water

Article
Electrocoagulation: A Promising Method to Treat and
Reuse Mineral Processing Wastewater with
High COD
Gaogui Jing 1,2 , Shuai Ren 1,2 , Yuesheng Gao 3 , Wei Sun 1,2 and Zhiyong Gao 1,2, *
1 School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China;
gaoguijing@csu.edu.cn (G.J.); renshuai@csu.edu.cn (S.R.); sunmenghu@126.com (W.S.)
2 Key Laboratory of Hunan Province for Clean and Efficient Utilization of Strategic Calcium-Containing
Mineral Resources, Central South University, Changsha 410083, China
3 Department of Chemical Engineering, Michigan Technological University, Houghton, MI 49931, USA;
ygao4@mtu.edu
* Correspondence: zhiyong.gao@csu.edu.cn




Received: 23 January 2020; Accepted: 18 February 2020; Published: 21 February 2020


Abstract: Mineral processing wastewater contains large amounts of reagents which can lead to
severe environmental problems, such as high chemical oxygen demand (COD). Inspired by the
wastewater treatment in such industries as those of textiles, food, and petrochemistry, in the present
work, electrocoagulation (EC) is applied for the first time to explore its feasibility in the treatment of
wastewater with an initial COD of 424.29 mg/L from a Pb/Zn sulfide mineral flotation plant and its
effect on water reuse. Typical parameters, such as anode materials, current density, initial pH, and
additives, were characterized to evaluate the performance of the EC method. The results showed that,
under optimal conditions, i.e., iron anode, pH 7.1, electrolysis time 70 min, 19.23 mA/cm2 current
density, and 4.1 g/L activated carbon, the initial COD can be reduced to 72.9 mg/L, corresponding to a
removal rate of 82.8%. In addition, compared with the untreated wastewater, EC-treated wastewater
was found to benefit the recovery of galena and sphalerite, with galena recovery increasing from
25.01% to 36.06% and sphalerite recovery increasing from 59.99% to 65.33%. This study confirmed
that EC is a promising method for the treatment and reuse of high-COD-containing wastewater in the
mining industry, and it possesses great potential for wide industrial applications.

Keywords: mineral processing; wastewater treatment; flotation; electrocoagulation (EC); chemical

oxygen demand (COD)

1. Introduction
Wastewater from mineral processing remains a headache for the mining industry not only because
of its large volume, but more importantly, its hazardous components. Among the complicated
residual reagents, the organic reagents receive the most attention due to their high chemical oxygen
demand (COD) levels. Direct discharge of wastewater causes serious environmental pollution, while
its reuse as feed water without proper treatments causes great harm to the recovery and grade
of valuable minerals [1]. To solve this problem, techniques for wastewater treatment have been
intensively developed in the mining industry, such as natural settling, flocculating setting, chemical
oxidation, adsorption, and biodegradation to remove COD [2]. However, these techniques possess
such disadvantages as inefficiency in COD removal, extreme operating conditions, high operation cost,
huge instrument investment, etc. It is worth noting that coagulation–flocculation, the most common
technique in beneficiation plants because of its economy, usually has a relative low COD removal rate
of only 35% [3].

Water 2020, 12, 595; doi:10.3390/w12020595 www.mdpi.com/journal/water

Water 2020, 12, 595 2 of 12

Electrocoagulation (EC) has become widely used as a wastewater treatment technology in the
past decade and has exhibited a satisfactory removal of COD in diverse fields, such as in textiles [4],
the food industry [5], dairying [6], brackish water [7], and potable water [8]. Its advantages include
easy operation, small area occupation, and a high degree of automation. In the process of EC, iron or
aluminum is usually adopted as the anode material, and each one can lead to a series of similar redox
reactions. Taking the iron electrode as an example, simplified reactions occurring in acidic and alkaline
solutions can be described as follows [9]:
Under acidic conditions:
+
Fe(s) → Fe2(aq )
+ 2e− (1)

