Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114

Contents lists available at ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers

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

Electrochemical treatment for simultaneous removal of heavy metals

and organics from surface finishing wastewater using sacrificial iron
anode
Vinh Ya a, Natacha Martin a,b, Yi-Hsuan Chou a, Yi-Ming Chen c, Kwang-Ho Choo d,
Shiao-Shing Chen e, Chi-Wang Li a,∗
a
Department of Water Resources and Environmental Engineering, Tamkang University, 151 Yingzhuan Road, Tamsui District, New Taipei City 25137, Taiwan
b
Ecole Nationale du Génie de l’Eau et de l’Environnement de Strasbourg, 1 quai Koch, 67000 Strasbourg, France
c
Department of Environmental Engineering, Vanung University, No.1, Wanneng Road, Zhongli District, Taoyuan City 32061, Taiwan
d
Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu 702-701, Republic of Korea
e
Institute of Environmental Engineering and Management, National Taipei University of Technology, No. 1, Sec. 3, Chung-Hsiao E. Road, Taipei 106, Taiwan

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

Article history: Surface finishing wastewater having low pH (∼2) and high conductivity (>11 mS/cm) was treated by
Received 30 October 2017 electrocoagulation (EC) or electrochemical Fenton (ECF) processes using sacrificial iron anodes. Under the
Revised 29 November 2017
same theoretical Fe dosage, the effects of electrolytic time, initial pH, and current density on the simul-
Accepted 4 December 2017
taneous removal of organic and heavy metal were investigated. A complete metal removal was achieved
Available online 24 December 2017
even at the low current density of 24.2 mA/cm2 and short electrolytic time of 4 min, whereas approx-
Keywords: imately 40% of chemical oxygen demand was removed. Increasing the electric current density did not
Sacrificing anode improve removal efficiencies, but consumed more electric energy. Low current conditions produced a
Precipitation brown color sludge associated with ferric hydroxide. On the contrary, a greenish color sludge was cre-
Fe(II)/Fe(III) species ated at a high current due to the formation of ferrous hydroxide. The formation of ferrous hydroxide
Surface finishing impacted the treated water quality. The ECF was employed to overcome the low COD removal by the EC,
Chemical sludge
achieving >67% of COD removal. The costs of ECF processes were slightly greater than that of chemical
coagulation, but achieving a lot greater heavy metal removals. ECF process can be a promising method
for simultaneous removal of heavy metal and organics from complex industrial wastewater.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction The conversion of Fe(II) to Fe(III) is facilitated under an alka-

Ferric salt is one of the most common coagulants used, al-
though ferrous salt is less expensive than ferric chloride [1–3]. Pre-
vious studies have explored the effectiveness of Fe(II) and Fe(III)
on contaminant removal [1,4-6]. Comparing ferric chloride, ferrous
sulfate, and alum for the treatment of landfill leachate, Aziz et al.
[4] reported that ferric chloride was the most effective coagulant
for the removal of contaminants (e.g., suspended solids, color, and
organics). For phosphate removal, the effectiveness of ferric has
been shown to be superior to that of ferrous [6]. To the best of
our knowledge, however, there have been no report on the com-
parison between ferric and ferrous ions with regard to contami-
nant removal in electrocoagulation (EC).
∗
Corresponding author.
E-mail address: chiwang@mail.tku.edu.tw (C.-W. Li).
line pH region in the presence of dissolved oxygen (DO). Hence,
increasing the electric current intensity can affect the ferrous-to-
ferric conversion rate since the rate of ferrous ion generation in-
creases with the electric current intensity and the oxidation of fer-
rous to ferric might be limited by the replenishing rate of DO. The
majority of previous studies did not pay much attention to the ef-
fect of electric current intensity/voltage on the conversion of fer-
rous to ferric ions [7–9]. Meanwhile, the most of EC studies nor-
mally examined the effect of the initial pH, allowing solution pH
to increase with time due to the reduction of protons to H2 on
the cathode [10–12]. Although the alkaline pH region might be
beneficial for the removal of metals [13] and the precipitation of
ferrous hydroxide, it can be detrimental to the organic matter re-
moval. Kobya et al. [14] showed that the chemical oxygen demand
of textile wastewater was preferably removed at acidic pH values.
Also, Can and Bayramoglu [15] showed that removal of dye and
two other organic molecules decreased with increasing pH.

https://doi.org/10.1016/j.jtice.2017.12.004
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
108 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114

