Desalination 363 (2015) 4450

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Desalination
journal homepage: www.elsevier.com/locate/desal

A combined ion exchangenanoltration process for water desalination:

I. sulphatechloride ion-exchange in saline solutions
Nidal Hilal a,b,, Victor Kochkodan b, Hasan Al Abdulgader c, Stephen Mandale a, Saad A. Al-Jlil d
a

Centre for Water Advanced Technologies and Environmental Research (CWATER), College of Engineering, Swansea University, Swansea SA2 8PP, United Kingdom
Qatar Environment and Energy Research Institute (QEERI), Dopha, Qatar
College of Engineering, King Faisal University, Al Ahsa, Saudi Arabia
d
King Adbul Aziz City for Science and Technology, Saudi Arabia
b
c

H I G H L I G H T S

Sulphate/chloride ion exchange in saline water has been studied both on laboratory and pilot scales.
Sulphatechloride exchange depends on the feed salt concentration and the nature of the functional group of the resin.
Exhausted anion exchange resins were successfully regenerated using 0.2 M Na2SO4 solution.
The osmotic pressure of sea water was signicantly reduced after SO4/Cl ion exchange.

a r t i c l e

i n f o

Article history:
Received 14 September 2014
Received in revised form 16 November 2014
Accepted 18 November 2014
Available online 21 November 2014
Keywords:
Desalination
Anion exchange resin
Sulphate/chloride exchange
Osmotic pressure

a b s t r a c t
Removal of chloride ions from saline water with seven different ion-exchange (IX) resins in sulphate form has
been studied both on laboratory and pilot scales. It was found that sulphatechloride exchange is very fast in
aqueous solutions and that the feed salt concentration and the nature of the functional group of the resin play
an important role in this process. It was shown that the chloride/sulphate separation factor depends on salt
content in feed water and the higher the substitution of hydrogen atoms in amine functional group of anion
exchange resin the higher chloride over sulphate selectivity. Exhausted IX resins were successfully regenerated
using 0.2 M Na2SO4 solution and multiple regeneration/saturation cycles proved that this did not affect the resin's
performance on chloride ion removal. It was shown that the osmotic pressure of sea water was signicantly
reduced after SO4/Cl ion exchange. Due to the drop of osmotic pressure lower energy consuming nanoltration
membranes compared with reverse osmosis membranes might be used for salty water desalination after IX
treatment.
2014 Elsevier B.V. All rights reserved.

1. Introduction
A sharp growth in the worlds' population coupled with urbanization
has resulted in a rapidly increased demand for fresh water [1]. A lot of
efforts are focused on suitable methods to obtain freshwater by sea
water or brackish water desalination and various desalination technologies, including thermal multi-stage ash distillation and reverse osmosis, which have been increasingly used to enhance a fresh water supply
around the world [2]. However, the cost-effectiveness of these technologies is still hampered by high energy consumption [3]. Therefore
the development of a technology capable of producing fresh water by
Corresponding author at: Centre for Water Advanced Technologies and Environmental
Research (CWATER), College of Engineering, Swansea University, Swansea SA2 8PP, United
Kingdom.
E-mail address: n.hilal@swansea.ac.uk (N. Hilal).

http://dx.doi.org/10.1016/j.desal.2014.11.016
0011-9164/ 2014 Elsevier B.V. All rights reserved.

desalting brackish and/or seawater at the lowest possible cost is of

crucial importance.
In this work we have studied the sulphatechloride exchange in
saline solutions. If monovalent chloride ions of salty water convert
into divalent sulphate ions using ion-exchange (IX), that would reduce
the osmotic pressure of the treated feed and in turn would essentially
reduce the energy required for further membrane desalination, because
nanoltration (NF) membranes, which efciently reject the sulphate
ions and operate at signicantly lower transmembrane pressures
compared with reverse osmosis membranes, can be used for water
desalination [4].
Many researchers have tested IX resins for the removal of chloride
ions, but in exchange of anions other than sulphate [58]. For example,
the removal of chloride, nitrate and sulphate ions from aqueous solutions with a macroporous resin Amberlite IRN 9766 in hydroxyl form was
studied by Dron and Dodi [5]. It was shown that Langmuir adsorption

