Sunteți pe pagina 1din 7

Separation and Purication Technology 144 (2015) 9096

Contents lists available at ScienceDirect

Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Membrane-free electrodeionization using strong-type resins for high


purity water production
Jiayuan Hu a, Zhixing Fang b, Xiaping Jiang a, Tianjun Li a, Xueming Chen a,
a
b

Environmental Engineering Department, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, China
Zhejiang Zheneng Energy Saving Technology Co, Ltd, 2 Miduqiao Road, Hangzhou 310005, China

a r t i c l e

i n f o

Article history:
Received 29 December 2014
Received in revised form 13 February 2015
Accepted 17 February 2015
Available online 24 February 2015
Keywords:
Membrane-free electrodeionization
Desalination
High purity water
Resins regeneration
Water dissociation

a b s t r a c t
A promising membrane-free electrodeionization (MFEDI) process has been proposed for high purity
water (HPW) production in our previous work. However, the employ of a large number of weak-acid
resins in MFEDI limits this process for purifying the reverse osmosis (RO) permeate of tap water with
a pH value below 6.0. In this work, a MFEDI system lled only with mixed strong-acid and strong-base
resins was tested to desalinate the synthetic acidic RO permeate. Results demonstrated that the resins
regeneration was achieved mainly by electrically enhancing water dissociation after a high current density was imposed to the resin layer. Both good purication and effective regeneration were achieved. The
conductivity of efuent was 0.0600.062 lS/cm only. The energy consumption uctuated in the range of
0.350.41 kW h/m3 water and the water recovery reached 93.1%. The mixed concentrate collected during
regeneration, with an average conductivity of 145 lS/cm and a pH value of 6.5, could be returned to a
pretreatment unit for recovery. No chemical was needed and no wastewater was produced. Repetitive
experimental results showed the MFEDI system could work stably.
2015 Elsevier B.V. All rights reserved.

1. Introduction
High purity water (HPW) is now broadly used in a number of
industrial applications, such as electric power generation, semiconductor manufacturing and chemical laboratories [13]. The
water source of most HPW equipments is the tap water that has
undergone pre-treatment in non-coastal areas, especially in China
[1,4,5]. Ion exchange desalination, composing of two-bed (cation
anion) ion exchange and mixed bed ion exchange (MBIE), has been
used for decades in HPW production [6]. Although it has satisfactory efcacy and reliable performance, the ion exchange process also
faces many drawbacks. The chemical regeneration of resins consumes hazardous chemicals with strong corrosive property, produces secondary wastewater containing high concentration of
acid, alkali and salt, and demands a plenty of auxiliary facilities
for chemicals storage and wastewater treatment, which is laborious, costly and non-environmentally friendly.
With the development of membrane desalination technology, a
hybrid separation process, consisting of reverse osmosis (RO) and
MBIE, has been applied for HPW production since 1970s [7].
Usually, individual RO membrane can reject 9598% of the total
Corresponding author. Tel.: +86 57187951239; fax: +86 57187952771.
E-mail address: chenxm@zju.edu.cn (X. Chen).
http://dx.doi.org/10.1016/j.seppur.2015.02.023
1383-5866/ 2015 Elsevier B.V. All rights reserved.

dissolved solids (TDS) in inuent, reducing the ionic species load


of the following MBIE greatly [8]. This can lower the frequency of
regenerating resins, save chemicals and reduce wastewater discharge. But the periodic chemical regeneration of MBIE is still
needed, which means that the original problems associated with
resin regeneration such as chemicals usage and wastewater discharge are not solved thoroughly. Electrodeionization (EDI), a
hybrid separation process consisting of ion exchange and electrodialysis, is now used as an alternative technique for MBIE in production of HPW [2,9]. Since the exhausted resins can be
regenerated continuously using H+/OH ions produced through
the electrically enhanced water dissociation, the chemical regeneration is not required for EDI which is considered as an environmentally friendly process [10,11]. When processing RO permeate
of tap water, EDI can achieve over 99.5% salt rejection, and the
resistivity of efuent can reach up to 18 MX cm [35]. That is
the reason why RO and EDI are often taken as complementary
technologies, and the ROEDI process is now broadly used to produce HPW from fresh water [4,12,13].
Although EDI has many advantages including no chemical
required, no wastewater discharge and easy operation [4,14], it is
much less popular than MBIE in many large scale applications
due to its complex conguration, expensive investment and low
yield of HPW [10,15]. Besides, EDI device contains many

