Chemosphere 217 (2019) 763e772

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Treatment of low-level Cu(II) wastewater and regeneration through a

novel capacitive deionization-electrodeionization (CDI-EDI)
technology
Chunxia Zhao, Lifang Zhang, Rongshu Ge, Ailin Zhang, Chunhui Zhang, Xiaoxin Chen*
College of Chemistry and Environmental Science, Hebei University, Key Laboratory of Analytical Science and Technology of Hebei Province, Baoding, 071002,
China

h i g h l i g h t s

A novel CDI-EDI reactor was developed to treat low-content heavy metal ions in high-salinity wastewater.

This technique exhibited stability and low-cost in resin and electrode regenerations.

CDI-EDI device achieved heavy metal enrichment and recycle from regeneration fluid.

This technique overcame regeneration difficulty and easy scaling defects of conventional mixed bed resin.

Tandem-type devices could effectively remove low-concentration heavy metal in wastewater.

a r t i c l e i n f o a b s t r a c t

Article history: It was difficult for mature technologies to manage the low-level heavy metal wastewater due to low
Received 4 August 2018 efficiency, secondary pollution and difficult enrichment. In this study, a novel capacitive deionization-
Received in revised form electrodeionization (CDI-EDI) technology was developed through coordination mechanism of electro-
2 November 2018
migration, electro-adsorption and ion exchange. Based on this technique, the low-content heavy metal
Accepted 11 November 2018
Available online 13 November 2018
ions in high-salinity wastewater could be removed efficiently. Moreover, a higher electro-adsorption CDI
electrode was applied in the CDI-EDI stack. EDI device was optimized by decreasing ion exchange
Handling Editor: Tsair-Fuh membranes from 4 to 2, thus reduced the stack cost. Based on the CDI-EDI stack, the simulated Cu(II)
wastewater (C0 ¼ 42.9 mg/L) was treated, and its average removal rate in 1st cycle cathode- and anode-
Keywords: effluent was 95.7% and 87.6%, respectively, under optimal direct current (DC) of 1.5 mA for 1.5 min, fol-
Heavy metal lowed by electroregeneration of resin and electrode. Besides, the actual electroplating wastewater
Copper wastewater containing Ni(II) (389.4 mg/L) was treated via this device after precipitation to verify its feasibility. The
Ion exchange results indicated that Ni(II) in the anode- and cathode-compartments were removed by 1.61 mg/L and
Electrodeionization
2.01 mg/L, respectively, only via one-stage CDI-EDI device under the operating voltage (0.10e0.20 V) and
Capacitive deionization
direct current (2.0e4.0 mA). It was possible to improve desalination efficiency of low-concentration
heavy metal using tandem-type multistage devices. The CDI-EDI technique could not only ensure sta-
ble effluent and lower regenerations cost, but also enrich heavy metal from regeneration fluid to achieve
resource recovery. This study would have obvious implications in treatment of low-content and salt-
containing heavy metal wastewater with high efficiency and low energy consumption.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction

As a class of important environmental contaminants, heavy

Abbreviations: CAC, capacitive activated carbon; DC, direct current; CDI,
capacitive deionization; EDI, electrodeionization; PTFE, polytetrafluoroethylene.
* Corresponding author.
E-mail addresses: zhaocx@hbu.edu.com (C. Zhao), zlf13546640905@163.com
(L. Zhang), 18931636269@163.com (R. Ge), zcxsea@163.com (A. Zhang), zchsky@
hbu.edu.cn (C. Zhang), xiaoxinchen518@126.com (X. Chen).
metals such as chromium (Cr), cadmium (Cd), lead (Pb), copper
(Cu), nickel (Ni), zinc (Zn) have been widely exploited and applied
by humans due to their unique physical and chemical properties.
However, these heavy metals posed a severe threat to human be-
ings and ecosystems attributing to their accumulation and toxicity

