Ocean Water
Ocean Water
Ocean Water
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.
91
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
RH Na ! RNa H
2RH Ca2 ! R2 Ca 2H
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
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
300
350
93
35
220
200
(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.
2H2 O 4e ! 4H O2 "
at the anode
at the cathode
water dissociation
H RNa ! RH Na
2H R2 Ca ! 2RH Ca
5
6
7
8
9
10
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
It
F
12
94
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.
1500
(a)
Voltage, V
1200
650C-H
650C-Na
650C-Ca
900
600
300
0
0
50
100
150
200
250
300
250
300
(b)
550A-OH
550A-Cl
550A-HCO3
500
Voltage, V
400
300
200
100
0
50
100
150
200
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.
Conductivity, S/cm
0.070
0.065
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-
0.7
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
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.
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