91

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

semi-permeable ion exchange membranes, which may result in


some membrane-associated problems such as concentration polarization and metal ions precipitation [10,16,17]. In our previous
work, a novel membrane-free electrodeionization (MFEDI) process,
combining the advantages of MBIE and EDI, was investigated and
tested successfully for HPW production [1820]. Since it does not
need any ion exchange membrane, MFEDI shows many advantages
such as simple conguration, convenient operation and easy maintenance. In the previous work, a large number of weak-acid resins
were used in MFEDI. They have features of good conductivity and
easy regeneration when they are saturated [18,20], nevertheless,
their deionization efcacy is very poor and the salt ions are also
prone to be desorbed from them in acidic solution [21]. When
MFEDI was used to purify the acidic RO permeate, the saturation
degree of the weak-acid resins in MFEDI was very low, usually less
than 3% [22], resulting in low desalination performance and poor
regeneration efciency which was positive correlation with the
saturation degree of resins [23]. Besides, overly high energy consumption was accompanied by the MFEDI regeneration owing to
the very high resistivity of the H-type weak-acid resins [20,22].
In other words, the employ of weak-acid resins in MFEDI greatly
limited the MFEDI process to desalinate the acidic RO permeate
of tap water whose pH value is below 6.0.
In the previous work, mixed strong-acid and strong-base resins,
which have excellent desalination performance over a broad band
of inuent pH [21], also showed a signicant electrical regeneration performance under a high current intensity of 200 A/m2
[18]. In view of this, in this work, we proposed and tested a MFEDI
system lled only with strong-acid and strong-base resins to purify
the slightly-acidic RO permeate. The major objectives of this work
are to explore the voltagecurrent relationship, to investigate the
purication and regeneration performances, and to examine the
operational stability of the MFEDI system lled with the mixed
strong-acid and strong-base resins.

2. Materials and methods

2.2. Electrode preparation


Reticular Ti/Pt electrodes, both with an effective area of 7.1 cm2,
were used as the anode and cathode in MFEDI. The Ti/Pt electrodes
were fabricated using a thermal decomposition method taking titanium mesh, 3 cm in diameter, as substrates. The precursor solution
was prepared by dissolving H2PtCl6H2O (99%, Adamas Reagent Co.,
Shanghai, China) in isopropanol (99.5%, Adamas Reagent Co.,
Shanghai, China) with a concentration of 0.5 M. After ultrasonic
cleaning, the titanium substrate was brushed with the precursor
solution, dried at 80 C for 5 min, and then calcinated at 500 C
for 5 min. This procedure was repeated for about 15 times, and
nally the electrode was annealed at 500 C for an hour.

2.3. MFEDI system


The MFEDI system is shown in Fig. 1 schematically. The height
and the inner diameter of the MFEDI column are 30 cm and 3 cm,
respectively. Mutually mixed 650C resins and 550A resins with a
ratio of 1:2 were packed compactly between the electrodes in
the column. A spring was used to compress the resin layer.
MFEDI system was operated in a batch mode, alternating with
purication and regeneration. In the purication step, valves 1
and 2 were open, while valves 3 and 4 were closed; feed water
entered the system through valve 1 and passed the ion exchange
bed upward; then HPW came out through valve 2. MFEDI started
the regeneration when the conductivity of HPW was beyond
0.066 lS/cm (25 C). In the regeneration step, valve 1 was closed
and valves 24 were open; HPW entered MFEDI through valve 2
and passed the ion exchange bed downward. At the same time,
direct-current (DC) electricity was supplied by an external power
source to regenerate the exhausted resins, and simultaneously
the salt ions desorbed by resins were taken away by the concentrate stream. In order to achieve equally effective regeneration
for both anion resins and cation resins and to neutralize the concentrate, the electrode polarity was reversed during regeneration:
the top electrode worked as an anode in the initial 10 min, whereas

2.1. Resins and solutions


The main characteristics of the ion exchange resins used in this
work are presented in Table 1. Before use, the gel-type strong-acid
cation resins (650C, Dow, Shanghai, China) and the gel-type
strong-base anion resins (550A, Dow, Shanghai, China) were
washed with deionized water until the conductivity of the solution
was below 2 lS/cm.
The conductivity of the RO permeate of tap water is usually
lower than 10 lS/cm [4,13,14,22]. Thus, the synthetic RO permeate
with a conductivity of 10 lS/cm was taken as the feed water of
MFEDI in this work. The feed water was prepared by dissolving
2.82 mg/L NaCl (AR, 99.5%, Aladdin, Shanghai, China), 1.11 mg/L
CaCl2 (AR, 96.0%, Aladdin, Shanghai, China) and 1.68 mg/L NaHCO3
(AR, 99.5%, Aladdin, Shanghai, China) in slightly-acidic deionized
water rstly, making the hardness of the inuent reached
1.0 mg/L in term of CaCO3; then its pH was adjusted to 5.66.0
by adding some dilute hydrochloric acid into it.