2H2 O → O2 + 4H+ + 4e− (2)

+
4Fe2(aq )
+ 10H2 O(l) + O2(g) → 4Fe(OH)3(s) + 8H+
(aq)
(3)

Under alkaline conditions:

+
Fe(s) → Fe2(aq )
+ 2e− (4)

Fe2+ + 2OH− → Fe(OH)2 (5)

As shown in above equations, the iron anode is used to generate ions in the aqueous
medium. The generated iron ions are then immediately hydrolyzed to form Fe(OH)3 , monomeric
ions, and polymeric hydroxy complexes such as Fe(H2 O)6 3+ , Fe(H2 O)4 (OH)2+ , Fe2 (H2 O)6 (OH)4 4+ ,
Fe2 (H2 O)8 (OH)2 4+ , and Fe(H2 O)5 (OH)2+ , depending on the solution pH [10]. These hydroxides and
polyhydroxides are excellent adsorbents for counter ions and organic pollutants. In some cases, they
can even form complexes with some of the organics [11]. Pollutants in the wastewater can be treated
by physical and chemical attachment to hydroxides or chemical reactions [12]. After the EC treatment,
separation of precipitation from the liquid is traditionally achieved via a filter process. Then, the filtered
and separated sludge is usually treated using the incineration and landfill treatments [13].
In this paper, EC treatment of sulfide mineral flotation wastewater was applied for the first time,
and the effects of different parameters like anode materials, current density, initial pH, electrolysis
time, and additives on COD removal rate were investigated. The treated water was then recycled as
feed water in the sulfide ore flotation. For comparison, untreated wastewater and fresh water were
used to assess the effects of EC-treated water on the grade and recovery of galena and sphalerite.

2. Materials and Methods

2.1. Samples, Reagents, and Analytical Methods

Samples of mineral processing wastewater and actual ores were all from a Pb-Zn beneficiation
plant located in Southern China. The plant had three different types of wastewater, namely Pb-Zn
flotation wastewater, pyrite concentrate wastewater, and pyrite tailing wastewater, accounting for
70%, 14%, and 16% of the total amount, respectively. In this study, three different types of wastewater
samples were mixed at the above ratio to obtain the mixed wastewater samples. The pH and COD
values of each wastewater are shown in Table 1.

Table 1. Chemical oxygen demand (COD) and pH values of mineral processing wastewater samples in
a Pb-Zn beneficiation plant.

Sample Name pH COD (mg/L)

Pb-Zn flotation wastewater 11.90 434.7
Pyrite concentrate wastewater 9.11 245.3
Pyrite tailing wastewater 8.29 603.2
Mixed wastewater 11.83 424.9
Water 2020, 12, 595 3 of 12