N. Hilal et al. / Desalination 363 (2015) 4450

isotherms provide a good estimation of the sorption capacity on the

contrary to Freundlich and DubininRadushkevitch models.
The strongly basic ion exchanger Amberlite IRA-420 resin in OH form
has been used for chloride ion removal from chloride-polyethylenimine
solution at different temperatures to evaluate the possibility to apply the
IX technology to convert the polyethylenimine occulant in chloride
form into an adhesive product for printing applications [6]. The equilibrium isotherms of chloride ions in aqueous solution on Amberlite IRA420 have been obtained and the kinetic studies indicated that the chloride ions are slowly removed when the polyethylenimine is in solution
due to the ionic pair formation.
The layered double hydroxides such ZnAlNO3 containing nitrate as
the interlayer anion has been studied as an anion exchanger material to
remove chloride ions from aqueous solution [9]. The effect of dosage of
IX material, solution pH and temperature on the removal efciency have
been investigated. It was found that the inuence of solution pH was not
very signicant in the range 5.08.0, and the rate of anion-exchange increases upon raising the temperature of aqueous solution.
Chloridesulphate exchange for sulphate removal from the sea
water fed to an evaporation plant by means of anion exchange resins
has been studied by Boari et al. [10,11]. It was shown that the selectivity
for the bivalent ion depends strongly on the basicity of the resin and the
afnity of every resin for the sulphate ion increases with the dilution of
the aqueous phase and with the equilibrium temperature. The obtained
results showed that in heterovalent exchange processes an important
role is played by the phenomena connected with the electrostatic
interactions.
Direct sulphatechloride ion exchange for removal of chloride ions
from water has been studied by few investigators. Sarkar and SenGupta
[12] illustrated that sulphate/chloride selectivity depends on degree of
the substitution of hydrogen atom in the amine functional group of
the anion exchange resin. For most of their experiments Purolite A850
anion-exchange resin of a gel type with quaternary ammonium functional group was used.
The aim of this work is to use various commercial anion exchange
resins and test their performance in exchange with chloride ions at
different water salinities. The IX studies were carried out in batch and
continuous modes to investigate the sulphatechloride exchange equilibrium, effect of resin dosage and operating conditions on the IX process and on the shape of breakthrough curves of the resins. For the
rst time we have used two mutually interlinked routes to study sulphatechloride exchange in aqueous solutions, which included both
the experimental studies on a laboratory scale and further scaling up
and optimization of a pilot scale IX system.