Gas

Spring
HPW
Electrode

Anion resin
Cation resin
Electrode

Table 1
Properties of ion exchange resins.
Designation

650C

550A

Type
Matrix structure
Function group
Porosity
Exchange capacity

Strong-acid
Polystyrene
Sulfo group
Gel
P2.0 eq/L

Strong-base
Polystyrene
Quaternary amine
Gel
P1.1 eq/L

Concentrate

Influent
1

3
Fig. 1. MFEDI system.

92

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

it worked as a cathode in the latter 10 min. The gases generated at


the anode and the cathode were exhausted through valve 4 using
its buoyant fore and taken away by the concentrate stream
through valve 3, respectively.
2.4. Analysis methods
Solution conductivity was measured using a Sension 5 conductivity meter (Hach, OH, resolution: 0.01 lS/cm); Ca2+ and Na+ concentrations were analyzed with an atomic absorption
spectrophotometer (AA-6300, Shimadzu, Japan); pH value was
measured using a pH/ISE meter (Orion Dual StarTM, Thermo Scientic, Singapore).
3. Results and discussion
3.1. Purication performance of MFEDI using new resins
The purication performance of the MFEDI system lled with
new resins was investigated, and the experiment results are shown
in Fig. 2. It could be found that the change trends of HPW conductivities were similar under different ow velocities investigated.
When the ow velocity was 15 m/h, the conductivity of HPW
was 0.055 lS/cm in the initial 48 h, then increased gradually,
and reached to 0.066 lS/cm at the end of service. This service
progress was a conventional deionization process of ion exchange,
which could be illustrated below:

RH Na ! RNa H

2RH Ca2 ! R2 Ca 2H

3.2. Voltagecurrent relationship of MFEDI


After adsorption, the MFEDI system needed to be electrically
regenerated. In order to explore the electrical characteristic of
the specially designed MFEDI process, the voltagecurrent (VI)
relationship of this MFEDI system was investigated and the results
are shown in Fig. 3. It was observed that, the shape of the VI curve
of MFEDI was very similar to that of EDI, demonstrating that the
ionic transport and water dissociation phenomena also appeared
in the MFEDI process after different current intensities were
applied to the resin layer [2,10,24]. Three main regions appeared
in the VI curve, and the corresponding turning points of current
density were 50 A/m2 and 130 A/m2, respectively. The low current
density region (Region I) contained a high resistance represented
the electrical transport region of salt ions; whereas the high current density region (Region III) had a low resistance represented
the water dissociation region in MFEDI [2,25,26]. A curvature
region (Region II) existed between those two linear regions (Region
I and Region III), which demonstrated the water dissociation in
MFEDI took place and became dominant gradually due to the
insufcient migration number of salt ions [10,25]. The critical current density was estimated to be around 75 A/m2 for this MFEDI
system. A signicant water dissociation phenomenon was needed
for MFEDI in order to obtain a high regeneration degree of resins,
which meant that a higher current density should be imposed to
the resin layer than the critical current density. Good regeneration
effects could be obtained under the high current conditions, nevertheless, this lowered the current efciency and increased the energy consumption [10,27]. Based on such considerations, the current
intensity of 200 A/m2 was selected for the MFEDI regeneration in
this work.
3.3. Regeneration performance of MFEDI system

ROH Cl ! RCl OH

ROH HCO3 ! RHCO3 OH

where RH and ROH represent H-type 650C resins and OH-type


550A resins, respectively. Such HPW, with a resistivity of 15.2
18.2 MX cm, proved the excellent purication performance of
MFEDI for the synthetic acidic RO permeate. The saturations of
650C cation resins and 550A anion resins were calculated to be
38.7% and 35.1%, respectively with the considerations of the
exchange capacity of resins, the inuent salinity and the volume
of HPW produced in the service process.