https://doi.org/10.1016/j.chemosphere.2018.11.071
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
764 C. Zhao et al. / Chemosphere 217 (2019) 763e772
in organisms, especially combination to other contaminants (Ji
et al., 2018; Xia et al., 2018; Lu et al., 2018). Usually, heavy-metal
wastewaters were produced from industries such as electro-
plating, minerals, smelting, batteries, and chemicals (Chowdhary
et al., 2018), with a high concentration as much as several hun-
dreds of ppm. To the best of our knowledge, chemical precipitation
method on basis of solubility product theory is the most cost-
effective pretreatment to reduce the post-processing load and
recycle heavy metal precipitation. However, it was almost impos-
sible to completely remove heavy metal in actual industrial
wastewater using chemical precipitation due to competitive effect
of salt ions. To decrease heavy metal ions to ppm level, there need
to combine primary precipitation treatment with other enrichment
methods such as adsorption, ion exchange, reverse osmosis (RO),
electrochemistry, biotechnology and so on. However, these
enrichment techniques still exhibit many problems such as the
regeneration difficulty of adsorbent and ion exchange resin
(Humelnicu et al., 2015; Sherlala et al., 2018), membrane and
electrode fouling (Feng et al., 2013; Wang et al., 2018), high energy
consumption, biological toxicity and high stability and so on (Hu
et al., 2018; Wen et al., 2018). In many mature technologies, it is
almost difficult to enrich low-concentration heavy metal from
wastewater for high efficiency and low energy consumption.
Especially, when salinity exceeds 1%, other cations in wastewater
will disturb significantly removal efficiency of heavy metal.
In these friendly electrochemical technologies, heavy metal ions
might be effectively removed and recycled under direct current
(DC) electric field, using electro-deionization (EDI) technique
combined with electrodialysis (ED) and ion exchange process.
These ion exchange resins were regenerated online by Hþ and OH
produced from water electrolysis (Hu et al., 2015, 2016; Melnikov
et al., 2017). Compared with specific energy consumption of ED,
EDI and RO processes, ED and EDI stacks are favorable at low inlet
salinities (<9000 ppm) while RO becomes favorable at high salin-
ities (Lopez et al., 2017). However, EDI technology exhibited many
drawbacks such as high energy consumption, more membrane
requirements, susceptibility to polarization and membrane fouling.
The deionization and fouling of EDI using the conventional mixed
beds was showed in Fig. 1. Hence, an EDI membrane stack with
reasonable structure, low power consumption and less membrane
fouling has attracted widespread concern. From another
Fig. 1. Schematic of deionization and fouling phenomena of EDI in the conventional
mixed beds.
perspective of the CDI principle, when a certain working voltage
was applied to capacitance electrode, the salt ions migrated to the
anode or cathode under the external electric field, subsequently
stuck on electrode surface and holes to form electric double layer
by electrostatic adsorption. The regeneration of the activated car-
bon electrode (CAC) was achieved by shorting or applying reverse
voltage so that the adsorbed salt ions on electrodes were desorbed
into solution to prepare for ion adsorption in the next cycle (Liang
et al., 2013; Porada et al., 2013; Suss et al., 2015; Salamat and
Hidrovo, 2018). However, the Faraday reaction was usually inevi-
table when the electrode working voltage was higher than
0.9e1.0 V, thus caused an unsatisfactory electrode regeneration (He
et al., 2016; Lee et al., 2010). Therefore, the long-term stability of
CDI was usually caused by the negative Faradaic reactions (Zhang
et al., 2018; Huang et al., 2014). The integration of EDI and CDI
techniques would improve obviously removal efficiency of heavy
metal ions.
To improve energy efficiency and reduce membrane fouling, a
novel capacitive deionization-electrodeionization (CDI-EDI) stack
was designed in this study on basis of the adsorption characteristics
of double layer capacitors of CDI electrode materials (Kim et al.,
2015; Chen et al., 2018; Remillard et al., 2018), simultaneous with
electromigration and ion exchange of EDI module (Melnikov et al.,
2017). The CDI-EDI structure was optimized to reduce ion exchange
membranes and fouling possibility, thus improved removal effi-
ciency of heavy metal ions. The weak-acid resin was capable of
adsorbing cations effectively in alkaline medium and desorbed
easily under slightly acidic conditions (Chai et al., 2005). These
important attributes of weak-acid resin enabled the EDI to work
successfully. This technique was firstly applied to desalination of
low-concentration copper wastewater with an apparent effect. This
study might provide a new strategy for enrichment and treatment
of other low-concentration and high-salinity heavy metal waste-
water with high-efficiency, low-cost and online regeneration.
2. Materials and methods
2.1. Reagents and chemicals
The capacitive activated carbon (CAC, specific surface area
2100 m2/g, particle size 10 mm) was provided by Fuzhou Yi huan
Carbon Co., Ltd. (Fuzhou, China). The battery-grade acetylene black
and polytetrafluoroethylene (PTFE) emulsion (pH 9e10, viscosity
25 cp, solid content 60%, specific gravity 1.52 g/cm3 at 25  C) were
provided by Taiyuan Yingze District Liyuan battery sales depart-
ment (Taiyuan, China). Titanium (Ti) net (purity 99.9%) was pur-
chased from Anping Oufulang metal wire mesh Manufacturing Co.,
Ltd. (Hengshui, China). D113 macroporous weak acidic cation ex-
change resin and D630 macroporous weak alkaline anion exchange
resin were obtained from Zhejiang Zhengguang Industrial Co., Ltd.
(Hangzhou, China). The cation- and anion-exchange membranes
were provided by Hangzhou Lvhe environmental protection tech-
nology Co., Ltd (Hangzhou, China). All of other reagents were
analytical-grade. The diluted PTFE solution 1% (v: v) was prepared
by diluting PTFE stock emulsion with deionized water according to
solid content equivalent of PTFE. An atomic absorption spectro-
photometer (WYX-9003A, Shenyang Yitong Technology Co., Ltd.,
China) was employed for metal ion detection. A multiparameter
water quality analyser (HQ30d, HACH Company, United States) was
used to determine other parameters.
2.2. Preparation of capacitance electrode
A titanium mesh (5 cm  10 cm) was placed in 10% oxalic acid
solution and heated to 100  C keeping faint boiling state for 2 h to
 C. Zhao et al. / Chemosphere 217 (2019) 763e772
etch, subsequently transferred and stored in 3% oxalic acid solution
before used. The carbon material, conductive agent acetylene black
and binder PTFE dilution (1%) were mixed in the proportion of 70:
25: 5 (w: w: w), following added a small amount of distilled water
and stirred to a paste. Subsequently, the paste mixture was coated
on Ti-net substrate that compacted repeatedly at 12 MPa. Finally,
the coated Ti-net was dried at 105  C for 2 h before further use. In
order to drive away the air inside micropores of electrode and
eliminate physical adsorption of the activated carbon, the capacitor
electrode with Ti wire was thoroughly soaked in Cu(II) solution
(50 mg/L) before used.
2.3. Structure and work principle of novel CDI-EDI stack
The structure of novel CDI-EDI stack was depicted in Fig. 2(a),
and the mechanisms of deionization and electroregeneration were
displayed in Fig. 2(b). In deionization operation process, a lower
intensity DC (<4.0 mA) was used to ensure the absence of hydro-
lysis. In the anode chamber, Cu(II) was removed by ion exchange
and electromigration while SO2 4 was removed via electrode
adsorption. On the contrary, the Cu(II) removal depended on elec-
trode adsorption in the cathode chamber, whilst the removal of
SO2
4 was achieved through ion exchange and electromigration. The
Fig. 2. Schematics of novel CDI-EDI device structure (a) and deionized-regeneration mechanism (b).
765
copper sulfate (CuSO4) was enriched in the concentrated chamber.
A combination between agents and electroregeneration was used
to regenerate the resins, thus reduced power consumption of water
electrolysis side reaction and reagent dosage (Yu et al., 2018).
Meanwhile, the Cu(II) in regeneration liquid could be enriched and
recycled effectively. During resin regeneration, H2SO4 (0.05 mmol/
L) and NaOH solution (0.1 mmol/L) were added into anode and