2. Materials and methods

45

It should be mentioned that Purolite A500TLSO4, Purolite A400TLSO4

and Ambersep 900SO4 resins are available in SO2
form, while Purolite
4
A850 resin was shipped in Cl form and it was transferred to SO2
4 form
by treatment with 2 M H2SO4.
Purolite A109, Purolite A149S and Purolite A111 resins were provided in free base form and according to a procedure suggested by the
manufacture the resins were treated with 5 wt.%. Na2SO4 and washed
with distilled water to convert the resin from free base to sulphate form.
Purolite A500TLSO4, Purolite A850, Purolite A109, Purolite A149S,
Purolite A111 and Ambersep 900SO4 are macroporous resins, while
Purolite A400TLSO4 is in a gel form.
2.2. Batch studies with IX resins
The batch studies with IX resins were performed using NaCl
solutions of various concentrations, considering that sodium chloride
(i.e. Na+ and Cl ions) is the primary constituent of brackish water or
sea water. NaCl stock solution (32.0 g/L) was prepared by weighing
and dissolving an appropriate amount of NaCl salt in Millipore-Q
water. The testing solutions were prepared by an appropriate diluting
of the stock NaCl solution. The pH values of the solutions were about
7, as was measured with a JenWay 3540 pH metre.
For batch IX studies, weighted amounts of air-dried sulphate-forms
of the resins were added in NaCl solutions with concentrations of
30550 meq/L. Then the samples were agitated with a shaker (Innova
44, New Brunswick Scientic) at a constant speed of 150 rpm for
0.124.0 h at room temperature. With time, 0.51.0 mL aliquots were
periodically collected and analyzed to determine contents of Cl and
SO2
ions in the probes using an ion chromatograph (Dionex IC900)
4
with AS14A (4 mm) anion-exchange column.
The removal efciency of Cl ions with IX resins was calculated as:
Removal efficiency c0 c=c0   100%;
where c0 and c are chloride concentrations (mg/L) in the solution before
and after IX treatment.
2.3. Column studies with IX resins
Column IX tests were performed to elucidate a shape of breakthrough curves of IX resins and to evaluate the effect of operating

conditions for optimization of SO2

4 /Cl exchange process. A glass chromatographic type column with an internal diameter of 2.0 cm and the
column aspect ratio (height: width) of 20:1 was used for these
experiments. The feed solution was delivered to the column using a
peristaltic pump (Watson-Marlow 101 U/R) at a ow rate of 0.12
0.45 mL/s. From the outlet of the column, the efuent fractions of
20 mL each were collected and analyzed with IC.

2.1. IX resins
2.4. Pilot scale IX system
Seven IX resins, Purolite A500TLSO4, Purolite A400TLSO4, Purolite
A850, Purolite A109, Purolite A149S, Purolite A111 and Ambersep
900SO4 which contain quaternary, tertiary, secondary and primary
aminogroups in the polymer matrix have been used in this work. The
characteristics of the resins are presented in Table 1.

To progress the experimental work to pilot scale trials a pilot scale IX

system has been designed and built. The process and instrumentation
diagram (P&ID) of the designed IX system is presented in Fig. 1. The system is constructed from polyvinylchloride pipe work and two 100 L

Table 1
Physical and chemical characteristics of IX resins used in the study.
IX resin

Polymer matrix

Functional group

Shipped form

Resin particle size

Purolite A500TLSO4
Ambersep 900SO4
Purolite A400TLSO4
Purolite A109
Purolite A149S
Purolite A111
Purolite A850

Polyacrylic crosslinked with divinylbenzene

Polystyrene crosslinked with divinylbenzene
Polystyrene crosslinked with divinylbenzene
Polystrene crosslinked with divinylbenzene
Polystrene crosslinked with divinylbenzene
Polystrene crosslinked with divinylbenzene
Polyacrylic crosslinked with divinylbenzene

Quaternary ammonium
Trimethyl ammonium
Quaternary ammonium
Primary amine
Secondary amine
Tertiary amine
Quaternary ammonium

SO2
4
SO2
4
SO2
4
Free base
Free base
Free base
Cl

425850 m
3001200 m
425850 m
4251000 m
4251200 m
3001200 m
3001200 m

46

N. Hilal et al. / Desalination 363 (2015) 4450

Fig. 1. P&ID of a pilot IX system.

poly-glass IX columns. Three large capacity tanks (1000 L) are used to

store and supply the feed, regeneration and rinse solutions required
for IX operation. A speed controllable pump P3 and xed speed
pumps P4 and P5 have been used for delivering the solutions to the IX
columns. All of the equipment is supported on a stainless steel frame
mounted on castors. Performance monitoring is facilitated by inclusion
of a ow metre and a pressure gauge linked back to a central display on
the control panel.
The designed pilot IX rig for water desalination have been used to
study the effect of ow rate through the IX column, the resins loading
and feed salinity on the efciency of sulphate/chloride exchange
process.
Osmotic pressure of saline water before and after IX treatment
has been measured with Gonotec Osmomat 030 osmometer (Gonotec
GmbH, Germany).