To better understand the regeneration performance of MFEDI,


the conductivity and pH value of the concentrate, the cation ions
concentrations in the concentrate stream and the voltage required
were recorded and analyzed systematically during electroregeneration.
Fig. 4(a) shows the concentrate conductivity variations during
regeneration. The concentrate conductivity decreased slowly from
173 lS/cm to 146 lS/cm in the initial 10 min, then declined to
108 lS/cm sharply at 11 min of regeneration; subsequently, it rose
gradually and remained around 135 lS/cm at the end of regeneration. The conductivity of the mixed concentrate was 145 lS/
cm, indicating that the exhausted resins were regenerated

0.075

600

10 m/h
15 m/h
20 m/h

500
400

0.065

Voltage, V

Conductivity, S/cm

0.070

0.060

Critical current density

Region

300
Region

200
0.055
100
0.050

Region

10

20

30

40

50

60

70

80

90

100 110

Time, h

0
0

50

100

150

200

250

Current density, A/m


Fig. 2. Purication performance of the MFEDI using new resins at an inuent
conductivity of 10 lS/cm under various ow velocities.

300

Fig. 3. Voltagecurrent curve of the MFEDI system.

350

93

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

35

220
200

Concentration of Cation (mg/L)

(a)

Conductivity, S/cm

180
160
140
120
100
80

(b)

Na
2+
Ca

30
25
20
15
10
5
0

60
0

10

12

14

16

18

20

22

10

12

14

16

18

20

22

14

16

18

20

22

Time, min

Time, min
420

10

(c)

(d)

410

400

Voltage, V

pH

7
6
5

390
380
370
360

350
340

3
0

10

12

14

16

18

20

22

10

12

Time, min

Time, min

Fig. 4. Regeneration performance of MFEDI under a current density of 200 A/m2 and a ow velocity of 15 m/h. (a) Conductivity variations; (b) Na+ and Ca2+ concentrations
variations; (c) pH value variations; and (d) voltage variations.

effectively by the H+ and OH ions produced through the water


electrolysis [18] and the electrically enhanced water dissociation
[10,28]. The following reactions were believed to occur at the electrodes and on the contact surface of resins:

2H2 O  4e ! 4H O2 "

at the anode

2H2 O 2e ! 2OH H2 "


H2 O ! H OH

at the cathode

water dissociation

H RNa ! RH Na

cation resins regeneration

2H R2 Ca ! 2RH Ca


OH RCl ! ROH Cl

cation resins regeneration


anion resins regeneration

5
6
7
8
9
10

OH RHCO3 ! ROH


HCO3

anion resins regeneration

11

where RNa, R2Ca, RCl and RHCO3 represent Na-type 650C resin,
Ca-type 650C resin, Cl-type 550A resin and HCO3-type 550A resin,
respectively. The slow decrease of the concentrate conductivity during the initial 10 min represented a reduction in the concentration
of the salt ions desorbed from resins by electricity, due to a decrease
of the salt ions concentration in resin phase during regeneration
[20]. When the electrodes polarity was reversed, the sharp decline

in the concentrate conductivity indicated the desorption process


of salt ions from the resin particles to the liquid was hindered temporarily. Soon later, the concentrate conductivity recovered to the
value as high as that before the electrode polarity reversion, meaning that a new ion migration process was reconstructed gradually
during 1114 min of regeneration. In the latter 5 min, the regeneration process of resins tended to be stabilized.
The Na+ and Ca2+ concentrations, which varied with time similar to the concentrate conductivity, are shown in Fig. 4(b). The
average concentrations of Na+ ions and Ca2+ ions measured were
23.2 mg/L and 5.6 mg/L, respectively in the concentrate. Since the
volume of concentrate stream was 3.55 L during regeneration for
each operational cycle, the total amount of the cation ions released
from 650C resins to aqueous phase was calculated to be
4.58  103 moles, which meant that around 7.6% of the exhausted
650C resins were regenerated and more than 4.58  103 moles H+
ions were generated during each regeneration. During the initial
10 min of regeneration, the top electrode worked as an anode
could produce H+ ions for the exhausted 650C resins regeneration.
The amount of H+ ions generated at the top electrode could be calculated using Eq.(12) according to Faradays law.