cathode cells, respectively, and the two chambers were exerted a
short-time high-intensity DC which was higher than the current of
water electrolysis. In the anode compartment, the cationic resin
that captured Cu(II) was regenerated by Hþ generated from water
electrolysis. In the cathode compartment, the anionic resin was
regenerated by OH produced from water electrolysis. At this
moment, the continuation absorptions of Cu(II) and SO2 4 were
occurred onto the cathode and anode, respectively, and CuSO4 was
further enriched in the concentrated chamber. The electrode
regeneration process was as follows. After the regeneration liquids
in the cathode and anode chambers were exchanged, a low-
intensity reverse DC was exerted on this device. At the same
time, the anode and cathode were endowed with negative- and
positive-potential, respectively. Thus, the adsorbed ions on the
anode and cathode were repelled and desorbed to the regenerated
solution. When this device was applied to low-level heavy metal
766 C. Zhao et al. / Chemosphere 217 (2019) 763e772
wastewater treatment, the regeneration liquids were recycled by
supplementing with a small amount of H2SO4 or NaOH solution,
respectively.
These winding channels were designed to avoid short flow in
the anode-, enrichment- and cathode-chamber, respectively. In
addition, the three chambers were separated by cation and anion
exchange membranes, respectively. The space between cathode
and anode was set as 1.5 cm. The effective volume for each single
chamber was 17.5 mL. The anode- and cathode-chambers were
loaded with 5.0 mL ion exchange resin, respectively, and electrolyte
sodium sulfate (Na2SO4) solution was injected into the concen-
trated chamber. The stack was capable of achieving deionization,
resin regeneration and electrode regeneration under direct current
(DC). Even if this device was in standby, it was necessary to keep the
stack always immersed into water to maintain resin and exchange
membrane activities. The flow rates of three chambers were
adjusted to 10 mL/min under device operation. In this study, 50 mL
copper sulfate (Cu2SO4) solution containing Cu(II) (42.9e54.8 mg/L)
was used as the simulated wastewater sample. 50 mL Na2SO4 so-
lution (0.04 mol/L) as electrolyte was injected into the concentrated
chamber. All 50 mL influent that outflowed from the CDI-EDI stack
was marked as the first effluent, and the first effluent (50 mL)
outflowed again from the stack was marked as the second-cycle
effluent, and so on. All of the resin load, electrolyte concentration,
performances of electrode plates and ion exchange membranes
affected the device resistance value. Usually, to control the oper-
ating voltage didn't well reflect the ion transmission power and
water electrolysis rate, while it was feasible able to be achieved via
current control (Nikonenko et al., 2014). Therefore, the current of
CDI-EDI stack was controlled to obtain stable operation and
regeneration effect in this study. The water splitting reaction was
observed in the cathode and anode chambers when the current was
beyond 4.0 mA.
2.4. Optimization of CDI-EDI stack
2.4.1. Single ion exchange and its electroregeneration
Keeping CDI-EDI device with no current, the simulated copper
wastewater (50 mL) was injected into the cathode- and anode-
chambers equipped with 5.0 mL cation- and anion-resins, respec-
tively, whilst 50 mL Na2SO4 electrolyte solution was injected into
the concentrated chamber. The concentration of Cu(II) in effluent
from three chambers was determined by an atomic absorption
spectrophotometer. Once the effluent was fully outflowed from the
device, a second 50 mL simulation wastewater was reinjected into
the cathode- and anode-chambers, respectively, while the solution
in the concentrated chamber was still circulated. After five repli-
cations of influent-effluent water, the resin electroregeneration was
carried out with a positive 9.0 mA DC for 5.0 min, as well as the
concentrated chamber solution was renewed. The average values of
two parallel results were analysed in this study.
2.4.2. Single electromigration and electroadsorption of Cu(II)
With no resin, the simulated copper wastewater (75 mL) was
injected into the cathode- and anode-chambers, respectively. The
CDI-EDI stack was connected to 2.0 mA positive DC. The concen-
tration of Cu(II) in effluent after three cycles was detected. The
electrode was regenerated after five cycles under 6.0 mA reverse DC
for 15 min. The Cu(II) content in effluent during the electro-
regeneration was determined. Meanwhile, the electrolyte in the
concentrated chamber was renewed. The average values of two
parallel results were analysed in this study.
2.4.3. Determination of internal circulation times and effect of
electrode regeneration
The simulated copper wastewater (50 mL) was injected into the
cathode- and anode-chambers equipped with 5.0 mL cationic and
anionic resin, respectively, and the two chambers were connected
to 1.5 mA positive DC. Five internal circulations for wastewater
were carried out in the CDI-EDI stack, the concentration of Cu(II) for
each cycle effluent was detected. Therefore, the number of internal
circulation was determined according to the effluent requirements
of Cu(II). To investigate the electrode stability, the concentration of
electrolyte Na2SO4 in the concentrated chamber was increased to
0.1 mol/L, as well as the cathode and anode were connected to
1.5 mA positive DC. The Cu(II) in the fifth effluent was quantified
after five successive internal circulation of the 50 mL copper
wastewater, subsequently the stack was jointed to 5.0 mA reverse
DC for 7.5 min for electroregeneration. The stabilities of cathode
and anode were assessed, based on the above trials with a total of
four influents and four electrode regenerations. The analysed data
were the average values of two parallel experiments.
2.5. Effluent stability with non-regeneration and frequent
electroregeneration of CDI-EDI stack
As shown in Fig. 2(b), the removal mechanisms of heavy metal
ions were cation resin exchange and electromigration in the anodic
chamber, and electro-adsorption in cathode chamber, respectively.
Therefore, the removal efficiency of Cu(II) under non-regenerative
treatment was investigated as follows. Loaded 8.0 mL ion ex-
change resin and 50 mL copper wastewater, the anode- and
cathode-chambers were connected to 1.5 mA positive DC. The
determination of Cu(II) in effluent was performed with an interval
of two cycles, then renewed the wastewater sample with a total of
six influent-effluent cycles.
On the other hand, the effluent stability with frequent electro-
regeneration of CDI-EDI stack was studied as follows. Increased the
loading amount of resins to 12 mL as well as reduced the influent
amount to 15 mL, the cathode- and anode-chambers of CDI-EDI stack
was attached to 1.5 mA positive DC for 1.5 min, then the parameters
including electrical conductivity, pH and Cu(II) content in effluents
were measured. Subsequently, the regenerations of resin and elec-
trode were carried out in turn as follows: (1) Resin regenerations.
The regeneration fluid sulfuric acid solution (20.0 mL, 0.05 mmol/L
H2SO4) and sodium hydroxide solution (20.0 mL, 0.1 mmol/L NaOH)
were added into anode- and cathode-cells, respectively. An addi-
tional 6.0 mA DC was exerted on this stack for 1.5 min (2) Electrode
regenerations. Reversed the regeneration fluid between anode- and
cathode-cells after resin regeneration and continued to recycle the
Na2SO4 solution (0.04 mol/L, 15 mL) in the concentrated chamber,
the anode and cathode were connected to 2.5 mA opposite DC for
1.5 min. There were five repetitions of the above produce. The
electrical conductivity, pH and Cu(II) content in each effluent from
three chambers were determined to assess the effects of frequent
resin and electrode regenerations on effluent quality. The average
values of two parallel results were analysed in this study.
2.6. CDI-EDI technique application in actual electroplating
wastewater
To evaluate reliability and applicability, the CDI-EDI stack was
applied in the actual wastewater collected from an electroplating
factory in Shenzhen. The major parameters of electroplating
wastewater included nickel ion concentration (389.4 mg/L), total
dissolved solid (5.67 g/L), ammonia nitrogen concentration
(503.5 mg/L), pH (3.1), and electrical conductivity (10.1 mS/cm). To
reduce the subsequent running burden of CDI-EDI stack, the
 C. Zhao et al. / Chemosphere 217 (2019) 763e772 767