The very fast kinetics of sulphatechloride IX process suggests that

in aqueous solutions of high salinity IX resistances from diffusion of
the counterions both through a liquid lm surrounding the IX resin in
solution (Nernst lm with no convection) and inside IX resins are insignicant. This assumption is conrmed by the data presented in Fig. 3. As
can be seen from this gure, the prolonging of IX treatment from 1 h to
42 h did not practically lead to increase the removal of chloride ions
from water.
The dependencies of dosage of Ambersep900SO4, Purolite A500TLSO4
and Purolite A500TLSO4 resins on concentration of Cl and SO2
4 ions in
feed water at IX treatment of NaCl solutions over a concentration range
of 1.032.0 g/L are presented in Fig. 4. As expected, a content of chloride
ions in the feed solutions decreases with an increase of the resin dosage.
This is attributed to higher IX capacity with an increase of the resin loading. Addition of more resin beads will increase the total number of available exchange sites and subsequently, the capacity to take in more
7000

3.1. Batch studies on sulphatechloride exchange with IX resins

6000

A set of experiments were conducted to determine the time required

for IX resin in sulphate form to reach SO24 /Cl equilibrium in saline
water in accordance with the following reaction:
(RN+)2SO42 + 2NaCl 2(RN+)Cl + SO42 + 2Na+,
is a polymer matrix of IX resin in sulphate form.
where (RN+)2SO2
4
It was found that the chloridesulphate exchange proceeds very fast
in aqueous solutions of high salinity. For example, as seen in Fig. 2, only
510 min is needed to reach SO2/
Cl equilibrium in 10 g/L NaCl
4
solution. The chloride removal efciency after equilibrium is in the
range of 54 59% for all three resins. Purolite A500TLSO4 managed to
remove 59% of chloride ions in the solution, while Purolite A400TLSO4
and Ambersep900SO4 removed 56% and 54% respectively.

Cl- Concentraon, mg/L

3. Results and discussion

Purolite A500TLSO4

5000

Purolite A400TLSO4

4000

Ambersep 900SO4

3000
2000
1000
0
0

100

200

300

400

500

Time, min
Fig. 2. Concentration of chloride ions over time during IX treatment of 10.0 g/L NaCl solution with Purolite A500TLSO4, Purolite A400TLSO4 and Ambersep 900SO4 resins.

N. Hilal et al. / Desalination 363 (2015) 4450

30

where YCl and YSO4 denote equivalent fractions of chloride and sulphate
ions in resin, while XSO4 and XCl are equivalent fractions of sulphate and
chloride ions in the aqueous phase, respectively.
To investigate a possibility to manipulate the chloride/sulphate separation factor by controlling the degree of substitution of the hydrogen
atom in the amine functional groups we have used Purolite A109,
Purolite A149S, Purolite A111 and Purolite AT500SO4 resins, which contain primary, secondary, tertiary and quaternary groups in the polymer
matrix, respectively. All these resins are of macroporous anion exchange
type with polysterene matrix cross-linked with divinylbenzene.
Based on the data on IX equilibrium, the IX isotherms for sulphate
chloride exchange have been calculated. The values of separation factor
can be determined from a constant-temperature equilibrium plot of
resin-phase concentration of chloride ion versus its aqueous-phase concentration as shown in Fig. 5.
As seen in this gure the relative chloride afnity over sulphate for
different amine functional groups can be present as Quaternary
(Purolite AT500SO4) N Tertiary (Purolite A111) N Secondary (Purolite
A149) N Primary (Purolite A109). It may be concluded that the higher
the substitution of the hydrogen atom in amine functional group by
an alkyl group is the higher chloride over sulphate selectivity for the
anion exchange resin. The obtained data are in good agreement with
previous studies on anion exchange resins demonstrated that the chemical nature of amine functionality in IX resins correlated to divalent
monovalent anion selectivity [12,14,15].
It was found that the efciency of sulphatechloride exchange
essentially depends on the concentration of feed solutions. As seen in
Fig. 6, a strong base anion exchange Purolite AT500 SO4 resin depicts
favourable isotherms (convex to X-axis) at NaCl concentrations
higher than 0.1 eq./L. At this condition chloride ion, with equivalent
fractions on the resin and in the solution plotted on Y and X axes, is preferred to sulphate ion during the IX process. At NaCl concentration in
the solution of 0.02 eq./L the resin depicts unfavourable isotherm
(convex to Y-axis) that means that sulphate ions are preferred to chloride ions. This phenomenon of reducing preference for higher-valent