Water 2020, 12, 595 3 of 12

The H2 O2 (30% pure), H2 SO4 , HCl, and NaOH used in the EC experiments were all of analytical
grades. The granular activated carbon (GAC) was made from a coconut shell.
The H2O2 (30% pure), H2SO4, HCl, and NaOH used in the EC experiments were all of analytical
The pH of the solution was measured by a pH meter (Leici, Shanghai, China). The COD values of
grades. The granular activated carbon (GAC) was made from a coconut shell.
the wastewater
The pH of were analyzedwas
the solution by measured
fast digestion–spectrophotometric
by a pH meter (Leici, Shanghai,method (HJ/TThe
China). 399-2007).
COD values
The chemical compositions of the actual ore samples were relatively simple.
of the wastewater were analyzed by fast digestion–spectrophotometric method (HJ/T 399-2007). SiO 2 and CaO were
the main Thenon-metallic ingredientsof[14].
chemical compositions The lead
the actual and zincwere
ore samples grades in the simple.
relatively samplesSiO took up 4.17% and
2 and CaO were
7.18%
the main non-metallic ingredients [14]. The lead and zinc grades in the samples took uppyrite.
of the total, respectively. The major metallic minerals were galena, sphalerite, and 4.17%Actual
and
ore7.18%
samples were
of the crushed
total, to belowThe
respectively. 3 mm using
major a stainless-steel
metallic hammer
minerals were and sphalerite,
galena, then ground in apyrite.
and conical
ballActual
mill. The ground were
ore samples products were
crushed toused
belowas3feed
mm samples for flotation tests.
using a stainless-steel hammer and then ground in
Diethyldithiocarbamate
a conical ball mill. The ground (95% purity)were
products and used
sodium n-butylxanthate
as feed (92% purity)
samples for flotation tests. were purchased
Diethyldithiocarbamate
from Aladdin Industrial, Shanghai, (95% China.
purity) The
and CaO
sodium n-butylxanthate
(analytically pure) (92% purity)
and CuSO were purchased
4 (analytically pure)
from
used in Aladdin
this study Industrial, Shanghai,
were provided by China.
KermelThe CaO (analytically
Company, pure) and
Tianjin, China. CuSO4oil
Terpenic (analytically
(chemically pure)
pure)
wasused in this from
obtained studyHaoshen
were provided
Chemicalby Kermel
Reagent,Company,
Shanghai,Tianjin,
China.China. Terpenic oil (chemically pure)
was obtained from Haoshen Chemical Reagent, Shanghai, China.
2.2. EC Experiments
2.2. EC Experiments
The EC set-up used in this study is shown in Figure 1. The total volume of the electrolytic cell
was 250The mL,EC andset-up used in this study
the experiments were is shownout
carried in Figure 1. The200
by treating total
mLvolume of the samples
wastewater electrolytic
forcell
each
was 250 mL, and the experiments were carried out by treating 200 mL wastewater
run at room temperature. Two pairs of plates (length = 6.5 cm; width = 5.6 cm; thickness = 0.2 samples for eachcm)
runplaced
were at room ontemperature.
the electrolyticTwocell
pairs of plates The
in parallel. (length = 6.5and
anode cm;cathode
width =plates
5.6 cm;were
thickness = 0.2 cm)
connected to the
were placed
positive on the ports
and negative electrolytic
of thecell in parallel. The
QW-MS3010D DC anode
powerand cathode
supply (0–5 plates
A, 0–80 were connected
V), with to the
constant load
positive and negative ports of the QW-MS3010D DC power supply (0–5 A, 0–80 V), with constant
current. NaOH and H2 SO4 solutions were used to adjust the pH. At the end of the experiment, water
load current. NaOH and H2SO4 solutions were used to adjust the pH. At the end of the experiment,
was transferred to beakers for two hours of settling, and then the COD value of the supernatant was
water was transferred to beakers for two hours of settling, and then the COD value of the supernatant
measured. Finally, the sludge produced by the EC was filtered, dried, and weighed.
was measured. Finally, the sludge produced by the EC was filtered, dried, and weighed.

Figure
Figure 1. 1.Electrocoagulation
Electrocoagulation (EC)
(EC) experimental
experimentalset-up:
set-up:(1)(1)
Magnetic stirrer;
Magnetic (2) DC
stirrer; (2) power supply;
DC power (3)
supply;
electrolytic cell; (4) anode plate; (5) cathode plate; (6) magnetic bar-stirrer.
(3) electrolytic cell; (4) anode plate; (5) cathode plate; (6) magnetic bar-stirrer.