It
F

12

where m is the amount of H+ ions, moles; I is the current, A; t is the


electrolysis time, s. In this work, I was 0.142 A, t was 600 s, and thus
m was estimated to be 0.88  103 moles. Therefore, it could be

94

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

calculated that the water electrolysis reaction occurred at the top


electrode only supplied less than 19.2% H+ ions for cation resins
regeneration. More than 80.8% H+ ions was provided by the electrically enhanced water dissociation reaction occurred on the contact
surface of resins [10,28]. In other words, the exhausted resins
regeneration was mainly contributed by the electrically enhanced
water dissociation in MFEDI under a high current density.
When the top electrode worked as an anode, the regeneration
process of MFEDI could be illustrated in Fig. 5(a). On the one hand,
the H+ ions, produced by the water electrolysis on the anode, were
released to the solution to regenerate the exhausted 650C resins.
On the other hand, under the electrostatic force of a DC electrical
eld, the cation ions (Na+ and Ca2+ ions) in 650C resins migrated
downward; while the anion ions (Cl and HCO
3 ions) in 550A
resins migrated upward. This process resulted in a rapid depletion
of the ions absorbed at the interfaces of the cation and anion resin
particles and caused water to split there. Subsequently, the H+ and
OH ions produced by water dissociation could substitute the salt
ions in the exhausted resins and realize resins regeneration. During
the initial 10 min, H+ ions were produced together by Reactions (5)
and (7) for cation resins regeneration. Correspondingly, as shown
in Fig. 4(b), the relatively high concentrations of Na+ and Ca2+ ions
were detected in the concentrate stream during this stage. Afterward, the polarity of electrodes was reversed, causing the change
of ions migrating direction in resin particles. When the anode
was on the top of the resin layer, the Na+ and Ca2+ ions were accumulated in the lower side of cation resin particles. After the electrodes polarity was reversed, these cation ions moved upward
the upper side of cation resin particles owing to the electrostatic
force [2]. The sudden change of ions migration direction caused a
temporary negative effect on the cation ions desorbed from the
resins to the solution, resulting in a sharp decrease in the cation
ions concentrations detected at 11 min of regeneration. As illustrated in Fig. 5(b), a new ion migration balance (adsorptiondesorption equilibrium) could be reestablished soon after the
electrode polarity reversion, which made the concentrations of
the cation ions desorbed from the resin phase tend to be stabilized.
In the latter 10 min, the H+ ions for cation resins regeneration were
produced only by Reaction (7), resulting in a decrease in the concentrations of the cation ions desorbed from cation resins.
The pH variation during regeneration is shown in Fig. 4(c). The
concentrate collected during the initial 10 min of regeneration was
alkali, with a pH value around 8.0. This was because the

regeneration of cation resins was more favorable and complete


than anion resins, when the top electrode worked as an anode.
As shown in Fig. 5(a), a part of OH ions generated in the cathode
were taken away by the concentrate stream before they regenerated the anion resins, resulting in the concentrate kept alkali. After
the electrode polarity was reversed, the top electrode worked as
a cathode, and thus the regeneration of the anion resins was
enhanced. As illustrated in Fig. 5(b), a part of H+ ions generated
in the anode was taken away by the concentrate, leading to an
acidic concentrate with a pH value about 5.0. The mixed concentrate collected during the whole regeneration had a pH value of
6.5, was near neutral, indicating that the equally effective regeneration for both anion resins and cation resins was achieved. The
mixed concentrate could be returned to a pretreatment unit, such
as RO, for recovery in real applications without the need of chemical neutralization.
Fig. 4(d) shows the variation of the regeneration voltage. It can
be seen clearly that the voltage decreased gradually from 407 V to
352 V during regeneration. In MFEDI column, the resin layer consists of densely packed resins and surrounded liquid. Since the conductivity of the resins is much superior to that of the liquid [29],
the voltage required for MFEDI is mainly determined by the conductive capacity of resins. As regeneration proceeded, the cation
resins with Na+ and Ca2+ forms in MFEDI changed gradually to their
H+ forms, while the exhausted anion resins with Cl and HCO
3
forms changed simultaneously to their OH forms. Thus, it can
be inferred that the decrease in the regeneration voltage above
was directly related to the reduction in the resins resistivity owing
to the change of their forms. To investigate the resin resistivity of
different forms, the correlation of voltage with current density
for different resin forms was examined, and the results are shown
in Fig. 6. It was calculated that the resistivity of RH, RNa, R2Ca,
ROH, RCl and RHCO3 are 0.64 X m, 5.52 X m, 19.34 X m,
1.16 X m, 3.99 X m and 6.32 X m, respectively. The resistivity difference above was essentially attributed to the different bonding
force between the ions (salt ions) and the xed sites of the resins.
Since both the conductivity of RH and ROH is superior to that of
RNa/R2Ca and RCl/RHCO3, respectively, the resistance of the
resin layer in MFEDI should decrease as the regeneration proceeded, which explained why the voltage required decreased gradually
during regeneration under a constant current. Moreover, it was
found that the average regeneration voltage required for this
MFEDI system was only 380 V, much lower than that required

