90
investigated. Chemical stability range (pH) 1–10

Experimental setup
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

Materials and methods

A three-compartment electrodialysis cell made of
All the chemicals used in the experiments were of Perspex sheet was employed for the recovery of
analytical grade. Cesium chloride (99.9%) and ammo- cesium from Cs+ sorbed AMP-PAN ion-exchange
nium sulphate (99.9%) were obtained from Sisco resin loaded in the central compartment of the ED
Research Laboratory Private Limited, Mumbai, and cell. A schematic of the experimental setup is shown
Qualigens Fine Chemicals Private Limited, Mumbai, in Fig. 1. The central compartment containing
respectively. Nitric acid (69–71%) was obtained from AMP-PAN is separated from the anode and cathode
Hi Pure Fine Chemical Industries, Chennai (India). compartments using anion- and cation-exchange
Platinum-coated titanium electrodes were used. Cs membranes, respectively. Before loading the central
concentration was analysed by Atomic Absorption compartment with 20 g of AMP-PAN, it was con-
Spectrophotometer (novAA 300, Analytik jena). verted to Cs+ form by equilibrating with 750 ppm
AMP-PAN ((NH4)3[PMo12O36] 3H2O) ion-exchange Cs in 4 N HNO3. The capacity of the resin was
resin was supplied by M/s. Thermax Ltd, Pune (India). found to be around 32
2 mg of Cs per gram of
Ion-exchange membranes (CMI-7000 and AMI-7000) resin. The central compartment was 5 mm in thick-
were from Membranes International, USA. The proper- ness and the anode and cathode compartments were
ties of AMP-PAN and ion-exchanger membranes used 8 mm in thickness. Platinum-coated titanium elec-
in the study are given in Tables 1, 2, and 3, respectively. trodes of dimensions 10 cm × 10 cm were used as
anode and cathode.
As the AMP-PAN should be regenerated only with
Table 1. Properties of AMP-PAN adsorbent resin. ammonium salts, ammonium sulphate was used as the
Trade name AMP-PAN eluant, passing once through the central compartment
Nature Cationic resin at 5 mL/min.
Particle size 0.4–0.5 mm
Shape Spherical Dilute nitric acid (0.1 N) of 1000 mL was used as
Pore diameter Macro porous
Bulk density 1.5 g/cm3
electrolytes, which were circulated in the anode and
AMP loaded on resin 65% cathode compartments at 200 mL/min using peristaltic
Moisture content 55%
pumps. The cell was operated for 10 h at different
current densities, different concentrations of eluant
and catholyte. Samples were collected from all the
Table 2. Properties of CMI-7000.
compartments at regular intervals of time and analysed
Technical specification CMI-7000S
for cesium concentration.
Functionality Strong acid cation exchange membrane
polymer structure Gel polystyrene cross linked with
divinylbenzene
Functional group Sulphonic acid
Standard thickness (mils) 18 ± 1
Total exchange capacity 1.3 ± 0.1 Calculations
(meq/g)
Water permeability(ml/hr/ft2) <10 Ion transport in ED cell
@5psi
Mullen burst test strength >80 The Nernst–Plank relationship describing the transport
(psi)
Thermal stability (C°) 90 of ions through a homogenous bed of ion-exchange
Chemical stability range (pH) 1–10 resin was used by several researchers for EDI.[4–10,18]
 1470 CH. MAHENDRA ET AL.
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

Figure 1. Schematic of the experimental setup.