electroplating wastewater was pretreated by chemical precipita- current. The removal efficiencies of Cu(II) from the simulated
tion as follows. The addition of SiO2 (1.5 g/L, 200e300 mesh) into wastewater were showed in Fig. 3(a and b). The results indicated
500 mL wastewater aimed at accelerating precipitation at 200 rpm that Cu(II) (C0 ¼ 54.7 mg/L) was effectively adsorbed via cation
following adjustment of pH to 13 via NaOH solution (5.0 mol/L). exchange resin and capacitor electrode in the anode chamber with
Subsequently, 0.5 mg polyacrylamide (PAM) solution (50 mg/L) was the average removal rate of 68.3%. After two electroregenerations,
added into this wastewater (500 mL) and stirred at 80 rpm for there was a significant decline of Cu(II) in the anode-chamber
25 min, then kept in static state for 20 min. Finally, the supernatant effluent, which indicated that the hydrogen ions from water elec-
was filtered via a 0.45 mm water microfiltration membrane and trolysis under 9.0 mA DC promoted the cation resin regeneration.
submitted for Nickel(Ⅱ) concentration analysis. The Nickel(Ⅱ) res- As observed from Fig. 3(a and b), 52.5% Cu(II) was removed through
idue in the primary sedimentation filtrate was 4.76 mg/L after the surface adsorptions of capacitor electrode and anion resin in the
above precipitation. cathode chamber. Furthermore, the higher current enhanced the
Under 2.0 mA positive DC, the primary sedimentation effluent cathode electroadsorption during resin regeneration, thus Cu(II)
filtrate (540 mL) was injected into the cathode- and anode- residue in the first cathode-chamber effluent was decreased
chambers loaded with 12 mL resin, respectively. Moreover, 15 mL significantly after regeneration. Fig. 3(a) indicated that Cu(II) was
Na2SO4 solution (0.04 mol/L) was circulated in the concentrated increased in the concentrated chamber, suggesting that a small
room. The Nickel(Ⅱ) content was monitored for every 30 mL amount of Cu(II) might cross the cation exchange membrane to the
effluent. After each treatment of 180 mL filtrate, the resin and concentrated chamber. This phenomenon was mainly attributed to
electrode were regenerated in turn as follows: (1) Resin re- the electric double layer theory and Donnan film balance theory
generations. The H2SO4 solution (0.05 mol/L, 15 mL) and NaOH so- (Strathmann et al., 2013). Usually, ion exchange efficiency and
lution (0.1 mol/L, 15 mL) were injected into the anode and cathode stability were affected by the properties of ion exchange resin.
chamber under 4.0 mA DC to regenerate resins for 9.0 min, Although the removal rate of Cu(II) from wastewater using strong
following the measurements of Nickel(Ⅱ) concentration, pH and acid ion exchange resin was higher than that of weak acid resin, the
electrical conductivity. (2) Electrode regenerations. Reversed the higher hydrogen ion (pH < 1) requirement and high-cost power
regeneration liquid and continued to recycle the electrolyte solu- consumption for former exhibited obvious inferiority than latter.
tion of the concentrated chamber, the CDI-EDI stack was connected Herein it was worth emphasizing that the Cu(II) removal efficiency
to 2.5 mA opposite DC for 15 min to regenerate electrodes. The could be significantly improved by tandem-type CDI-EDI stacks.
three parameters of the effluents from three chambers were Taking a comprehensive consideration, therefore, the weak acid
measured. The average values of two parallel results were analysed cation exchange resin was applied in this study to avoid electric
in this study. energy waste in the adverse reaction of water electrolysis.