In addition, previous studies reported contaminant removal by

Fenton process with hydrogen peroxide being produced through
the cathodic reduction of DO and ferrous ions being added chemi-
cally and/or generated electrolytically on a cathode [16–18]. It was
denoted as an electro-Fenton (EF) process [19,20]. When hydrogen
peroxide is added chemically and ferrous iron is generated elec-
trolytically from iron anodes, it is denoted as an electrochemical
Fenton process (ECF). Comparing the EC, EF, and ECF for treating
textile wastewater, Ghanbari and Moradi [19] reported that the ECF
was the most effective treatment method for the removal of chem-
ical oxygen demand and color removal. Yet, there is still the need
to conduct further studies for the simultaneous removal of heavy
metals and organics by electrochemical methods.
Therefore, this study focused on the treatment of plating
wastewater using the EC and ECF processes in terms of the simul-
taneous removal of heavy metals and organic matter. The effects of
electric current density and initial pH on the removal efficiencies
of contaminants were investigated under the same theoretical iron
dose. The content of ferrous and/or ferric hydroxides in the sludges
produced was investigated while discussing the implication of the
iron oxide species on the contaminant removal and the treated wa-
ter quality was discussed. Finally, the economical cost and treat-
ment efficiency of the electrochemical process for the treatment
of surface finishing wastewater was evaluated and compared with
Fig. 1. Schematic diagram of the experimental set-up used for EC and ECF.
chemical coagulation.