i
dC (Rc), eluant (Re) and both membrane resistances
i
Ni ¼ D iu
þ zi C i
i gradφ þ vC (1)
dx (Rm) from the total resistance of the cell (Rcell):
where values with an overbar belong to the solid phase. The Rbed ¼ Rcell  Ra  Rc  Re  2Rm (5)
first term on the right-hand side describes the diffusion of where Rcell is the cell resistance, Ra is the anolyte
ion i with concentration C i and diffusion coefficientDi . The
resistance, Rc is the catholyte resistance, Rm is the
second term is for the migration of ion i with valence state membrane resistance and Re is the eluant resistance.
zi and mobility ui . The bed potential gradient is denoted by Similar to bed resistance, bed voltage drop also can
gradφ. The third term describes the movement of pore be calculated as
liquid within the ion-exchange particles.
It has been reported that diffusion and convection ΔEbed ¼ Ecell  ðEa þ jEc jÞ  Re Ie  2Em (6)
effects are negligible compared to migration in the where Ecell is the cell potential, Ea is the anode electrode
presence of sufficient electric field. The Nernst–Plank potential, Ec is the cathode electrode potential, Em is the
equation applied for ion transport in EDI cells reduces membrane potential and ReIe is the eluant ohmic drop
to the migration term. calculated from the conductivity of the solution.
N  iu
 Cs ¼ zi C i gradφ (2) The average gradient can be expressed as the
ratio of the ohmic drop in the bed, ΔEbed , over its
i , is defined
The mobility of the ions in the particles, u thickness, δbed .
by Eq. (3):
ΔEbed
 iF Δ; ¼ (7)
i ¼
u
D
(3) δbed
RT
ðEa þ jEc jÞ was found to be 1.8 V from the current–
Equation (2) becomes voltage measurements[28] of the electrodialysis cell. The
 resistance of the membranes was neglected compared
N  i Di;eff F gradφ
 Cs ¼ zi C (4) to the cell resistance.
RT

Ohmic resistance and potential gradient of the Results and discussion

packed bed
The electric resistance of the ion-exchange bed was
calculated using the following equation by subtract-
ing resistances offered by the anolyte (Ra), catholyte
Effect of current density on Cs migration
In electrochemical separation processes, current density
plays a vital role. In the present EDI process,
 SEPARATION SCIENCE AND TECHNOLOGY 1471

application of current across the cell results in the 2

20 mA/cm²
migration of anions and cations through the middle
30 mA/cm²

Cs recovery. (mmoles)
compartment towards the anode and cathode, respec- 1.6 40 mA/cm²
tively. The eluant containing 10 g/L NH4+ flowing in 60 mA/cm²
the middle compartment replaces the cesium ions on 1.2
the AMP-PAN resin when it comes in contact with the
resin. Some part of the total eluted cesium from the 0.8
resin migrates towards the cathode compartment under
0.4
the applied current and the remaining is convected by
the eluant flowing once through the middle compart- 0
ment. The recovery of cesium from cesium-sorbed 0 2 4 6 8 10
AMP-PAN was determined at different current densi- Time (h)
ties ranging from 20 to 60 mA/cm2. The amount of
Figure 2. Cs recovered by migration for different current den-
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

cesium recovered with time from the middle and cath-

ode compartments is shown in Figs. 2 and 3 for differ- sities (NH4+ =10000 ppm).
ent current densities. From Fig. 2 it can be seen that the
migration of cesium to the cathode compartment
4
increased with increase in the current density from 20 20 mA/cm²
to 60 mA/cm2, due to increased ion movement. The 30 mA/cm²

Cs recovery. (mmoles)
40 mA/cm²
migrated cesium was about 0.6 millimoles for 20 mA/ 3
60 mA/cm²
cm2 and it increased to more than 1.6 millimoles for 60
mA/cm2 in 10 h of operation. From Fig. 3 it can be seen
that the total cesium convected by the eluant through 2
the middle compartment decreased with increase in the
current density. Increase in migration rate at higher 1
current densities decreased the convection of cesium
ions by the eluant. After 10 h, both cesium migration
and convection were found to be negligible. 0
As the middle compartment was separated from the 0 2 4 6 8 10
anode compartment with an anion-exchange membrane, Time (h)
which restricts the diffusion of cations towards the anode, Figure 3. Cs recovered by convection for different current den-
negligible amounts of cesium were found in the anode sities (NH4+ =10000 ppm).
compartment. The total amount of cesium recovered
from all the compartments is shown in Fig. 4. With increas-
ing current density from 20 to 30 mA/cm2 the total recov- 70
61.41
65.07
59.82 58.21
ery of cesium increased from 61.41% to 64.07% and further 60
50.08
47
increase in current density from 40 to 60 mA/cm2 resulted 50
% Recovery