2.7. Charge efficiency calculation of CDI-EDI stack

3.2. Effects of electromigration and electrosorption on Cu(II) and
In this study, the energy consumption of the novel CDI-EDI stack electrode regeneration
under different conditions were evaluated as the following formula.
To study the effects of electromigration and electro-adsorption
E ¼ UIt=V on wastewater treatment, CDI-EDI device was applied to current
without ion exchange resins. The effects of anode electromigration
where, U was the value of voltage, V; I was the current at time t, A; V and cathode electro-adsorption under 2.0 mA DC were showed in
was the volume of the simulated wastewater, mL. Fig. S1(a, b). It was observed that the mean concentration of Cu(II) in
the anode-chamber effluent was decreased by 21.8 mg/L after three
3. Results and discussions circulation, while it increased from zero to 20.9 mg/L in the
concentrated chamber effluent. These findings suggested that Cu(II)
3.1. Effects of ion exchange on Cu(II) and the resin electro- from the anode chamber to the concentrated chamber was attrib-
regeneration uted to electromigration, and its removal rate was 44.5%. To study
the effects of electroregeneration on effluent, the electrodes were
To investigate the effect of individual ion exchange on waste- regenerated once every five influent-effluent cycles through con-
water treatment, CDI-EDI device was operated under free of necting to 6.0 mA reserve DC for 15 min, thus, the adsorbed ions
CCu of anode and cathode chamber (mg/L)

40 10 100
a Effect of ion exchange
CCu of concentrated chamber (mg/L)

Anode chamber
Cathode chamber
b Effect of ion exchange
30 8 80
Removal rate of Cu2+ (%)

20 6 60
10 1 cycle
effluent Regeneration every 5 effluent 4 40
0 Regeneration Regeneration
Concentrated chamber 2 20 Anode chamber
-10 Cathode chamber
0
2+

0
2+

0 20 40 60 80 0 20 40 60 80
Time (min) Time (min)

Fig. 3. Concentration of Cu(II) in effluents (a) and the corresponding average removal rate with standard deviation (b) by ion exchange (C0 ¼ 54.7 mg/L).
768 C. Zhao et al. / Chemosphere 217 (2019) 763e772