Removal, %

25
20
42h

15

1h

10
5
0
0,2

0,5

Resin dosage, g/100 ml

Fig. 3. Removal of chloride ions from 32.0 g/L NaCl solution after IX treatment with
Ambersep 900SO4 resin at various resin dosages. Contact time is 1 h and 42 h.

chloride ions will increase. It is seen that, all resins performed quite similarly with 1015% variation between them in chloride removal efciency. Nevertheless, Purolite A500TLSO4 resin managed to outperform the
other resins in the chloride removal tests.
It might be also seen in Fig. 4 that chloride removal from water with
resins increases with a decrease of feed salinity and, for example, for
Purolite A500SO4 resin the removal reaches 80, 68, 54 and 32% for
NaCl concentrations of 1.0; 5.0; 10.0; and 32.0 g/L respectively.

3.2. Effect of amine functional group in IX resins on SO2

4 /Cl exchange in
saline conditions

The relative preference of chloride over sulphate ion in IX process

with the anion-exchange resin may be evaluated using a separation factor Cl
SO4, which represented as [13]:

Cl

SO4

Y Cl X SO4

X Cl Y SO4

80

Removal eeciency, %

Removal eeciency, %

100
80
60

A500TLSO4

40

A400TLSO4

20
Ampers ep 900

0
0

60
A500TLSO4

40
A400TLSO4

20
Ampersep 900

Resin dosage, g

a)

2
3
4
Resin dosage, g

b)
40

60
A500TLSO4

40

A400TLSO4

20
Ampersep 900

Removal eeciency, %

80

Removal eeciency, %

47

30
A500TLSO4

20
A400TLSO4

10
Ampersep 900

0
0

2
4
Resin dosage, g

c)

2
4
Resin dosage, g

d)

Fig. 4. Removal of Cl ions in (a) 1.0 g/L; (b) 5.0 g/L; (c) 10.0 g/L; (d) 32.0 g/L NaCl solutions at different dosages of Purolite A500TLSO4, Purolite A400TLSO4 and Ambersep 900SO4 resins.

48

N. Hilal et al. / Desalination 363 (2015) 4450

3200

10

0,1

0,2

0,3

0,4

0,5

C, meq/l

Separaon factor

2400

Chloride (3)
Sulphate (3)

1600

Chloride (2)
Sulphate (2)

AT500

0,1

800

Chloride (1)
Sulphate (1)

A111
A149

0
0

A109

0,01

10

NaCl concentraon, eq/L

Fig. 5. Cl
SO4 separation factor for Purolite resins with different amino groups at various feed
NaCl concentrations.

ions with increasing ionic strength of the solution has been called
electroselectivity and it might be explained in terms of the Donnan
potential [16]. As the aqueous phase dilution increases the Donnan
potential attracts the mobile charges with a force that is proportional
to their charge density. At low feed concentrations therefore, the diva
lent SO2
ion. The absolute value of
4 , ion will be preferred to the Cl
Donnan potential decreases as the aqueous concentration increases
and will eventually become zero at certain values of the concentrations.
These values are typical for each particular resin and once they are
exceeded, there will be an inversion of selectivity when the separation
factor Cl
SO4 = 1.
As seen in Fig. 6, for the strong base anion exchange resin Purolite
AT500SO4 the reversal of chloridesulphate selectivity occurs at NaCl
concentration of approximately 0.1 eq./L. At higher NaCl concentration
the separation factor Cl
SO4 N 1 and this means that chloride ion will be
preferred to the sulphate ion for the resin. The higher the solution concentration, the higher the Cl
SO4 separation factor (Fig. 5).