38.41
in decrease of recovery. Although migration of cesium 40 32.49
26.72
increased from 13.04% to 32.49% with increase in current 30
21.41
18.07
density, total recovery decreased. In electromembrane pro- 20 13.04

cesses, water splitting results in H+ and OH− formation, at 10

the bipolar interface of the cation-exchange resin and the 0

20 30 40 60
anion ion-exchange membrane. Water splitting is more Current density (mA/cm2)
intensive at the anion-exchange membrane.[29] The gen- % Total recovered % Middle % Cathode
eration of H+ at the anion ion-exchange membrane
increased the eluant conductivity after 1 h of operation. Figure 4. Total percentage of cesium recovered from all com-
partments for different current densities (NH4+ =10000 ppm).
Since AMP-PAN is highly selective for Cs+ in acidic med-
ium and regeneration of the resin is possible only in alka-
line medium, increase in H+ ions in the eluant might have the bed conductivity and consequently the potential gradi-
reduced the desorption of Cs from the resin. This resulted ent over the bed decreased at higher current densities. This
in decrease in total recovery at higher current densities. is also evident from the increase in voltage drop across the
The increased presence of H+ ions in the eluant increased cell with increase in current densities (Fig. 5). At any given
 1472 CH. MAHENDRA ET AL.

14 8
12 20mA/cm²
30mA/cm² 20 mA/cm²
Voltage drop (volts)

10 40mA/cm² 6 30 mA/cm²

DCs x 10 -9 (m2/s)
60mA/cm²
8 40 mA/cm²
60 mA/cm²
6 4

4
2
2

0
0 2 4 6 8 10 12 0
Time (h) 0 2 4 6 8 10
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

Time (h)
Figure 5. Variation of voltage drop for different current densities
(NH4+ =10000 ppm). Figure 6. Variation of diffusion coefficient of Cs for different
current densities.

current density, the cell voltage decreased slowly with
increase in time of operation, the drop being more pro-
nounced at higher current densities as shown in Fig. 5.
The migration of cesium as presented in Fig. 2 can be
analysed by the empirical model of resin regeneration pro-
posed by P.B. Spoor et al.[6] for electromigration of nickel.
The model assumes first-order kinetics with respect to
metal ion concentration in the resin and predicts the flux
of the metal ion in terms of the maximum amount of ions
extracted from the resin, which can be determined experi-
mentally. Using this model, the experimental curves (Fig. 2)
were fitted to the following exponential equation to predict
nCs, the amount of cesium present in the catholyte:

might have reduced with time. In the initial hours of
nCs ¼ nCs;max 1  ekm t (8)
where nCs;max is the maximum amount of Cs present in
the catholyte at the end of the experiment and km is the
mass transfer coefficient, a model parameter.
The cesium flux from the bed can be calculated
using the derivative of Eq. (8):
1 dnCs km nCs;max km t
NCs ¼ ¼ e
Abed dt Abed
The apparent diffusion coefficient of cesium in the bed,
DCs; can be found out using the migration term of the
Nernst–Planck equation:[6]
 Cs F
D The recovery of cesium from AMP-PAN in the electro-
 Cs
NCs ¼ zCs C
RT
 Cs was calculated by Eqs. (9) and
The average value of D
(10) as follows:
km t
 Cs ¼ ncs;max km e
where subscript t refers to time t. The effective diffu-
sion coefficient, Deff (m2/s), was calculated at time t = 0.
The diffusion coefficient for the migration of cesium
from AMP-PAN to catholyte was calculated for the 10 h
of operation and the variation of diffusion coefficient is
shown in Fig. 6. The diffusion coefficient continuously
decreased with time except in the first 1 h, during which
period the system attains equilibrium. Continuous applica-
tion of current results in the deionization of the ion-
exchange resin, which further decreases the ionic content
of the exchanger. As diffusion coefficients are functions of
Cs concentration of the resin, which decreases continuously
with deionization of the exchanger, diffusion coefficient
operation (up to 5 h), diffusion coefficients were observed
to increase with increase in the applied current density and
 cs reached a
for the later hours of operation (after 5 h), D
constant value for all the current densities studied. In the
region of 6–10 h, D  cs is almost independent of current
density and decreased with time of operation. The effective
diffusion coefficients determined at time t = 0 increased
with increase in current density up to 40 mA/cm2 and then
(9)
decreased with further increase in current density as seen in
Table 4.
Effect of eluant concentration
gradφ (10)
dialysis setup was investigated for different eluant con-
centrations at a constant current density of 40 mA/cm2.
The concentration of eluant passing through the ion-
exchange resin in the middle compartment was varied
from 1 to 25 g/L. On application of current, the migra-
D X 
RT
 (11)
Abed  þ tion of cesium ions towards the cathode is shown in
zCs F Cs  Ñφ
t Fig. 7 for different eluant concentrations. Cs

Table 4. Effective diffusion coefficient of Cs migration for dif-
ferent current densities.
Current density nmax km × 10−5 grad∅
(mA/cm2) (moles) (s−1) (V/m)
20 0.71 6.313
30 1 8.145
40 1.16 8.443 1000
60 1.7 8.547 1680
1.2
1000 ppm
1 5000 ppm
Cs recovery (mmoles)
10000 ppm
0.8 25000 ppm
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017
0.6
0.4
0.2
0
0 2 4 6
Time (h)
Figure 7. Cs recovered by migration for different eluant con-
centrations (current density = 20 mA/cm2).
concentration in catholyte slowly increased with time
when 1, 5 and 10 g/L solutions were used. For 25 g/L
solution, negligible migration was observed after 4 h.
The total Cs recovered by migration decreased from
1.02 to 0.54 mmoles in 10 h of operation, when the
eluant concentration increased from 1 to 25 g/L. The
migration of cesium from the central compartment to
the cathode compartment depends on the applied cur-
rent and the available membrane area. When high
eluant concentrations were used to recover the sorbed
Cs from AMP-PAN, high concentration gradients led
to more elution of Cs ions from the ion-exchange resin.
Since constant current is applied, out of these only a
few ions were able to migrate and the remaining ions
would be convected by the eluant flowing through the
middle compartment. For a low concentration of eluant
(1 g/L), the eluted ions were also low in quantity and
most of them migrated due to the applied current.
The “Porous-Plug” model[12–14,30] explains the pas-
sage of electric current through ion-exchange media in
terms of three different paths. The first path is alter-
nating layers of ion-exchange resin and interstitial solu-
tion; the second is the bridge connecting the ion-
exchange resin beads, which are in contact with each
other; and the third is the channel through the inter-
stitial solution. At low eluant concentrations, the con-
ductivity of the solution is low and the conductivity of
the solid is high. Hence, the preferred path for electric
SEPARATION SCIENCE AND TECHNOLOGY 1473
current is through the ion-exchange resin and across
the cation-exchange membrane into the catholyte. Thus
Deff × 10−9 it results in high migration and low convection. As the
(m2/s)
600 1.002
concentration of the eluant increases, the roles are
800 1.135 reversed and convection is preferred to migration.
1.407 Also, it can be seen that increased eluant concentration
1.262
increases the overall Cs recovery, as expected.
The amount of cesium recovered by convection
from the middle compartment increased with increase
in the eluant concentration from 5 to 25 g/L as shown
in Fig. 8. It reached equilibrium within 5 h and after
that no more cesium was convected from the middle
compartment. As observed from Fig. 8, around 2.5
millimoles of cesium were recovered from the middle
compartment outlet (by convection) in the first 1 h and
totally 3.5 millimoles were recovered at the end of 10 h
when 25 g/L eluant was used for the recovery of
cesium. A negligible amount of cesium was observed
in the outlet of the central compartment when 1 g/L
8 10 NH4+was passed through the ion-exchange resin, as
most of the Cs was recovered by migration only. The
overall percentage recovery of cesium from different
compartments of the electrodialysis setup is shown in
Fig. 9. The total recovery increased from 21.77% to
77.58% with increase in the eluant concentration from
1 to 25 g/L. For 1 g/L, most of the total recovery is by
migration and for 25 g/L it was by convection.
Increasing the eluant solution concentration enhanced
the convection term in the Nernst–Plank equation, thus
reducing the migration of Cs ions to the cathode
compartment.
The curves showing the migration of cesium were fitted
to the exponential Eq. (8) to estimate the diffusion coeffi-
cients. The migration diffusion coefficient was found to be
the least for 1 g/L (Table 5) in spite of its high % migration,
compared to the other concentrations, as shown in Fig. 9.
5 1000 ppm
Cs reccovery. (mmoles)
5000 ppm
4 10000 ppm
25000 ppm
3
2
1
0
0 5 10
Time (h)
Figure 8. Cs recovered by convection for different eluant con-
centrations (current density =20 mA/cm2).
 1474 CH. MAHENDRA ET AL.