Water flow

Water flow

Anode

2H2O-4e4H +O2

2H2O+2e2OH-+H2

Cathode

Cl

Na

Cl+

HCO3-

Cl

OH-

Cl-

Na+
HCO3-

Cl-

Na+

Cl-

Cl-

Na+

HCO3

Na+

Ca2+

HCO3-

Cl-

HCO3-

Na+

Cl-

Na+

: Water-splitting

Cl

Na

Ca2+

Ca2+

HCO3-

Cl-

HCO3-

Na+

Cl-

Ca2+

: Water-splitting
Cl-

HCO3-

2H2O+2e2OH-+H2

2H2O-4e4H++O2

Cathode
Na+,Ca2+,Cl-,HCO3-,OH-

Na+,Ca2+,Cl-,HCO3-,H+

(a)

(b)

Anode

Fig. 5. Electro-regeneration process of MFEDI. (a) Anode is on the top; (b) cathode is on the top.

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

1500

(a)

Voltage, V

1200

650C-H
650C-Na
650C-Ca

900

600

300

0
0

50

100

150

200

250

300

250

300

Current density, A/m2


600

(b)

550A-OH
550A-Cl
550A-HCO3

500

Voltage, V

400
300
200
100
0

50

100

150

200

Current density, A/m2

after regeneration kept constant at 0.059 lS/cm in the initial


160 min, revealing that the exhausted resins had resumed their
deionization ability during electro-regeneration. Nevertheless,
the efuent quality of MFEDI after regeneration was not as good
as that using new resins. This was because that the resins in MFEDI
were regenerated partially and the regenerated resins distributed
haphazardly throughout the whole resin layer as shown in Fig. 5.
As expected, the efuent conductivity then increased slowly as
the service time increased. After 290 min (4.83 h), the conductivity
of HPW reached 0.066 lS/cm, indicating that the MFEDI system
needed to be regenerated again. This meant that the MFEDI system
used in this work produced a total of 51.5 L of HPW during service
and consumed 3.55 L of HPW during regeneration for each operational cycle. It should be noted that the service time of MFEDI was
shortened after regeneration, in comparison with that using new
resins. This is understandable because only 7.6% of the exhausted
resins in MFEDI resumed their deionization ability during 20 min
regeneration. The regeneration degree of resins could be improved
continuously as the regeneration time passed. However, the regeneration efciency of resins decreased gradually with regeneration
time, as shown in Fig. 4(a). Therefore, the proper time for regenerating was determined to be 20 min in this work, and the resins
were only partially regenerated for the energy saving purpose.
The total amount of the cation ions absorbed by MFEDI was calculated to be 4.53  103 moles according to the HPW volume and
the ions concentrations of inuent, in good agreement with the
amount of Na+ and Ca2+ ions (about 4.58  103 moles) desorbed
form resins during regeneration, demonstrating the desalting capacity of resins was unchanged after electro-regeneration.
The energy consumption and the water recovery could be calculated according to Eqs. (13) and (14), respectively.

UIt
V1  V2

13

V1  V2
 100%
V1

14

Fig. 6. Voltagecurrent correlations of the resins in different forms: (a) 650C cation
resin and (b) 550A anion resin.

for the MFEDI system using weak-acid resins [1820]. This phenomenon showed the excellent electrical conductivity of the mixed
strong-types resins, which was benecial to reduce energy consumption for MFEDI regeneration.

3.4. Purication performance of MFEDI after regeneration


After regeneration, the MFEDI system could turn to service
immediately. As shown in Fig. 7, the efuent conductivity of MFEDI
0.075

Conductivity, S/cm

0.070

0.065

where E is the energy consumption of MEEDI, kW h/m3 water; U is


the average regeneration voltage, V; I is the current, A; t is the regeneration time, h; V1 is the total volume of HPW, L; V2 is the HPW
volume consumed for regeneration, L; R is the water recovery of
MFEDI, %. In this work, U = 380 V, I = 0.142 A, t = 0.33 h, V1 = 51.5 L
and V2 = 3.55 L. Using Eqs.(13) and (14), the energy consumption
(E) and the water recovery (R) were calculated to be 0.38 kW h/m3
water and 93.1%, respectively. In contrast, it was reported that the
energy consumptions for EDI were 0.390.90 kW h/m3 water at a
feed water conductivity of 15 lS/cm [12], 0.60 kW h/m3 water at a
feed water conductivity of 2.3 lS/cm [14] and 0.70 kW h/m3 water
at a feed water conductivity of 520 lS/cm [30], respectively. Obviously, the MFEDI system used in this work is lower in energy consumption than EDI.
3.5. Operation stability of MFEDI

0.060

0.055

0.050

95

50

100

150

200

250

300

Time, min
Fig. 7. Efuent conductivity variation of the MFEDI after resin regeneration at an
inuent conductivity of 10 lS/cm and a ow velocity of 15 m/h.