15
Bed volume

20

25

30

Fig. 7. Breakthrough curves of chloride and sulphate ions during ltration of 5 g/L NaCl
solution through a column with (1) Purolite A400TLSO4, (2) Ambersep 900SO4 and
(3) Purolite A500TLSO4 resins.

of IX resin proceeds faster (a breakthrough point shifts to smaller BV

values), but breakthrough curves for chloride ions are sharper.

3.4. Pilot scale IX column studies on SO2

4 /Cl exchange

An effect of ow rate through the IX column in a range of 1.0 5.0

L/min on chloride removal from feed NaCl solution is shown in Fig. 9.
As seen in this gure, the slower ow velocities through the column the
sharper the breakthrough curve for Cl ions and the shorter the length of
mass transfer zone. Higher ow rates through the column tend to atten the breakthrough curve and lengthen the mass transfer zone.
These nding may be explained by the fact that slow ow rate through
the column facilitates the reaching of ion exchange sites in the resin
beds with targeted chloride ions.
An effect of resin loading in the column in a range of 10.050.0 L on
chloride removal from NaCl solution is shown in Fig. 10. As seen in this
gure, an increase in resin dosage sharply elongates the operation time
until the breakthrough point of Cl ions takes place in treated water.

3.3. Small scale IX column studies on SO2

4 /Cl exchange

3.5. Osmotic pressure of salty water after IX treatment

Fig. 7 illustrates the breakthrough curves of Cl and SO4 2.ions with
various IX resins during IX treatment of 5 g/L NaCl solution. It is seen
that all the resins were able to remove almost all chloride ions in the
rst 67 bed volumes (BV) of the feed solution but the breakthrough
points for the Purolite resins started approximately one BV later than
for Ambersep 900SO4 resin.
Fig. 8 compares breakthrough curves of chloride and sulphate ions at
different NaCl feed concentrations using Purolite A500TLSO4 resin. As
seen in this gure the breakthrough points and the sharpness of the
breakthrough curves are strongly affected by the level of NaCl concentration in the feed. At high concentration of NaCl solutions, saturation

It is known that osmotic pressure of the solution depends on the

number of osmotic active particles in the solutions according to the
Vant-Hoff equation [17]:
nCRT;
where is osmotic pressure in kPa; n is number of osmotic active particles per mole; C is molar concentration in mol/L; R is universal gas constant (8.31441 Nm/molK) and T is temperature in K.
1

Relave concentraon

1
0,8

Y,Cl

0,6
0,4

Chloride, 5 g/L

0,8

Sulphate, 5 g/L
Chloride, 10 g/L

0,6

Sulphate, 10 g/L
Chloride, 15 g/L

0,4

Sulphate, 15 g/L
Chloride, 32 g/L

0,2

Sulphate, 32 g/L

0.1 eq/L
0,2

0.02 eq/L
0.2 eq/L

0
0

0,2

0,4

0,6

X, Cl

10

15

20

Bed volume

0,8

Fig. 6. Chloride IX isotherms for Purolite AT500SO4 resin during treatment of NaCl solutions of different concentrations.

Fig. 8. Breakthrough curves of the chloride and sulphate ions during ltration of NaCl
solution through the column with Purolite A500TLSO4 resin at various feed concentrations, g/L: 5, 10, 15 and 32. Relative ion concentration corresponds to outlet over inlet IX
concentration.