77.58 Effect of catholyte concentration

80 71.55 67.1
70 61.38 Dilute acids or salts are used as electrolytes in electro-
58.32
60 dialysis systems. In the present investigation of ED for
50 44.46 recovery of Cs from AMP-PAN, HNO3 was used as
40 both anolyte and catholyte. Since Cs was recovered in
30 21.77 21.23 16.91
the catholyte, the effect of concentration of catholyte is
13.23
20 10.48 studied by varying the concentration from 0.1 to 1 N,
10 0.54 keeping the other parameters constant. The amount of
0 Cs recovered by migration for different catholyte con-
% Total % Migration % Convection
centrations is shown in Fig. 11. The rate of migration of
1000 ppm 5000 ppm 10000 ppm 25000 ppm
Cs marginally increased with increase in concentration
Figure 9. Total percentage of Cs recovered for different eluant of catholyte. At the end of 10 h, almost 0.7 millimoles
concentrations (current density = 20 mA/cm2). of Cs were recovered by migration for all the catholyte
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017

concentrations studied.
Table 5. Effective diffusion coefficient of Cs migration for dif- The Cs convected from the middle compartment by
ferent eluant concentrations. the eluant was found to increase slightly with increase in
grad∅ Deff × 10−9 catholyte concentration. The total recovery from all the
Eluant conc. (mg/L) nmax (moles) km × 10−5 (s−1) (V/m) (m2/s) compartments increased from 66.28% to 72.44% with
1000 1.31 4.067 2320 0.312
5000 0.89 6.944 840 0.973 increase in catholyte concentration from 0.1 to 1 N
10000 0.74 6.613 680 0.965 (Fig. 12). It was observed that as the catholyte concentra-
25000 0.52 13.888 660 1.443
tion was increased from 0.1 to 1 N, the initial cell voltage
decreased from 6 to 5.6 V, which is due to increase in the
Figure 10 shows the cell voltage as a function of time for conductivity of catholyte. The decrease in cell voltage
different eluant concentrations. A high voltage drop in case might have reduced the secondary reactions such as
of 1 g/L eluant resulted in low diffusion coefficient. For water splitting at the bipolar interface and water dissocia-
other concentrations the diffusion coefficient was found to tion at the electrode surface. This would have resulted in
decrease with time. the increase of Cs recovery, when catholyte concentration
The variation of diffusion coefficient for different eluant is increased. The diffusion coefficients for Cs migration
concentrations was found using Eq. (11) and the effective for different catholyte concentrations were found to be
diffusion coefficients (at t = 0 h) were determined and increasing with increasing catholyte concentration, as
tabulated in Table 4. The effective diffusion coefficients seen in Table 6. The increased acidic concentration of
increased with increase in the eluant concentration from catholyte would increase the conductivity of the catholyte,
1 to 25 g/L as seen from Table 5. which resulted in high diffusion migration coefficients.