were desorbed by changing electrode polarity. Under electrode As shown in Fig. 4(a and b), an increasing removal rate was
regeneration, however, exceeding water-electrolysis current might observed along with the growing cycle times of wastewater in the
lead to the migration of a small amount of Cu(II) from the concen- stack due to ion exchange, electromigration and electro-adsorption.
trated chamber to the anode chamber, thus a slight decrease of In the cathode chamber, the concentration of Cu(II) was reduced
Cu(II) was observed in the concentrated chamber after regeneration from 47.7 mg/L to 25.6 mg/L after the first cycle treatment with the
(Fig. S1(a)). There was occurred partial Cu(II) electroadsorption removal rate of 46.4%, and up to 80.0% after total five cycles. These
when anode was converted to a negative potential, leading a findings suggested that increasing residence time might improve
continuing decline of Cu(II) in the regenerated effluent of the anode the adsorption of Cu(II) on cathode on. As seen from Fig. 4(a), Cu(II)
chamber. As observed in Fig. S1(b), the cathode electroadsorption in the anode-chamber effluent was significantly decreased to
exerted an average removal rate (42.6%) of Cu(II). However, a slight 1.23 mg/L after five cycles. A significant decline might be mainly
increase of Cu(II) in the regenerated effluent of the cathode chamber attributed to cation exchange and electromigration. Based on a
was observed when the cathode potential convertion occurred from comparison of three factors, it could be easily found that cation
negative to positive for electroregeneration. This result was mainly exchange played a dominant role on Cu(II) removal from waste-
attributed to desorption of the adsorbed Cu(II). Compared with water, following the cathodic electro-adsorption, and electro-
anode chamber, the less Cu(II) immigration in the concentrated migration exhibited a slight effect. Therefore, it was particularly
chamber might be attributed to its partial retention when Cu(II) important to determine cation exchange resin type, resin loading
passed through the anode chamber membrane after the activation capacity and regeneration conditions.
of cation exchange membrane. However, this phenomenon was To investigate the effects of the cathode and anode re-
gradually disappeared due to the performance improvement of ion generations on Cu(II) removal in effluents, the CDI-EDI stack was
exchange membrane with the repetition use of CDI-EDI device. electrified by 5.0 mA reverse DC for 7.5 min following the method of
Hence, the above results demonstrated that the efficiency and sta- section 2.4.3. The results were depicted in Fig. 4(c and d). As shown
bility of electromigration were not only closely related to the per- in Fig. 4(d), the stability of Cu(II) removal depending on ion ex-
formance of ion exchange membrane (Bunani et al., 2018), but also change in the anode chamber was observed and its average
the obvious correlation with regenerative current. removal rate was up to 94.9%. Moreover, a further reduction of
Cu(II) in the anode-chamber effluent might be illustrated by the
following fact. A small portion of Cu(II) might be simultaneously
3.3. Internal circulation times of CDI-EDI and effect of electrode
adsorbed by cation resin and electrode when the anode was con-
regeneration on effluent quality
verted to a negative potential to desorb anion. In other words,
under weak acid condition (4 < pH < 7), the exchange adsorption
The circulation times of CDI-EDI stack were investigated to
might be occurred between cationic resin and Cu(II) to a certain
assess the effect of residence time of wastewater on Cu(II) removal.

100 10
CCu of anode and cathode chamber (mg/L)

Removal rate of different methods (%)

50 3

Removal rate of electromigration (%)

b Internal circulation times
CCu of concentrated chamber (mg/L)

a Internal circulation times

40 Concentrated chamber 8
Anode chamber 80
Cathode chamber 2
30 6
60
20 4
1
40 Electromigration
10 2
Resin+Electromigration
Resin Cathode adsorption
2+

0 0 20 0
0 1 2 3 4 5 0 1 2 3 4 5
2+

Number of cycles Number of cycles

60 50 100
CCu of anode and cathode chamber (mg/L)

c Electrode regeneration Anode chamber d

CCu of concentrated chamber (mg/L)

50 Cathode chamber
40
Removal rate of Cu2+ (%)

40 80
30
30 Electrode regeneration Electrode regeneration
20 5 cycles Electrode 60
regenerant
10 effluent 20
0 40
Concentrated chamber
-10 10 Anode chamber
20 Cathode chamber
-20
2+