In order to know if frequent regeneration could cause a deterioration in MFEDI performance, the average conductivity of efuent and the energy consumption variations were investigated for a
total of 30 operational cycles, and the results are shown in Fig. 8.
The average conductivity of efuent was found to be only 0.060
0.062 lS/cm, with the resistivity of efuent reaching up to 16.1
16.7 MX cm. There was no deterioration tendency in the HPW
quality after 30 operational cycles, which proved the MFEDI was
still very effective in ions removal after repeated regeneration. Furthermore, it was noticed that the energy consumption uctuated in
the range of 0.350.41 kW h/m3 water, and yet no increase in ener-

J. Hu et al. / Separation and Purication Technology 144 (2015) 9096

0.7

Effluent conductivity, S/cm

0.080
Average conductivity
Energy consumption

0.075

0.6
0.5

0.070

0.4
0.065
0.3
0.060

0.2

0.055
0.050

0.1

0.0

Energy consumption, kWh/m 3 water

96

8 10 12 14 16 18 20 22 24 26 28 30 32

Operational cycles
Fig. 8. Efuent conductivity and energy consumption variations in 30 operational
cycles.

gy consumption appeared in these operational cycles. The results


above demonstrated the good purication performance and high
stability of the MFEDI system.
4. Conclusions
The MFEDI lled only with mixed strong-acid and strong-base
resins was tested successfully to purify the synthetic acidic RO permeate of tap water. Water dissociation reaction could occur on the
contact face of the cation and anion resins after the MFEDI system
was supplied with a current density higher than the critical current
density, 75 A/m2. Good purication and effective regeneration
were achieved. After desalination, the conductivity of the synthetic
RO permeate was reduced from original 10 lS/cm to 0.060
0.062 lS/cm. After regeneration, the exhausted resins could
resume their ability to desalinate. The energy consumption and
the water recovery were 0.350.41 kW h/m3 water and 93.1%,
respectively. The mixed concentrate collected during regeneration,
with an average conductivity of 145 lS/cm and a pH value of 6.5,
could be returned to a pretreatment unit, such as RO, for recovery.
No chemical was needed and no wastewater was produced. Repetitive experimental results showed the MFEDI system could work
stably without any performance decay detected after long-term
frequent regeneration.
Acknowledgement
The authors are grateful for the nancial support from China
Postdoctoral Science Foundation (2014M561763).
References
[1] R. Singh, Production of high-purity water by membrane processes, Desalin.
Water Treat. 3 (2009) 99110.
[2] L. Alvarado, A.C. Chen, Electrodeionization: principles, strategies and
applications, Electrochim. Acta 132 (2014) 583597.
[3] J. Lu, Y.X. Wang, Y.Y. Lu, G.L. Wang, L. Kong, J. Zhu, Numerical simulation of the
electrodeionization (EDI) process for producing ultrapure water, Electrochim.
Acta 55 (2010) 71887198.