2.2. Electrochemical system

2. Materials and methods

A schematic diagram of the experimental setup used in this

2.1. Wastewater samples
work is shown in Fig. 1. A 0.25-L Pyrex glass was used as the
reactor. Both anode and cathode electrodes were made of iron
Wastewater samples were collected from a local surface finish-
plates with a dimension of 20 cm x 3 cm x 0.3 cm (effective area
ing plant, which generates three different streams of wastewaters,
of 20.7 cm2 ), and the spacing between two electrodes was 1 cm.
namely Cr-containing, CN-containing, and heavy metal-containing
The experiments were conducted at constant current mode using
wastewater. Both Cr- and CN-containing wastewaters are pre-
a direct current power supply (GPS-3030DD, Taiwan) with the vari-
treated with reduction and oxidation processes, respectively, to
ation of electric voltage being recorded using a multimeter (CEN-
convert Cr(VI) to Cr(III) and to oxidize cyanide ions before being
TER 122, Taiwan). The reactor was mixed with a magnetic stirrer
mixed with heavy metal-containing wastewater in an equalization
(Cimarecۛ Stirring Hot Plates, MA, USA) and an octagon magnetic
tank. The mixed wastewater (flow rate approximately 30 m3 /h)
stir bar of 51 mm (VWR Spinbar®) at the agitation rate of 100 rpm.
is then treated with traditional chemical coagulation, sedimenta-
The pH value was maintained only for the ECF experiments with
tion, and sand filtration before being discharged into a local river
a pH controller (PC3200, Suntex Instruments, Taiwan) using 1 M
stream. The wastewater sample used in this work was collected
H2 SO4 .
from the equalization tank. Table 1 summarizes the qualities of
the wastewater used. The solution pH was acidic (2.0). Zinc was
2.3. Electrocoagulation tests
the main heavy metal present in the wastewater at a concentration
of 190 mg/L, whereas the nickel, copper, and chromium ions were
For EC experiments, a 0.2-L wastewater sample was placed in
also present (<1 mg/L). The conductivity (11.4 mS/cm) of wastew-
the reactor with the pH being adjusted to predetermined pH val-
ater was high enough to apply the EC treatment. For the experi-
ues using 5 N NaOH or 1 M H2 SO4 solution. After the electric cur-
ments to examine the effects of electrolytic time and current, the
rent intensity was set to the desired value, the experiment was
wastewater sample pH was first adjusted to 7. The neutralization
started by turning on the power supply. At the end of the reaction,
step is the pretreatment step employed in the surface finishing
the solution was poured into a sedimentation column and set qui-
plant, and is adopted in this study before EC. Flocs were created
escently for 10 min to separate the sludge from the solution. The
after the pH adjustment due to the precipitation of Cr(OH)3 .
final pH of the treated water was recorded after the sludge sepa-
ration. Sampling was done for the determination of the total dis-
Table 1 solved iron concentration under completely mixed condition. Sam-
Qualities of raw wastewater collected from a surface ples for heavy metals and COD concentration analyses were col-
finishing plant. lected and filtered through a 0.45 μm membrane filter. Three repli-
Item Value cates were performed, and the mean and one standard deviation
from the mean were reported.
pH 2
Conductivity, mS/cm 11.35
COD, mg/L 246.81 2.4. Electrochemical Fenton tests
TOC, mg/L 91.4
Zinc, mg/L 190.10 For ECF experiments, the iron dose was determined based on
Total Cr, mg/L 87.50 the optimum iron dose obtained from the EC process. The solu-
Iron, mg/L 24.88
Nickel, mg/L 0.94
tion pH level (pH 3) was maintained during the reaction using
a pH controller. A desired amount of H2 O2 was added into 0.2 L
 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114
of wastewater to commence the experiment. After the ECF reac-
tion, the solution was transferred to a jar test apparatus to extend
the Fenton reaction for another 15 min. The solution pH was then
raised to 7 to precipitate out the dissolved iron, and the solution
was mixed for another 15 min. Sampling was done as described
above in Section 2.3. Three replicates were performed, and the
mean and one standard deviation from the mean were reported.
2.5. Chemical coagulation tests
To evaluate the treatment efficiency of chemical coagulation as
a control, wastewater (1 L) was treated using ferric chloride with
rapid mixing at 100 rpm for 5 min. The mixture was then slowly
mixed (30 rpm) for another 20 min with the pH maintained at 7.
The coagulant dosage of 174 mg Fe/L was chosen based on the op-
timum dosage for complete removal of metals in EC experiments
(see Section 3.1). Sampling was done as described in Section 2.3.
The same chemical coagulation procedure was applied for syn-
thetic wastewater containing 1 mM of Ni using either ferrous sul-
fate or ferric chloride to compare Ni removal. Three replicates were
performed, and the mean and one standard deviation from the
mean were reported.
2.6. Analytical methods
A flame atomic absorption spectrophotometer (GBC 932 plus,
Australia) was used for analysis of zinc, nickel, total iron, and
total chromium concentrations. The total organic carbon (TOC)
was analyzed using a TOC analyzer (TOC-V, Shimadzu, Japan),