-30 0
2+

0 20 40 60 80 100 120 140 0

Time (min) 0 30 60 90 120
Time (min)
Fig. 4. Influences of the internal circulation times on effluent using CDI-EDI device (a, b) (C0 ¼ 47.7 mg/L), and effects of electrode regenerations on the effluent stability (c, d)
(C0 ¼ 45.3 mg/L).
 C. Zhao et al. / Chemosphere 217 (2019) 763e772
extent. Fig. 4(d) showed that the average removal rate of Cu(II) was
up to 86.6% with the cathode electro-adsorption and it was possible
to enhance its electro-adsorption by increasing the cycled times of
wastewater. In addition, a slight decline of Cu(II) concentration in
the cathode-chamber effluent might be attributed to adsorption of
the desorbed Cu(II) by the electric double layer of anionic resin,
when a positive electric potential was applied to the cathode. Be-
sides, when the concentration of Na2SO4 electrolyte solution was
increased from 0.04 mol/L to 0.1 mol/L, the removal rate of Cu(II)
only by electromigration was enhanced from 5.20% to 19.0% as
shown at Fig. 4(b and c). This finding indicated that Na2SO4 was
able to promote the enrichment of heavy metal ions by electro-
migration. However, it was unfavourable for the Cu(II) detection
with the electrolyte increase. In addition, the high salinity would
reduce the membrane life and corrode the pipe.
3.4. Treatment effect of simulation wastewater via CDI-EDI device
under non-regeneration and frequent regeneration
Fig. 5(a and b) showed the removal rates of Cu(II) via different
actions (ion-exchange, electrosorption, electromigration) under no
Fig. 5. Stabilities of CDI-EDI stack without regeneration (a, b) (C0 ¼ 54.8 mg/L) and effects of frequent regenerations on effluent (c) with different electrical conductivity (d) and pH
values (e) (C0 ¼ 42.9 mg/L).
769
regeneration. The voltages and currents of the stack during the
operation were shown in Fig. S2a. With once effluent every two
cycles and total treatment amount of 300 mL simulation waste-
water, the average removal rate of Cu(II) (C0 ¼ 54.8 mg/L) on the
anode was 82.3%, in which resin ion exchange and electromigration
accounted for 75.3% and 7.0%, respectively (Fig. 5(a and b)). The
contribution of resin on Cu (II) removal was the most obvious,
following electrosorption, and electromigration was the least
obvious. The effluent quality was better than that in Fig. 4(a)
because the resin load was increased from 5.0 mL to 8.0 mL. In
addition, it was stable of effluent quality in a certain range of
treatment capacity under free of resin and electrode regenerations.
To improve the contact probability between wastewater and resin,
a continued increase in resin loading amount from 8.0 mL to 12 mL
and a decrease of each wastewater treatment capacity from 50 mL
to 15 mL were set, and the result was showed in Fig. 5(c and d). That
was to say, the processing load of resin was decreased to 40%
compared with that of trials in Fig. 5(a). The average removal rates
of Cu(II) in effluents collected from anode- and cathode-chambers
were 95.7% and 87.6%, respectively. The above findings indicated
that increasing cycle times and resin load amount or reducing
770 C. Zhao et al. / Chemosphere 217 (2019) 763e772
water treatment capacity exhibited a certain effectiveness of Cu(II)
removal.
To investigate the effects of frequent resin and electrode re-
generations on Cu(II) removal rates, the resin regenerating liquids
were injected to two chambers for resin regeneration under 6.0 mA
positive DC for 1.5 min. Subsequently, the two regenerative solu-
tions were exchanged for electrode regeneration under 2.5 mA
reverse DC for 1.5 min. The voltages and currents of the stack during
the operation were shown in Fig. S2b. As shown in Fig. 5(c), there
exhibited a negligible effect on effluent quality after each regen-
eration. However, Cu(II) (0.671 mg/L) in the cathode regenerative
liquid was far below the amount of Cu(II) removed by the cathodic
electroadsorption under a lower current of electrode regeneration,
suggesting that there was less Cu(II) degeneration from the cathode
due to incomplete regeneration (Siekierka et al., 2018; Yu et al.,
2018).
As seen from the conductivity data in Fig. 5(d), a decline in
salinity was mainly attributed to the following two factors. On one
hand, the anions and cations that generated from the cathode- and
anode-chamber effluents after wastewater treatment were
enriched to the concentrated chamber. On the other hand, the
reverse adsorption of electrodes caused decline of anions and cat-
ions in the regeneration liquid from the cathode and anode
chambers during their electrode regenerations. Besides, it could be
seen from Fig. 5(d), there was a decline of the conductivity in
effluent of the concentrated chamber at the startup stage of CDI-
EDI stack because of the storage and transport of ion exchange
membranes. In spite of this, the conductivity was steadily increased
after stable operation, suggesting enrichments of anions and
cations.
The variations of pH values during the whole process including
wastewater treatment, resin and electrode regenerations were
depicted in Fig. 5(e). The results indicated that the initial pH of
Fig. 6. Removal rates of Nickel(Ⅱ) in primary settling filtrate using CDI-EDI stack (a), and the removal amounts of different chambers (b) with changing electrical conductivity (c) and
pH values (d) (CNi0 ¼ 4.76 mg/L, TDS 10.43 g/L, pH 12.84, electrical conductivity 17.82 mS/cm).
simulation wastewater that injected into the cathode- and anode-
chambers was 5.68, subsequently it exhibited an upward trend
with the deionization. It seems to be more reasonable that the
hydrogen ions in wastewater were mainly generated from copper
ion hydrolysis, thus the pH was rised again as Cu(II) was removed.
There was a decline in pH during the electroregeneration of cation
exchange resin, which mainly attributed to hydrolysis of water
molecules. Similarly, the emergence of hydroxyl caused a slight rise
of pH in cathode chamber during the electroregeneration of anion
exchange resin. Exerting a reverse direct current during the cath-
ode and anode regenerations, however, the previous Hþ and OH
were partially adsorbed, thus caused the rise of pH in the anode
chamber and the decline of pH in the cathode chamber. Besides, the
pH of electrolyte Na2SO4 in the concentrated chamber was gradu-
ally increased from 7.28 to 8.04, suggesting that the selectivity of
anion exchange membrane was preferred than that of cation ex-
change membrane.
3.5. Treatment effect of actual electroplating nickel-containing
wastewater using the novel EDI-CDI device
To avoid unnecessary waste during the frequent resin and
electrode regenerations, the actual electroplating nickel-containing