21
1
18 1N
Cs recovery (mmoles)

0.8 0.5N
15 0.1N
Cell voltage (V)

0.6
12 1000 ppm
5000 ppm
9 10000 ppm
0.4
25000 ppm
6 0.2
3
0
0 0 2 4 6 8 10
0 2 4 6 8 10 Time (h)
Time (h)
Figure 11. Recovery of Cs by migration for different catholyte
Figure 10. Cell voltage for different eluant concentrations (cur- concentrations (current density =20 mA/cm2, NH4+ =10000
rent density =20 mA/cm2). ppm).

100
90
80
72.44
70 66.58 69.12
58.62
% Recovery
60 53.56 55.25
50
40
30
20
10
0
% Total Convection
Figure 12. Percentage recovery of Cs for different catholyte
concentrations (current density =20 mA/cm2, NH4+ =10000
ppm).
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017
Table 6. Effective diffusion coefficients of Cs migration for
different catholyte concentrations.
Catholyte conc. (N) nmax (moles) km × 10−5 (s−1)
0.1 2.61 11.6
0.5 2.9 12.7
1 3.41 13.8
Conclusions
Investigations were carried out for the recovery of cesium
from cesium-sorbed AMP-PAN using a hybrid electrodia-
lysis ion-exchange system. The eluant was passed through a
bed of AMP-PAN loaded in the central compartment of an
electrodialysis cell. Cs recovery from the system occurred
in two ways, by migration into the cathode compartment
under the influence of applied voltage and by convection of
the eluant through the central compartment. The stream
collected from the central compartment contains a high
concentration of ammonium ions, used for regeneration of
the resin. Effect of the operating parameters on the recov-
ery of cesium by both the ways is experimentally deter-
mined and using the Nernst–Plank equation, diffusivities
of cesium were estimated. Since diffusion coefficient is a
function of concentration gradients in the bed, it decreased
with time due to the deionization of Cs from the packed
bed for all the parameters studied.
Total recovery of cesium increased with increase in
current density from 20 to 30 mA/cm2, but decreased
when the current density is increased to 40 and 60 mA/
cm2, due to water splitting reactions. The total recovery
increased with eluant concentration, due to better elu-
tion, whereas increase in the catholyte concentration
did not have a significant effect on the recovery.
Recovery by convection decreased with the increase
in current density, whereas it increased significantly
with eluant concentration and slightly with catholyte
concentration. Recovery by migration, which is the
desirable phenomenon, increased with current density
and decreased with increase in eluant concentration,
SEPARATION SCIENCE AND TECHNOLOGY 1475
whereas increase in the catholyte concentration did
0.1N 0.5N 1N
not have a significant effect. The maximum recovery
of cesium obtained by migration in the present work is
32.49% for 10 h of operation for a current density of 60
mA/cm2, eluant concentration of 10 g/L of NH4+, and
catholyte of 0.1 N HNO3. This corresponds to a total
13.14 14.21 14.47 recovery of 58.21% and hence more than half of the
total recovery is by migration, which results in a stream
% Migration with a very low concentration of ammonia.
References