whereas the chemical oxygen demand (COD) was analyzed ac-
cording to the Standard Method (5220 C) [21]. Three repeated
measurements were performed for each sample. After the reaction
with dichromate, the COD was determined using a potentiometric
automatic titrator (AT-420, Japan) equipped with an auto piston
burette (APB-410, Japan). A hand-held conductivity/total dissolved
solid meter (CON6 & TDS6, USA) was employed to determine the
conductivity of wastewater. The ferrous iron concentration was
determined colorimetrically at a wavelength of 510 nm (Cary 50,
Varian, USA) using phenanthroline as the indicator following the
Standard Methods (3500-Fe B). Samples (50 ml) were directly
acidified using concentrated HCl (1 ml) at the time of collection.
The ferric iron concentration was determined by subtracting the
ferrous iron concentration from the total iron concentration.
To check the distribution of ferrous and ferric iron in the sludge,
the percentage of Fe(II) in the sludge was determined after re-
dissolving the sludge with sulfuric acid [22]. After the sample was
centrifuged (60 0 0 rpm, 4 min) and the supernatant was decanted,
a peanut size of sludge was collected and re-dissolved in a glass
vial with concentrated sulfuric acid (5 ml) for the determination of
iron content.
3. Results and discussion
3.1. Effects of electrochemical iron dosage
The theoretical coagulant dose, which is supplied electrochemi-
cally from sacrificial iron anodes is a function of electric current in-
tensity (0.5 A) and time (1–8 min), and so can be estimated based
on the Faraday’s law. The effects of electrochemical Fe coagulant
dose on heavy metals and COD removal efficiencies were first in-
vestigated and the results are shown in Fig. 2. Rapid and substan-
tive removal of Zn and COD (>95% and >40%, respectively) oc-
curred within 1 min, but no further removal was achieved with
extended reaction times. The average current efficiency was esti-
mated to be 118 ± 8.3% (see Fig. S1), suggesting that anodic release
109
120 10
COD removal Zn removal
Ni removal Reaction time
100
8
Removal efficiency, %
Reaction time, min
80
6
60
4
40
2
20
0 0
44 87 174 261 348
Electrochemical iron dose, mg Fe/L
Fig. 2. Variations in removal efficiency of COD, Zn, and Ni with theoretic elec-
trochemical Fe dose. Initial pH = 7; magnetic stirring rate 100 rpm; current = 0.5 A
(corresponding to a current density of 24.15 mA/cm2 ). Error bars represent one stan-
dard deviation from the mean of triplicate experiments.
of iron was possibly boosted via galvanic cell potentials in wastew-
ater. In other words, other coexisting metal ions (e.g., Ni2+ ), which
has greater reduction potential, may be reduced on Fe anode and
be responsible for the extra iron released from the anode.
Because Ni ions have a stronger affinity toward organic lig-
ands than Zn ions [23] and the formation of metal complexes
[24,25] may affect metal removal, the amount of Fe dose needed to
achieve a complete removal of nickel was higher than that for Zn
(174 vs. 44 mg Fe/L). On the other hand, Cr removal was complete
(∼100%) simply with a quick pH adjustment (data not shown). The
overall energy consumption increased linearly with time (Fig. S2).
Fig. 3 shows the variations of sludge color and Fe(II) content
in the sludge when they were settled in a sedimentation column.
The sludge color was brown when the solution was treated for less
than 2 min, but it turned greenish with longer reaction times. It
can be hypothesized that the change of colors should be associ-
ated with the oxidation state of iron ions [i.e., Fe(II) and Fe(III)].
After short reaction times, the Fe(II) released from the Fe an-
ode should be further oxidized to Fe(III) by dissolved oxygen and
thereby, formed brownish ferric hydroxide precipitates. However, a
large amount of Fe(II) generated with longer electrolysis may not
well converted to Fe(III) due to the depletion of dissolved oxygen
and thus, the Fe(II) remained and formed greenish ferrous hydrox-
ides. Indeed, the percentage of ferrous ion to the total iron ions
increased from ∼30% to >60% with reaction time (Fig. 3b).
Previous studies [4,6] reported that ferric salts were superior
for removing contaminants (color, COD, phosphate) than ferrous
salts during chemical coagulation. In this study, however, discrim-
inating the effects between Fe(II) and Fe(III) appeared to be very
complicated because the solution chemistry (e.g., pH, dissolved
oxygen, etc.) changed with time simultaneously. Considering the
amount of iron ions theoretically generated (e.g., 43.5 mg/L and
87 mg/L at reaction times of 1 and 2 min, respectively), >10% of
the iron remained dissolved in the aqueous phase since the final
solution pH was still unfavorable for the precipitation of ferrous
hydroxide (see Fig. S3).
Fraction of the electro-coagulated sludge floated due to the
gases (e.g., H2 ) formed and trapped in the sludge floc [26]. There
was an exception for the case of 1-min reaction, with which
the sludge was well settled at the bottom of the column reactor
(Fig. 3a), possibly due to small gas bubbles inside iron hydroxide
flocs (i.e., denser flocs). As a result, proper removal of gas bubbles
generated is required for enhanced sludge settling.
110 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114