The COD removal rate was employed to evaluate the electrocoagulation efficiency, which is
calculated according to the following Equation (6).
Water 2020, 12, 595 4 of 12

Water The
2020, COD
12, 595 removal rate was employed to evaluate the electrocoagulation efficiency, which
4 of is
12
calculated according to the following Equation (6).
R(%) COD
= × 100, (6)
0 − COD1
R(%) = × 100, (6)
COD0
where R represents the removal rate of COD (%), COD 0 represents the initial COD value of the

wastewater
where before electrocoagulation
R represents the removal rate (mg/L),
of CODand
(%),COD 1 represents
COD the COD value of the wastewater
0 represents the initial COD value of the
after electrocoagulation (mg/L).
wastewater before electrocoagulation (mg/L), and COD1 represents the COD value of the wastewater
after electrocoagulation (mg/L).
2.3. Flotation Experiments
2.3. Flotation Experiments
Fresh water, wastewater, and treated water were then used for flotation at room temperature.
Fresh water,
The whole processwastewater, and into
can be divided treated
twowater were
stages: thenflotation
Galena used forfollowed
flotationbyat sphalerite
room temperature.
flotation.
The
For whole process experiment,
each flotation can be divided an into
800 two
g orestages:
sampleGalena flotationby
was ground followed
a conicalbyball
sphalerite
mill to flotation.
obtain a
For each flotation
product of 85 wt.% experiment,
passing 74anμm.800After
g oregrinding,
sample was the ground
ore pulpbywasa conical ball mill
transferred to obtain
to the galenaa flotation
product
of 85 wt.%
stage, passing
including 74 µm. After
single-stage grinding,
roughing, the ore pulp
three-stage was transferred
cleaning, to thescavenging.
and single-stage galena flotation stage,
The tailing
including single-stage roughing, three-stage cleaning, and single-stage scavenging.
of galena flotation was used later for sphalerite flotation, where single-stage roughing, two-stage The tailing of
galena flotation
cleaning, was used later
and single-stage for sphalerite
scavenging were flotation,
adopted.where single-stage
In both flotationroughing,
stages, thetwo-stage cleaning,
concentrates of
and single-stage
roughing scavenging
were reground towere adopted.
80 wt.% In both
passing flotation
44 μm stages,
in a Φ150 the conical
× 100 concentrates
mill. of roughingto
According were
the
reground to 80 wt.%
existing process passing
of the beneficiation a Φ150
44 µm inplant, × 100 conical
sequential mill.ofAccording
addition regulator,tocollector,
the existing
andprocess
frother of
to
the
the beneficiation
flotation cellplant,
were sequential
carried out,addition of regulator,
as shown in Figurecollector,
2. After and frotherthe
flotation, to the flotation
products werecelldried,
were
weighed,
carried out,and assayed,
as shown and then
in Figure the recovery
2. After flotation,was calculated
the products on dried,
were the basis of theand
weighed, mass and metal
assayed, and
balance,
then as shownwas
the recovery in Equation
calculated(7).
on the basis of the mass and metal balance, as shown in Equation (7).

Unit:g/t
raw minerals/800g
SH:sodium humate
H:50%KBX+50%NA
Grinding:5min30s CaO:6000 H:100
2min terpenic oil:25

2min H:10
Grinding:6min30s CaO:2000
2min H:20
3min CaO:1000 CuSO4:400

midding 4 3min KBX:400

3min CaO:1000 midding 3 1min terpenic oil:15
2min H:2.5
2min KBX:25
Grinding:5min CaO:1000
3min CaO:500
2min SH:100 2min CuSO4:400
2min KBX:30
midding 2
midding 7 tailing
3min CaO:500

Pb concentrate midding 1
midding 6

Zn concentrate midding 5

Figure
Figure 2. Flowsheet and
2. Flowsheet and corresponding
corresponding experimental
experimental conditions
conditions of
of batch
batch flotation
flotation tests
tests using
using different
different
types of water.
types of water.

×
ɛ(%) = ∑ × 100, (7)
( × )

where ɛ is the recovery of product, γi is the yield, and βi is the grade.