[1] Ganzi, G.C.; Wood, J.H.; Griffin, C.S. (1992) Water
purification and recycling using the CDI process.
Environmental Progress, 11: 49–53.
[2] Wang, J.Y.; Wang, S.C.; Jin, M.R. (2000) A study of the
electrodeionization process-high-purity water produc-
grad∅ Deff × 10−9
(V/m) (m2/s) tion with a RO/EDI system. Desalination, 132: 349–352.
680 6.43 [3] Glueckauf, E. (1959) Electrodeionization through a
640 8.31 packed bed. British Chemical Engineering, 4: 646–651.
600 11.3 [4] Spoor, P.B.; Koene, L.; Veen, W.R.T.; Janssen, L.J.J.
(2002) Continuous deionization of a dilute nickel solu-
tion. Chemical Engineering Journal, 85: 127–135.
[5] Spoor, P.B.; Veen, W.R.T.; Janssen, L.J.J. (2001)
Electrodeionization 1: Migration of nickel ions
absorbed in a rigid, macroporous cation-exchange
resin. Journal of Applied Electrochemistry, 31: 523–530.
[6] Spoor, P.B.; Veen, W.R.T.; Janssen, L.J.J. (2001)
Electrodeionization 2: The migration of nickel ions
absorbed in a flexible ion-exchange resin. Journal of
Applied Electrochemistry, 31: 1071–1077.
[7] Spoor, P.B.; Koene, L.; Veen, W.R.T.; Janssen, L.J.J.
(2002) Electrodeionization 3: The removal of nickel
ions from dilute solutions. Journal of Applied
Electrochemistry, 32: 1–10.
[8] Spoor, P.B.; Veen, W.R.T.; Janssen, L.J.J. (2002) poten-
tial and concentration gradients in a hybrid ion-
exchange/electrodialysis cell. Journal of Applied
Electrochemistry, 32: 369–377.
[9] Dzyazko, Y.S. (2006) Purification of a diluted solution
containing nickel using electrodeionization.
Desalination, 198: 47–55.
[10] Dzyazko, Y.S.; Ponomaryova, L.N.; Rozhdestvenskaya,
L.M.; Vasilyuk, S.L.; Belyakov, V.N. (2014)
Electrodeionization of low-concentrated multicompo-
nent Ni2+containing solutions using organic-inorganic
ion-exchanger. Desalination, 342: 43–51.
[11] Yeon, K.H.; Song, J.H.; Moon, S.H. (2004) A study on stack
configuration of continuous electrodeionization for
removal of heavy metal ions from the primary coolant of
a nuclear power plant. Water Research, 38: 1911–1921.
[12] Yeon, K.H.; Moon, S.H. (2003) A study on removal of
cobalt from a primary coolant by continuous electro-
deionization with various spacers. Separation Science
and Technology, 38: 2347–2371.
[13] Song, J.H.; Yeon, K.H.; Moon, S.H. (2004) Transport
characteristics of Co2+ through an ion exchange textiles
in a continous electrodeionization (CEDI) system
unsdr electro-regenreation. Separation Science and
Technology, 39: 3601–3619.
 1476 CH. MAHENDRA ET AL.
[14] Yeon, K.H.; Song, J.H.; Rengaraj, S.; Moon, S.H. (2003)
Electrochemical characterization of ion –exchange
resin beds and removal of cobalt by electrodeionization
for high purity water production. Separation Science
and Technology, 38: 443–462.
[15] Alvarado, L.; Ramírez, A.; Rodríguez-Torres, I. (2009) Cr
(VI) removal by continuous electrodeionization: Study of
its basic technologies. Desalination, 249: 423–428.
[16] Zhang, Y.; Wang, L.; Xuan, S.; Lin, X.; Luo, X. (2014)
Variable effects on electrodeionization for removal of
Cs+ ions from simulated wastewater. Desalination, 344:
212–218.
[17] Kotvitskyy, A.G.; Maltseva, T.V.; Belyakov, V.N. (2005)