b 100 9.0
Pecentage of Fe(II)/Tot Fe
Final pH
8.5
80

8.0
Fe(II)/Tot Fe, %

60

Final pH
7.5

40
7.0

20
6.5

0 6.0
1 2 4 6 8
Reaction time, min
Fig. 3. (a) Photos of sludge settling after EC with reaction times and (b) the percentage of Fe(II) in the sludge and solution pH as a function of reaction time. Fixed current
of 0.5 A; sedimentation time of 10 min. Error bars represent one standard deviation from the mean of triplicated experiments.

3.2. Effects of electric current density charge applied, i.e., the same theoretical iron dose of 174 mg/L and
pH 7.0. The current density applied was in the range from 4.83
The electric current density is an important parameter that af- to 77.29 mA/cm2 , while the reaction time in the range from 20 to
fects the efficiency of EC processes [27,28]. The electric current 1.25 min. As indicated in Fig. 4, both COD and heavy metal removal
density can affect the size and production rate of bubbles, which efficiencies were independent of the current density applied. The
will have impacts on the flotation of the sludge [27]. With this, color of sludge was all greenish, showing that the dominant pre-
the effects of electric current density on the treatment of elec- cipitate was ferrous hydroxide (see Fig. S4). The flotation of sludge
troplating wastewater were explored under the same total electric occurred markedly with increasing the electric current due to more
gases produced, which was expectable from the result of Fig. 3.

120 25
COD removal Zn removal
8.0 16
Ni removal Reaction time
100
20 14
Energy (kwh/m3) or Voltage (V)
Removal Efficiency, %

Reaction time, min

80 7.9 12
15
y = 0.1609x + 1.0108 10
60 R² = 0.9998
pH

7.8 Final pH 8
10
40 Energy consumption 6
Voltage
5 7.7 4
20 y = 0.0289x + 0.1426
R² = 0.9998
2
0 0
4.83 9.66 19.32 38.65 77.29 7.6 0
Current density, mA/cm2 0 20 40 60 80
Current density, mA/cm2
Fig. 4. Effects of electric current density on the removal efficiencies at a constant
total theoretical Fe dose of 174 mg Fe/L. Error bars represent one standard deviation Fig. 5. Effects of electric current intensity on electric voltage, energy consumption,
from the mean of triplicate experiments. and final pH at a constant total theoretical Fe dose of 174 mg Fe/L.
 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114 111