Water 2020, 12, 595 5 of 12

γ × βi
ε(%) = Pn i × 100, (7)
1 (γi × βi )
where
Water ε is
2020, 12,the
595recovery of product, γi is the yield, and βi is the grade. 5 of 12

3.3.Results
Resultsand
andDiscussion
Discussion

3.1. Effect of EC Parameters on COD Removal Rate of Mixed Wastewater

3.1. Effect of EC Parameters on COD Removal Rate of Mixed Wastewater
Unlike anode materials, cathode materials do not have a significant effect on EC efficiency except
Unlike anode materials, cathode materials do not have a significant effect on EC efficiency except
in electro-Fenton processes [15]. We have learned that stainless steel is the most widely-used cathode
in electro-Fenton processes [15]. We have learned that stainless steel is the most widely-used cathode
material in industry, considering its economy and durability [16]. In addition, the distance between
material in industry, considering its economy and durability [16]. In addition, the distance between
the anode and cathode is suggested to be 1~2 cm, according to previous publications and industrial
the anode and cathode is suggested to be 1~2 cm, according to previous publications and industrial
experience [17]. After verification, 2 cm was the optimal distance to be adopted in our following
experience [17]. After verification, 2 cm was the optimal distance to be adopted in our following
experiments. As the anode material is a prime consideration for EC technique [18], iron and aluminum
experiments. As the anode material is a prime consideration for EC technique [18], iron and
plates were used as anode materials in this study. The results of COD removal efficiency with the two
aluminum plates were used as anode materials in this study. The results of COD removal efficiency
anode materials are shown in Figure 3. When using an iron electrode, the COD value decreases from
with the two anode materials are shown in Figure 3. When using an iron electrode, the COD value
424.9 to 158.6 mg/L, which is equivalent to a removal rate of 62.7%. However, when an aluminum
decreases from 424.9 to 158.6 mg/L, which is equivalent to a removal rate of 62.7%. However, when
anode is used, the COD value is reduced to 265.1 mg/L, corresponding to a removal rate of 37.7%.
an aluminum anode is used, the COD value is reduced to 265.1 mg/L, corresponding to a removal
The results indicate that in this study, Fe performs better as the anode material of the EC process.
rate of 37.7%. The results indicate that in this study, Fe performs better as the anode material of the
Therefore, an Fe anode was adopted in the subsequent experiments.
EC process. Therefore, an Fe anode was adopted in the subsequent experiments.

500

424.9
400
COD/mgL-1

300
265.1

200
158.6

100

0
wastewater treated water treated water
with Al anode with Fe anode

Figure
Figure 3. Effect
Effect ofofanode
anode materials
materials forfor EC treatment
EC treatment on mixed
on mixed wastewater
wastewater COD(cathode
COD value value (cathode
material:
material: Stainless steel, current density: 2
13.74 mA/cm 2, pH: 7.1, electrolysis time: 50 min).
Stainless steel, current density: 13.74 mA/cm , pH: 7.1, electrolysis time: 50 min).

Current density
Current density isis another
another important
important parameter
parameter that that determines
determines the the amount
amount of of coagulant
coagulant
produced in
produced inthe
thereactor [19].[19].
reactor It has
It ahas
significant effect oneffect
a significant the EC onefficiency
the EC and electricity
efficiency and consumption.
electricity
The experimental
consumption. The results are summarized
experimental results arein summarized
Figure 4. Figure 4 shows
in Figure 4. that
FigureCOD removal
4 shows rateCOD
that first
increasesrate
removal andfirst
then declinesand
increases with thedeclines
then increasewith
of current density.
the increase COD removal
of current density. rate
CODincreases
removalfromrate
49.41% tofrom
increases 77.46% as the
49.41% to current
77.46% density rises todensity
as the current rises to2 .24.73
24.73 mA/cm Then, it decreases
mA/cm 2. Then, toit60.42%
decreasesas the
to
current density continues to increase to 30.22 mA/cm 2 . The current 2density is related to the amount of
60.42% as the current density continues to increase to 30.22 mA/cm . The current density is related to
dissolved
the amountiron ions and the
of dissolved ironformation
ions and theof Fe(OH) 3 , which
formation determines
of Fe(OH) 3, which thedetermines
COD removal the CODefficiency [20].
removal
It can also affect
efficiency [20]. Itthecan
cellalso
voltage through
affect various
the cell overpotentials,
voltage which may
through various be conducive
overpotentials, to the may
which removalbe
efficiency of the COD. If the current density is relatively low, the lack of coagulant
conducive to the removal efficiency of the COD. If the current density is relatively low, the lack of may restrict the
removal efficiency.
coagulant may restrictTherefore, the curve
the removal presentsTherefore,
efficiency. an upwardthe trend
curve at an early stage.
presents However,
an upward when
trend at the
an
current
early density
stage. continueswhen
However, to increase
the current mA/cm2 ,continues
to 32.22 density the temperature of treated
to increase to wastewater
32.22 mA/cm increases
2, the