N. Hilal et al. / Desalination 363 (2015) 4450

49

3000

16000

C, m-eg/l

2500

C, mg/L

2000
1500

1.5 L/min
2.5 L/min

1000

12000
8000
Cl
4000

SO4

5 L/min

500

0
0

50

100

150

200

250

Fig. 9. Chloride concentrations in the eluent versus time of operation of the IX column with
Purolite AT500SO4 resin at various ow rates through the column, L/min: 1.5; 2.5 and
5.0 Vresin is 10 L. Concentration of NaCl is 2.3 g/L.

3.6. Regeneration of exhausted IX resins

A need for frequent regeneration using external regeneration
solutions is a weak side of IX when the process is used to treat water
with a high salt concentration [13]. The IX operational costs may be
sharply reduced if internal reagent solution is used for regeneration.
In this study we have evaluated a possibility to use Na2SO4 solutions
for regeneration of the exhausted IX resins. Such concentrated Na2SO4

Osmotic pressure, kPa

2500

Sea water
2000

IX-treated sea water

1500

1000
0

Bed volume

b)
Fig. 11. Concentration of chloride and sulphate ions (a) and osmotic pressure of the solutions (b) during IX treatment of Swansea Bay sea water with Purolite A500TLSO4 resin.

solutions will be produced as NF reject stream, when salty water after

IX treatment will be further desalted with NF membranes. Na2SO4 solution when passing through an exhausted IX resin in chloride form
would transform it back to the sulphate form according to following
reaction:
2(RN+)Cl + Na2SO4 f (RN+)2SO42 + 2NaCl
where (RN+)Cl is a polymer matrix of IX resin in chloride form.
1

2500

Relevent concentraon

0.8
10 L

2000

20 L

C, mg/L

a)

Time of IX operaon. min

If salty water with a high content of chloride ions is passed through

an anion exchange resin in sulphate form then, due to exchange of two
chloride ions with one sulphate ion, the feed after IX treatment will have
lower osmotic pressure and as a result a lower operating pressure might
be used to run the further membrane desalination process.
Fig. 11 illustrates the breakthrough curves of Cl and SO4 2.ions and
osmotic pressure of the solutions during IX treatment of Swansea Bay
sea water with Purolite AT500SO4 resin. The total salt content in sea
water was 32.0 g/L, the concentrations of sulphate and chloride ions
were 2.43 and 17.46 g/L, respectively. As can be seen in Fig. 11a, almost
all chloride ions were removed from the feed sea water due to exchange
with sulphate ions until a break through point of the IX column has been

reached. As a result of efcient SO2

4 /Cl exchange the osmotic pressure
of sea water dropped essentially after IX treatment (Fig. 11b). This
reduction of osmotic pressure gives a possibility to reduce the required
energy for further NF desalination of the saline water after IX treatment,
since NF membranes, which efciently reject the sulphate ions and
operate at signicantly lower transmembrane pressure compared
with RO membranes, can be used for water desalination.

Bed volume

50 L

1500

1000

500

Chloride (10 g/L)

0.6

Sulphate (10 g/L)

Chloride (28 g/L)

0.4

Sulphate (28 g/L)

Chloride (50 g/L)

0.2

Sulphate (50 g/L)

0
0

50

100

150

200

250

Time of IX operaon, min

0
0

10

15

20

25

30

Bed volume
Fig. 10. Chloride concentrations in the eluent versus time of operation of the IX column
with Purolite AT500SO4 resin at various resin loading, L: 10, 20 and 50. CNaCl is 2.3 g/L;
ow rate through the column is 1.5 L/min.

Fig. 12. Regeneration of Purolite A500TLSO4 resin with 10.0, 28.0 and 50.0 g/L Na2SO4
solutions. Relative ions concentration corresponds to outlet over inlet IX concentration.