b
100 10
Percentage of Fe(II)/Tot Fe
Final pH
80 8
% of Fe(II)/Tot Fe

60 6

Final pH
40 4

20 2

0 0
2 3 4 5 6 7 8 9
Initial pH
c 200 200

175 175
Sludge concentration, mg Fe/L
Fe(II) in solution, mg/L

150 150

125 125
Fe(II) in solution
100 Sludge concentration 100

75 75

50 50

25 25

0 0
2 3 4 5 6 7 8 9
Initial pH
Fig. 6. (a) Photos of sludge settling after EC with various initial pH values. (b) The percentage of Fe(II) in the sludge and final pH as a function of initial pH values. (c)
Fe(II) concentration in solution and sludge concentration. Total theoretical Fe dosage = 174 mg Fe/L; electric current = 0.5 A; reaction time = 4 min; and sedimentation time of
10 min. Error bars represent one standard deviation from the mean of triplicated experiments.

Fig. 5 shows the effects of electric current density on the elec-
tric voltage, energy consumption, and final pH values. There was a
linear relationship between current density and voltage since wa-
ter conductivity remained identical. The energy consumption was
also linearly correlated to the current because the time required to
dose the same iron amount was inversely proportional to electric
current intensity. When the current density increased from 4.83 to
77.3 mA/cm2 , the voltage increased from 1.68 to 13.4 leading to the
energy consumption rise from 0.28 to 2.38 kW h/m3 . The final pH
level was always higher than the initial pH while being stabilized
in the range 7.7–8.0.
3.3. Effects of solution pH
The initial pH may affect the performance of EC processes
[27–29] and thus, this study investigated the effects of initial
pH values (from 2 to 9) while conducting the EC experiments
at the fixed current intensity (0.5 A) and reaction time (4 min)
112 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114
120
COD renoval Zn removal Ni removal Tot. Cr removal
100
Removal efficiency, %
80
60
40
20
0
2 3 4 5 6 7
Initial pH
Fig. 7. Contaminants removal as a function of initial pH levels when the constant
total theoretical iron dose of 174 mg Fe/L was applied at an electric current den-
sity of 24.15 mA/cm2 . Error bars represent one standard deviation from the mean of
triplicate experiments.
corresponding to the total theoretical Fe dose of 174 mg/L. The
original electroplating wastewater pH level was 2. Fig. 6(a) shows
the characteristics of flocs settling and treated water color. The
brown color sludge produced with an initial pH of <7 indicates
the precipitation of ferric hydroxide, whereas the greenish color of
the sludge collected from pH 7–8 indicates the possibility of fer-
rous hydroxide precipitation. As shown in Fig. 6(b), the content of
ferrous iron in the sludge was <16% when produced at the initial
pH values ranging from 2 to 4. However, the Fe(II) content kept in-
creasing with pH, e.g., 32% at pH 5 and ∼80% at pH > 8. With the
initial pH values of >8, the final pH values reached >8.6, at which
ferrous hydroxide starts to precipitate out (see Fig. S5). Although
the final pH values (2–7.23) obtained with the initial pH levels of
<7 are still below the levels to form ferrous hydroxide solids, local-
ized elevated pH near the cathode should induce the precipitation
of ferrous hydroxide. Although the sludge produced is mainly com-
posed of ferric hydroxide at low initial pH values, the majority of
iron species, which are anodically generated, are still in the aque-
ous phase. When the initial pH was <5, the Fe(II) concentration in
the aqueous phase was in the range of 140–180 mg/L, correspond-
ing to 79–100% of the theoretic iron added (Fig. 6(c)).
Fig. 7 shows the effect of initial pH on the COD and heavy metal
removal efficiencies. They increased with higher initial pH value
from 2 to 7 and leveled off afterward. The removal efficiency of
zinc and nickel increased dramatically and reached almost 100%
when the initial pH value exceeded 7. The COD removal reached a
maximum of about 50% when pH was >6. The low removal effi-
ciencies observed under the acidic pH conditions were attributed
to the small amount of iron hydroxide precipitated. As indicated in
Fig. 6(c), the iron hydroxide sludge concentrations are in the range
of 22–53 mg Fe/L, corresponding to only 12.6–30% of iron dosed. It
is interesting to note that at the initial pH of 6, the COD removal
reached a maximum value of ∼50%, even though only half of the
anodically produced iron was precipitated out (see Fig. 6(c)). The
result implies that the removable portion of the organic materi-
als may account for only 50% of the COD. In addition, the sludge
produced at pH 6 had a larger amount of ferric hydroxide and so
provided a better capability to remove COD than those produced
at alkaline initial pH values, where ferrous hydroxide was domi-
nant. Consequently, ferric ions should be superior in contaminants
removal to ferrous ions due to the charge effect on chemical coag-
ulation [4,6].
a
120
COD removal Zn removal Ni removal
100
Removal Efficiency, %
80
60
40
20
8 9
0
0 3 5 7 10
H2O2:Fe(II) ratio
b
100
80
Ni Removal Efficiency, %
60
40
20
0
Fe(II) Fe(III)
Coagulant
Fig. 8. (a) Effect of H2 O2 :Fe2+ molar ratio on the removal efficiencies at a fixed
theoretical Fe dose of 174 mg Fe/L. Mixing = 100 rpm; electrode area = 20.7 cm2 . (b)
Ni removals achieved by chemical coagulation using ferrous sulfate and ferric chlo-
ride under the following conditions. Initial Ni = 1 mM. Fe dose = 174 mg Fe/L; pH 7;
reaction time = 25 min (5 min rapid mixing and 20 min slow mixing).
3.4. Electrochemical Fenton process for enhanced COD removal
Due to the high COD concentration remaining in the EC treated
water [30], the ECF process was further considered so as to meet