Selective removal of Cs+ ions by means of electro-deio-
nisation. Separation Science and Technology, 41: 329–334.
[18] Mahmoud, A.; Muhr, L.; Vasiluk, S.; Aleynikoff, A.;
Downloaded by [Visvesvaraya Technological University - VTu] at 23:19 10 August 2017
Lapicque, F. (2003) Investigation of transport phenom-
enon in a hybrid ion exchange-electrodialysis system
for the removal of copper ions. Journal of Applied
Electrochemistry, 33: 875–884.
[19] Mahmoud, A.; Muhr, L.; Vasiluk, S.; Grevillot, G.;
Valentin, G.; Lapicque, F. (2006) Ohmic drops in the
ion-exchange bed of cationic electrodeionisation cells.
Journal of Applied Electrochemistry, 36: 277–285.
[20] Mahmoud, A.; Hoadley, A.F.A. (2012) An evaluation of
a hybrid ion exchange electrodialysis process in the
recovery of heavy metals from simulated dilute indus-
trial waste water. Water Research, 46: 3364–3376.
[21] Arar, O.; Yuksel, U.; Kabay, N.; Yuksel, M. (2011)
Removal of Cu2+ by a micro-flow electrodeionization
system. Desalination, 277: 296–300.
[22] Alvarado, L.; Chen, A. (2014) Electrodeionization:
Principles, strategies and applications. Electrochimica
Acta, 132: 583–597.
[23] Carla J. Miller; Arlin L. Olson; Calvin K. Johnson (1997)
Cesium absorption from acidic solutions using ammonium
molybdophosphate on a polyacrylonitrile support (AMP-
PAN). Separation Science and Technology, 31: 37–50.
[24] Tood, T.A.; Mann, N.R.; Tranter, T.J.; Sebesta, F.; John,
J.; Motl, A. (2002) Cesium sorption from concentrated
acidic tank wastes using ammonium molybdopho-
sphate–polyacrylonitrile composite sorbent. Journal of
Radioanalytical and Nuclear Chemistry, 254: 47–52.
[25] Younjin, P.; Lee, Y.C.; Shin, W.S.; Choi, S.J. (2010)
Removal of cobalt, strontium and cesium from radio-
active laundry wastewater by ammonium molybdopho-
sphate–polyacrylonitrile (AMP–PAN). Chemical
Engineering Journal, 162 (2): 685–695.
[26] Tranter, T.J.; Herbst, R.S.; Todd, T.A.; Olson, A.L.;
Eldredge, H.B. (2003) Application of a second order
kinetic model for the preliminary design of an adsorp-
tion bed system using ammonium molybdophosphate–
polyacrylonitrile for the removal of 137Cs from acidic
nuclear waste solutions. Advances in Environmental
Research, 7: 913–923.
[27] Mahendra, Ch.; Bera, S.; AnandBabu, C.; Rajan, K.K.
(2013) Separation of cesium by electro dialysis ion
exchange using AMP-PAN. Separation Science and
Technology, 48: 2473–2478.
[28] Mahendra, Ch.; Satya Sai, P.M.; Anand Babu, C. (2014)
Current-voltage characteristics in a hybrid
Electrodialysis- Ion exchange system for the recovery
of cesium ions from ammonium molybdophosphate-
polyacrylonitrile. Desalination, 353: 8–14.
[29] Nikonenko, V.V.; Kovalenko, A.V.; Urtenov, M.K.;
Pismenskaya, N.D.; Han, J.; Sistat, P.; Pourcelly, G.
(2014) Desalination at overlimiting currents: State of
the art and perspectives. Desalination, 342: 85–106.
[30] Spiegler, K.S.; Yoest, R.L.; Wyllie, M.R.J. (1956) Electrical
potentials acrossporous plugs and membranes, ion-
exchange resin-solution system. Discussions of the
Faraday Society, 21: 174–183.