significantly.ofHigh
temperature temperature
treated wastewatercauses the significantly.
increases instability of High coagulation,
temperaturewhich can lead
causes to a low EC
the instability of
coagulation, which can lead to a low EC efficiency. Furthermore, energy consumption grows
gradually with the increase of current density [21]. Taking both the COD removal rate and electricity
consumption into account, 19.23 mA/cm2 was used as the current density for subsequent
experiments.
Water 2020, 12, 595 6 of 12

efficiency. Furthermore, energy consumption grows gradually with the increase of current density [21].
TakingWater 2020,
both 12, COD
the 595 removal rate and electricity consumption into account, 19.23 mA/cm2 was6 used
of 12
Water 2020, 12, 595 6 of 12
as the current density for subsequent experiments.

80
80

Removal rate of COD/%

Removal rate of COD/%

70
70

60
60

50
50

5 10 15 20 25 30
5 10 15 20 25 -2 30
Current density /mA·cm
Current density /mA·cm-2
Figure
Figure 4. Effect
4. Effect of current
of current densitydensity on wastewater
on mixed mixed wastewater COD removal
COD removal ratematerial:
rate (anode (anode material: Fe,
Fe, cathode
Figure 4.
cathode Effect of
material:current density
Stainless steel, on
pH: mixed
7.1, wastewater
electrolysis
material: Stainless steel, pH: 7.1, electrolysis time: 50 min). COD
time: 50 removal
min). rate (anode material: Fe,
cathode material: Stainless steel, pH: 7.1, electrolysis time: 50 min).
To evaluate
To evaluate the effect
the effect of theofinitial
the initial
pH, the pH, the wastewater
wastewater samples samples were adjusted
were adjusted to a preset
to a preset pH valuepH
To
usingvalue evaluate
sodiumusing the effect
sodium hydroxide
hydroxide of the
or sulfuric initial
or acid.pH,
sulfuric Thethe
acid.wastewater
The effects
effects samples
of initial
of initial were
pH value adjusted
pH value
on COD to
on COD a preset
removalremoval pH
raterate
are
value
shown areinusing
shown
Figuresodium
in 5.
Figurehydroxide
The 5. or sulfuric
The results
results show show acid.
thatCOD
that the TheCOD
the effects of initial
removal
removal inpH
raterate in value
thethe
EC EC on CODremains
process
process removalaround
remains rate
around
are showninin Figure 5. value
The results show that the COD removal rate in thepHEC increases
process remains around
75.0%75.0%
in a wide a wide pH
pH value rangerange
from from
3 to3 9.
to However,
9. However, when
when thethe initial
initial pH increases to11,
to 11, the
the removal
removal
75.0% in a wide
efficiency pH value
presents a range fromtrend
downward 3 to 9.with
However,
a when the initial
corresponding removalpHrate
increases
of to 11,this
71.08%; the is
removal
probably
efficiency presents a downward trend with a corresponding removal rate of 71.08%; this is probably
efficiency
because presents a downward
offormation
the formation trend with
of soluble Fe(OH)a−4corresponding
−4, which is notremoval rate to
conducive of 71.08%;
thefloc this is probably
flocformation.
formation. On the
the
because of the of soluble Fe(OH) , which is not conducive to the On
because of the formation of soluble Fe(OH) −4, which is not conducive to the floc formation. On the
contrary, at a neutral or acidic pH, higher removal rates occur as most of the iron complexes are
contrary, at a neutral or acidic pH, higher removal rates occur as most of the iron complexes are formed.
contrary,
formed.atHence,
a neutral or acidicexperiments
subsequent pH, higher removal
were carriedratesout
occur
under as most
neutral of pH
the conditions.
iron complexes pH 7.1 arewas
Hence,
formed.
subsequent
Hence,
experiments
subsequent
were carried
experiments were
out underout
carried
neutral
under
pH conditions.
neutral pH
pH 7.1 was
conditions. pH
employed
7.1 was
employed in the following experiments.
in employed
the followingin theexperiments.
following experiments.
90
90
Removal Rate of COD/%