the more stringent COD discharge limit (e.g., 100 mg/L in Taiwan).
Experiments were performed at a fixed current of 0.5 A for 4 min,
corresponding to the theoretical Fe dose of 174 mg/L. The ratio
of H2 O2 :Fe2+ dictates the relative contribution of oxidation and
coagulation processes in ECF. At a low H2 O2 :Fe2+ ratio, coagula-
tion is the dominant process while chemical oxidation dominates
at a high H2 O2 :Fe2+ ratio [31]. Fig. 8(a) shows the effects of the
H2 O2 :Fe2+ molar ratio on the contaminant removal efficiency. No
H2 O2 addition (i.e., H2 O2 :Fe2+ ratio = 0) corresponds to the EC pro-
cess at a fixed pH of 3.0. The overall COD removal efficiency in-
creased until the H2 O2 :Fe2+ ratio reached 5, and started decreas-
ing thereafter, possibly due to the scavenging effect of the excess
H2 O2 by OH radicals [19]. The H2 O2 :Fe2+ molar ratio of 5 appeared
to be optimal in the COD removal efficiency (67% of the COD was
removed with the residual COD of ∼70 mg/L).
Zn removal was quite substantial (>97%) without any signif-
icant difference between EC and ECF. However, Ni removal de-
creased slightly for ECF process with the increase of H2 O2 dose.
The decrease may be associated with the relative amount of fer-
ric and ferrous hydroxide in the sludge. In the EC process, the flocs
produced may contain both Fe(OH)2 and Fe(OH)3 , but all Fe(II) ions
 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114
Table 2
A summary of the operation costs of EC process at different current densities.
Current density, mA/cm2 Electricity cost, USD/m3 Electrode cost, USD/m3
4.83 0.04 0.24
9.66 0.06 0.24
19.32 0.10 0.24
38.65 0.18 0.24
77.29 0.35 0.24
Table 3
Comparisons of the operation costs of EC and ECF processes.
Current density, mA/cm2 EC process, USD/m3 ECF process, USD/m3
4.83 0.28 –
9.66 0.30 – chemical coagulation is less than that of ECF, the heavy metal re-
19.32 0.34 0.88
38.65 0.42 –
77.29 0.59 –
are oxidized to Fe(III) by H2 O2 added in the ECF process. To eluci-
date the possible cause for the decrease of Ni removal in ECF, a
comparison of Ni removal by chemical coagulation using ferric or
ferrous salt was then conducted. As shown in Fig. 8(b), ferrous salt
removed nickel greater than ferric salt at the same coagulant doses
(e.g., 72.6% and 53.6%, respectively), although the reason of Fe(OH)2
being superior than Fe(OH)3 for Ni removal is unclear.
3.5. Economic evaluation
The economic evaluation of the EC and ECF was conducted and
compared with normal chemical coagulation. Electricity, chemi-
cal costs, and electrode material prices were obtained from local
markets. The electricity price is assumed to be 0.15 USD/kW h
during summer time in Taiwan. The prices of ferric salt, H2 O2 ,
and iron electrode are 2.91, 1.43, and 1.37 USD/kg, respectively.
Table 2 shows the energy and electrode costs for EC operated at
various current densities, but with a fixed iron dosage of 174 mg/L.
The total operation cost ranged from 0.28 to 0.59 USD/m3 for
EC, whereas the ECF process costs 0.88 USD/m3 as indicated in
Table 3. The cost of chemical coagulation process using ferric salt
was evaluated at the same iron dose, and was estimated to be
∼0.57 USD/m3 . Although the cost of chemical coagulation is less
than that of ECF and is almost the same as that of EC operated at
the highest current density, the heavy metal removal efficiency by
chemical coagulation is much lower. The Zn and Ni removal effi-
ciencies are only 87.6 and 44.7%, respectively, while almost 100%
removal could be achieved by both EC and ECF (Table S1).
4. Conclusions
Both EC and ECF processes using iron anodes were applied
to remove heavy metals and organic contaminants simultaneously
from surface finishing plant wastewater. With a theoretical Fe
dosage of 174 mg/L, the EC achieved almost complete removal of
metals, but only 40% of COD. Because the limitation of DO and
the increase of pH favor the formation of ferrous hydroxide, the
color of sludge generated changed from brown to greenish with
reaction time. The COD removal increased with higher initial pH
levels and reached a maximum of about 50% at a pH of >6. The
low COD removal efficiency observed under acidic pH conditions
was attributed to the formation of iron oxyhydroxides and their
amphoteric behaviors. The heavy metals removal efficiencies in-
creased dramatically with higher initial pH levels, reaching almost
100% when the initial pH value was >7.
Ferric hydroxide was the main precipitate with an initial pH
of <7, whereas ferrous hydroxide was dominant for the initial
113
pH range between 7 and 9. The ferrous iron content in chemical
sludge was 16% with acidic initial pH values ranging from 2 to 4.
It increased to 32% at pH 5 and even to ∼80% at initial pH levels
of >8. Although the sludge produced was mainly composed of fer-
ric hydroxide at low initial pH values, the majority of iron species
anodically generated remained dissolved as Fe(II) in the solution
phase for the initial pH levels of <5, being present in the range
of 140–180 mg Fe/L (corresponding to 79–100% in theoretical iron
dose).
ECF enhanced the COD removal efficiency exceeding >67% at
the H2 O2 :Fe2+ molar ratio of 5, which met the regulatory COD
guideline of 100 mg/L. However, the cost of ECF process was the
highest among three processes investigated. Although, the cost of
moval efficiency by the chemical coagulation is much lower.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2017.12.004.
References
[1] Zhang Z, Wang Y, Leslie GL, Waite TD. Effect of ferric and ferrous iron addi-
tion on phosphorus removal and fouling in submerged membrane bioreactors.