50

N. Hilal et al. / Desalination 363 (2015) 4450

5000

C, meq/l

4000
Chloride (1 run)

3000

Sulphate (1 run)
Chloride (2 run)

2000

Sulphate (2 run)
Chloride (3 run)
Sulphate (3 run)

1000
0
0

6
8
Bed volume

10

12

14

Fig. 13. Breakthrough curves of chloride and sulphate ions with regenerated Purolite
A400TLSO4 resin during treatment of 10 g/L NaCl solution (three exhaustion runs).
0.2 M Na2SO4 solution has been used for IX resin regeneration after each saturation run.

If successful, using this internal regent would sharply reduce the

cost of water desalination because no external regeneration solution is
required for regeneration of an exhausted IX column after SO24 /Cl
exchange.
Na2SO4 solutions of concentration of 10.0, 28.0 and 50.0 g/L were
tested for the regeneration of Purolite A500TLSO4 resin. As seen in
Fig. 12, it took around 25 BV of the 10 g/L Na2SO4 solution to regenerate
Purolite A500TLSO4 resin. On the other hand, only 16 BV of the 28 g/L
Na2SO4 solution were needed to regenerate the same resin, while
50 g/L Na2SO4 solution performed only slightly better and 15 BV were
needed for regeneration. Hence, Na2SO4 regeneration solution with
concentration of 28 g/L was used for further studies. It may be assumed
that solutions of similar concentration would be produced as a retentate
during NF treatment of brackish water with sodium chloride content of
2.5 g/L.
To evaluate whether the resins performance changes after the
regeneration the IX resins were exhausted and regenerated multiple
times. The multiple breakthrough curves of chloride and sulphate ions
with regenerated Purolite A500TLSO4 resin during treatment of 10 g/L
NaCl solution are presented in Fig. 13. After each exhaustion run the
resin was regenerated with 0.2 M Na2SO4 solution. As seen in this gure
the regenerated resin performs very consistently on each run after
regeneration. This nding of reversibility of the sulphatechloride
exchange process is very important because no external regeneration
solution is required for regeneration of exhausted IX column after

SO2
4 /Cl exchange.
4. Conclusions
Seven different IX resins, namely Ambersep 900SO4, Purolite A850,
Purolite A500TLSO4, Purolite A400TLSO4, Purolite A109, Purolite A149S
and Purolite A111, which contain primary, secondary, tertiary and quaternary amino groups in the polymer matrix, were used in the work to
study sulphatechloride exchange process in saline solutions. It was
found that sulphatechloride exchange is very fast at saline conditions
and less than 10 min is needed to reach the sulphatechloride equilibrium. Very fast kinetics of sulphatechloride exchange suggests that in
salty solutions IX resistances from the liquid phase lm- and intraparticle diffusion are insignicant. It was shown that optimization of
sulphatechloride exchange process may be done by adjusting the
ow rate through the column.

The experimental results clearly indicate that the feed water concentration and the nature of the functional group of the resin play an impor
tant role in the SO2
4 /CI exchange process. It was found that the higher
the substitution of hydrogen atoms in amine functional group of anion
exchange resin is the higher chloride over sulphate selectivity and
that the chloride/sulphate separation factor depends on salt content in
feed water. It was found that Purolite A500TLSO4 resin is the most ben
ecial among the used IX resins for SO2
4 /CI exchange process in saline
solutions.
Saturated IX resins were successfully regenerated using 0.2 M
Na2SO4 solution and multiple regeneration and saturation cycles proved
have no affected on the IX performance.
It was shown that the osmotic pressure of sea water dropped essentially after IX treatment and due to such drop NF membranes would be
used for further water desalination instead of RO membranes, which are
currently used for removal of chloride ions from brackish water and sea
water. Because NF membranes operate at signicantly lower transmembrane pressure compared with RO membranes, the required energy for
membrane desalination might be essentially reduced.

Acknowledgement
The authors would like to thank King Adbul Aziz City for Science and
Technology for funding this work.

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