[4] J.Y. Wang, S.C. Wang, M.R. Jin, A study of the electrodeionization process
high-purity water production with a RO/EDI system, Desalination 132 (2000)
349352.
[5] A. Grabowski, G.Q. Zhang, H. Strathmann, G. Eigenberger, Production of highpurity water by continuous electrodeionization with bipolar membranes:
inuence of concentrate and protection compartment, Sep. Purif. Technol. 60
(2008) 8695.
[6] I.G. Wenten, F. Aranto, Bench scale electrodeionization for high pressure
boiler feed water, Desalination 314 (2013) 109114.
[7] C. Fritzmann, J. Lowenberg, T. Wintgens, T. Melin, State-of-the art of reverse
osmosis desalination, Desalination 216 (2007) 176.
[8] A. Bennett, Water processes and production: high purity and ultra-high purity
water, Filtr. Separat. 46 (2009) 2427.
[9] R.M. Wen, S.Q. Deng, Y.F. Zhang, The removal of silicon and boron from ultrapure water by electrodeionization, Desalination 181 (2005) 153159.
[10] J.H. Song, K.H. Yeon, S.H. Moon, Effect of current density on ionic transport and
water dissociation phenomena in a continuous electrodeionization (CEDI), J.
Membr. Sci. 291 (2007) 165171.
[11] J.W. Lee, K.H. Yeon, J.H. Song, S.H. Moon, Characterization of
electroregeneration and determination of optimal current density in
continuous electrodeionization, Desalination 207 (2007) 276285.
[12] O. Arar, U. Yuksel, N. Kabay, M. Yuksel, Demineralization of geothermal water
reverse osmosis (RO) permeate by electrodeionization (EDI) with mixed bed
conguration, Desalination 342 (2014) 2328.
[13] J.H. Song, K.H. Yeon, J.W. Cho, S.H. Moon, Effects of the operating parameters
on the reverse osmosis-electrodeionization performance in the production of
high purity water, Korean J. Chem. Eng. 22 (2005) 108114.
[14] A. Grabowski, G.Q. Zhang, H. Strathmann, G. Eigenberger, The production of
high purity water by continuous electrodeionization with bipolar membranes:
inuence of the anion-exchange membrane permselectivity, J. Membr. Sci. 281
(2006) 297306.
[15] J. Wood, J. Gifford, J. Arba, M. Shaw, Production of ultrapure water by
continuous electrodeionization, Desalination 250 (2010) 973976.
[16] J.S. Park, J.H. Song, K.H. Yeon, S.H. Moon, Removal of hardness ions from tap
water using electromembrane processes, Desalination 202 (2007) 18.
[17] W. Rukapan, B. Khananthai, C. Chiemchaisri, W. Chiemchaisri, T. Srisukphun,
Short-and long-term fouling characteristics of reverse osmosis membrane at
full scale leachate treatment plant, Water Sci. Technol. 65 (2012) 127134.
[18] W.Q. Su, R.Y. Pan, X.M. Chen, Membrane-free electrodeionization for high
purity water production, Desalination 329 (2013) 8692.
[19] W.Q. Su, T.J. Li, X.P. Jiang, X.M. Chen, Membrane-free electrodeionization
without electrode polarity reversal for high purity water production,
Desalination 345 (2014) 5055.
[20] X.L. Shen, T.J. Li, X.P. Jiang, X.M. Chen, Desalination of water with high
conductivity using membrane-free electrodeionization, Sep. Purif. Technol.
128 (2014) 3944.
[21] I.M. Abrams, Cation exchange resins having phosphorus acid functional groups
and method of preparation thereof, U.S. Patent 2,844,546, July 1958.
[22] R.Y. Pan, RO/MFEDI for High Purity Water Production, Zhejiang University,
Hangzhou, 2014 (In Chinese).
[23] K.H. Yeon, J.H. Song, S.H. Moon, A study on stack conguration of continuous
electrodeionization for removal of heavy metal ions from the primary coolant
of a nuclear power plant, Water Res. 38 (2004) 19111921.
[24] L. Fu, J.Y. Wang, Y.L. Su, Removal of low concentrations of hardness ions from
aqueous solutions using electrodeionization process, Sep. Purif. Technol. 68
(2009) 390396.
[25] L. Alvarado, I.R. Torres, A.C. Chen, Integration of ion exchange and
electrodeionization as a new approach for the continuous treatment of
hexavalent chromium wastewater, Sep. Purif. Technol. 105 (2013) 5562.
[26] Y.L. Su, J.Y. Wang, L. Fu, Pure water production from aqueous solution
containing low concentration hardness ions by electrodeionization, Desalin.
Water Treat. 22 (2010) 916.
[27] K.E. Bouhidel, A. Lakehal, Inuence of voltage and ow rate
on electrodeionization (EDI) process efciency, Desalination 193 (2006)
411421.
[28] H. Meng, C.S. Peng, S.X. Song, D. Deng, Electro-regeneration mechanism
of ion-exchange resins in electrodeionization, Surf. Rev. Lett. 11 (2004) 599
605.
[29] K. Vuorilehto, A. Tamminen, Application of a solid ion-exchange electrolyte in
three-dimensional electrodes, J. Appl. Electrochem. 27 (1997) 749755.
[30] Y.Q. Li, S. Guan, E.Q. Tang, Development of a spacer for the diluting
compartment of EDI-LB (electrodeionization-layered bed) device, J. Sustain.
Dev. 3 (1) (2010) 202207.

S-ar putea să vă placă și