Water Res. 2015;69:210–22.
[2] Li T, Wang H, Dong W, Liu T, Ouyang F, Zhang Q. Phosphate removal during
Fe(II) oxidation in the presence of Cu(II): characteristics and application for
electro-plating wastewater treatment. Sep. Purif. Technol. 2014;132:388–95.
[3] Kim M-K, Zoh K-D. Occurrence and removals of micropollutants in water en-
vironment. Environ. Eng. Res. 2016;21:319–32.
[4] Aziz HA, Alias S, Assari F, Adlan MN. The use of alum, ferric chloride and fer-
rous sulphate as coagulants in removing suspended solids, colour and COD
from semi-aerobic landfill leachate at controlled pH. Waste Manage. Res.
2007;25:556–65.
[5] Oikonomidis I, Burrows LJ, Carliell-Marquet CM. Mode of action of fer-
ric and ferrous iron salts in activated sludge. J. Chem. Technol. Biotechnol.
2010;85:1067–76.
[6] Zhang M, Qiu L, Yu XQ, Ding S, Ji JY, Zheng P. Comparison of phosphorus
removal processes by ferrous salts and ferric salts. J. Chem. Eng. Chin. Univ
2013;27:519–25.
[7] Jin W, Du H, Zheng S, Zhang Y. Electrochemical processes for the environmen-
tal remediation of toxic Cr(VI): a review. Electrochim. Acta 2016;191:1044–55.
[8] Hossain MM, Mahmud MI, Parvez MS, Cho HM. Impact of current density,
operating time and pH of textile wastewater treatment by electrocoagulation
process. Environ. Eng. Res. 2013;18:157–61.
[9] Sahu O, Mazumdar B, Chaudhari PK. Treatment of wastewater by electrocoag-
ulation: a review. Environ. Sci. Pollut. Res. 2014;21:2397–413.
[10] Harif T, Khai M, Adin A. Electrocoagulation versus chemical coagulation: coag-
ulation/flocculation mechanisms and resulting floc characteristics. Water Res.
2012;46:3177–88.
[11] Al-Qodah Z, Al-Shannag M. Heavy metal ions removal from wastewater us-
ing electrocoagulation processes: a comprehensive review. Sep. Sci. Technol.
2017;52:1–28.
[12] An C, Huang G, Yao Y, Zhao S. Emerging usage of electrocoagulation technology
for oil removal from wastewater: a review. Sci. Total Environ. 2017;579:537–56.
[13] Al Aji B, Yavuz Y, Koparal AS. Electrocoagulation of heavy metals contain-
ing model wastewater using monopolar iron electrodes. Sep. Purif. Technol.
2012;86:248–54.
[14] Kobya M, Bayramoglu M, Eyvaz M. Techno-economical evaluation of electro-
coagulation for the textile wastewater using different electrode connections. J.
Hazard. Mater. 2007;148:311–18.
[15] Can OT, Bayramoglu M. A comparative study on the structure–performance re-
lationships of chemically and electrochemically coagulated Al(OH)3 flocs. Ind.
Eng. Chem. Res. 2014;53:3528–38.
[16] Özcan A, Gençten M. Investigation of acid red 88 oxidation in water
by means of electro-Fenton method for water purification. Chemosphere
2016;146:245–52.
[17] Ren G, Zhou M, Liu M, Ma L, Yang H. A novel vertical-flow electro-Fenton re-
actor for organic wastewater treatment. Chem. Eng. J. 2016;298:55–67.
[18] Ma L, Zhou M, Ren G, Yang W, Liang L. A highly energy-efficient flow-through
electro-Fenton process for organic pollutants degradation. Electrochim. Acta
2016;200:222–30.
[19] Ghanbari F, Moradi M. A comparative study of electrocoagulation, electro-
chemical Fenton, electro-Fenton and peroxi-coagulation for decolorization of
real textile wastewater: electrical energy consumption and biodegradability
improvement. J. Environ. Chem. Eng. 2015;3:499–506.
[20] Khataee A, Sajjadi S, Rahim Pouran S, Hasanzadeh A. Efficient electrochemical
generation of hydrogen peroxide by means of plasma-treated graphite elec-
trode and activation in electro-Fenton. J. Ind. Eng. Chem. 2017;56:312–20.
114 V. Ya et al. / Journal of the Taiwan Institute of Chemical Engineers 83 (2018) 107–114
[21] APHA, AWWA, WEF. Standard Methods for the Examination of Water and
Wastewater. Washington, DC: American Public Health Association American
Water Works Association Water Environment Federation; 1998.
[22] Stucki JW. The quantitative assay of minerals for Fe2+ and Fe3+ using
1,10-phenanthroline: II. A photochemical method 1. Soil Sci. Soc. Am. J.
1981;45:638–41.
[23] MINEQL+ Version 4.6, Environmental Research Software.
[24] Li C-W, Yu J-H, Liang Y-M, Chou Y-H, Park H-J, Choo K-H, Chen S-S. Ni removal
from aqueous solutions by chemical reduction: impact of pH and pe in the
presence of citrate. J. Hazard. Mater. 2016;320:521–8.
[25] Chou Y-H, Yu J-H, Liang Y-M, Wang P-J, Li C-W, Chen S-S. Recovery of Cu(II)
by chemical reduction using sodium dithionite: effect of pH and ligands. Water
Sci. Technol. 2015;72:2089–94.
[26] Bassyouni DG, Hamad HA, El-Ashtoukhy ESZ, Amin NK, El-Latif MMA. Com-
parative performance of anodic oxidation and electrocoagulation as clean pro-
cesses for electrocatalytic degradation of diazo dye Acid Brown 14 in aqueous
medium. J. Hazard. Mater. 2017;335:178–87.
[27] Adhoum N, Monser L, Bellakhal N, Belgaied J-E. Treatment of electroplating
wastewater containing Cu2+ , Zn2+ and Cr(VI) by electrocoagulation. J. Hazard.
Mater. 2004;112:207–13.
[28] Al-Shannag M, Al-Qodah Z, Bani-Melhem K, Qtaishat MR, Alkasrawi M. Heavy
metal ions removal from metal plating wastewater using electrocoagulation:
kinetic study and process performance. Chem. Eng. J. 2015;260:749–56.
[29] Akbal F, Camci S. Treatment of metal plating wastewater by electrocoagulation.
Environ. Prog. Sustain. Energy 2012;31:340–50.
[30] Sandhwar VK, Prasad B. Comparative study of electrocoagulation and electro-
chemical Fenton treatment of aqueous solution of benzoic acid (BA): optimiza-
tion of process and sludge analysis. Kor. J. Chem. Eng. 2017;34:1062–72.
[31] Neyens E, Baeyens J. A review of classic Fenton’s peroxidation as an advanced
oxidation technique. J. Hazard. Mater. 2003;98:33–50.