wastewater (Nickel(Ⅱ), 389.4 mg/L, pH 3.1, and salinity 0.567%) was
precipitated before injected into CDI-EDI stack. Moreover, the
purpose of precipitation was to overcome undesirable exchange
effect of cation exchange resin on heavy metal ion in acidic
wastewater. Therefore, the Nickel(Ⅱ) residue in the primary sedi-
mentation filtrate was 4.76 mg/L (salinity 0.998%) with pH 13 after
precipitation. The removal effect, electrical conductivity and pH of
the filtrate using the CDI-EDI stack was studied as shown in Fig. 6(a,
b, c, d). The voltages and currents of this stack during the operation
were shown in Fig. S2c. It was easily observed from Fig. 6(a), the
 C. Zhao et al. / Chemosphere 217 (2019) 763e772
average concentration of Nickel(Ⅱ) in effluents of anode- and
cathode-chambers were 1.61 mg/L and 2.01 mg/L, respectively. In
addition, there exerted a stable removal effect in the anode-
chamber effluents after the treatment of 540 mL nickel-
containing filtrate. The average removal rate of Nickel(Ⅱ) in the
anode-chamber effluent was 66.2% with a more stable removal
effect, showing a negligible effect of resin and anode regeneration
on effluent quality. However, the average removal of Nickel(Ⅱ) in
the cathode chamber was reduced from 62.2% to 55.4%. The slight
drop of effluent quality in the cathode chamber might be associated
with cathode desorption regeneration, thus it was possible to
improve effluent quality by increasing regeneration current and
time according to Fig. 4(b). Fig. 6(b) showed that a small amount of
Nickel(Ⅱ) might electro-migrate to the concentrated chamber
because the most of Nickel(Ⅱ) in the anode chamber underwent
cation exchange. It was easily observed from Fig. 6(c), the con-
ductivities of the cathode- and anode-effluents were decreased
significantly when the primary sedimentation filtrate was treated
using the CDI-EDI device. In addition, the effluent conductivities
after the resin and electrode regenerations were lower than that
before their regenerations. These findings revealed that the re-
generations of resin and electrode were capable of ensuring
effluent stability.
As seen from Fig. 6(d), an addition of 15 mL regeneration liquid
H2SO4 into the anode chamber was failure to maintain acid pH of
effluent after anode regeneration, because the initial pH of the
treated primary sedimentation filtrate was 12.8. Nevertheless, the
removal rate of Nickel(Ⅱ) in anode-chamber effluent was still
increased, suggesting that the cation exchange resin has been
partially regenerated. On the other hand, the nickel precipitation
was easily produced in the cathode-chamber effluent because of
the close pH values between cathode-chamber effluent and pri-
mary sedimentation filtrate. Under these circumstances, therefore,
it was unfavourable for anion adsorption of anion exchange resin as
well as electro-adsorption of Nickel(Ⅱ) by cathode, leading a lower
removal rate of Nickel(Ⅱ). Furthermore, the lower electro-
deregeneration current (2.5 mA) in this study caused an incomplete
regeneration of cathode, leading decline in removal rate of
Nickel(Ⅱ) in the cathode-chamber effluent. To sum up, it was not
feasible for anode compartment to treat the strong acid heavy
metal wastewater, whilst the cathode compartment could not be
applied in strong-alkaline heavy metal wastewater. It was worth
emphasizing that widening the current scope of resin regeneration
to a certain extent might effectively improve effluent quality from
the anode-chamber. It was necessary to optimize electrode-
regeneration current to prevent cathode incomplete regeneration,
thus improved the cathode-chamber effluent.
3.6. Charge efficiency evaluation of CDI-EDI stack
The energy consumptions were calculated as the results of
9.22 Wh/m3 (no regeneration) and 29.77 Wh/m3 (frequent regen-
eration), respectively, according to the voltage and current values
(Fig. S2(a, b)). Besides, the electricity efficiency of actual electro-
plating nickel wastewater was evaluated in this study. Meanwhile,
the energy consumption was evaluated as the result of 1.35 Wh/m3
according to the voltage and current values (Fig. S2(c)).
To sum up, the novel CDI-EDI stack was well integrated through
EDI and CDI techniques. The loaded resins reduced effectively the
internal resistance of CDI-EDI stack, thereby reduced the power
consumption during regeneration process. No matter how to treat
the simulated copper wastewater or the actual electroplating nickel
wastewater, the novel CDI-EDI stack exhibited more superiority in
energy consumption than that of the reported literature. Therefore,
the developed CDI-EDI stack might exhibit better practical
771
application in the treatment of heavy metal wastewater.
4. Conclusion
A novel CDI-EDI technology was designed and developed on
basis of the coordination mechanism of electromigration, electro
adsorption and ion exchange. This technique not only overcome
some defects of the conventional mixed bed resin in regeneration
difficulties and membrane fouling because of an individual loading
way of anion and cation resin, but also reduced the cost due to the
decrease of ion exchange membrane from four to two. It was easily
to remove heavy metal cations via electromigration and cation
exchange that was dominant way in anode chamber, as well as
anions by anode electro-adsorption. Reducing the processing load
of cation resin was capable of improving Cu(II) removal rate obvi-
ously. The introduction of high-adsorption CDI-activated carbon
electrode into the double-bed-double-film EDI device improved
obviously the removal rates of heavy metal ions. It was feasible to
effectively remove low-concentration heavy metal ions in waste-
water by tandem-type multistage devices. In addition, this CDI-EDI
stack exhibited lower energy consumption in resin and electrode
regenerations. Meanwhile, heavy metal ions could be enriched and
reused from regeneration fluid achieving resource recovery pur-
pose. Therefore, CDI-EDI would be a high efficiency, stability, en-
ergy saving and environment-friendly technique to treat the low-
concentration heavy metal wastewater.
Competing financial interest
The authors declare no competing financial interest and human
conflicts.
Acknowledgements
This work was supported by financial support from Natural
Science Foundation of Hebei Province (Project NO. E2016201179) as
well as National Natural Science Foundation of China (Project NO.
51308179). The authors are grateful for the Education Department,
Hebei Province (QN20131016) for their support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2018.11.071.
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