80
Removal Rate of COD/%

80

70
70

60
60

50
50 2 4 6 8 10 12
2 4 6 pH 8 10 12
pH
Figure 5. Effect of initial pH value on mixed wastewater COD removal rate (anode material: Fe,
Figure
Figure 5. 5.
cathode Effect
Effect of initial
of initial
material: pHpH
Stainless value
value on mixed
on current
steel, mixed wastewater
wastewater
density: COD
19.23 COD 2removal
removal
mA/cm rate (anode
, electrolysis
rate (anode 50material:
material:
time: Fe,
Fe, cathode
min).
cathode Stainless
material: steel,
Stainless steel,density:
current density: 19.23 2mA/cm 2, electrolysis time: 50 min).
material: current 19.23 mA/cm , electrolysis time: 50 min).
Electrolysis time is another important parameter affecting COD removal efficiency [22]. The
Electrolysis
Electrolysis
results time
of thetime
effect is
of another
is another important
important
electrolysis onparameter
timeparameter
the COD affecting
affecting
removal COD COD
rate areremoval
removal efficiency
efficiency
provided [22].[22].
in Figure The The
results
6. Figure 6
of results
theshowsof that
effect the effect of
of electrolysiselectrolysis
time on time
the CODon the COD
removal removal
rate are rate are
provided provided
in Figure in
6. Figure
Figure
the COD removal rate increases rapidly in the initial phase, which is due to the increase6.6 Figure
shows 6
that
theshows
COD that the COD
removal
of coagulant; yet, removal
ratethe
increases
growth rate increases
rapidly
trend of in rapidly
thethe
CODinitialinphase,
removaltherate
initial
which phase,
is due
gradually which is increase
to the
slows duewith
down to the
ofincrease
the coagulant;
extension
of coagulant; yet, the growth trend of the COD removal rate gradually slows
of electrolysis time. When electrolysis time increases to 70 min, the COD removal rate down with the extension
reaches a
of electrolysis time. When electrolysis time increases to 70 min, the COD removal rate reaches a
Water 2020, 12, 595 7 of 12

yet, the growth trend of the COD removal rate gradually slows down with the extension of electrolysis
Water 2020, 12, 595 7 of 12
time. When electrolysis time increases to 70 min, the COD removal rate reaches a plateau at7 77.62%
Water 2020, 12, 595 of 12
because
plateautheat adsorption of organic
77.62% because pollutants
the adsorption of reaches
organic an equilibrium
pollutants state.
reaches The electrolysis
an equilibrium state.time
The of
subsequent
plateau at experiments
77.62% was
because set
the to be 70 min.
adsorption of organic pollutants
electrolysis time of subsequent experiments was set to be 70 min. reaches an equilibrium state. The
electrolysis time of subsequent experiments was set to be 70 min.
90
90
80
80
of COD/%

70
of COD/%

70
60
60
rate

50
rate
Removal

50
Removal

40
40
30
30
20
20
0 20 40 60 80 100 120
60
Time/Min 80 0 100 20
120 40
Time/Min
Figure 6. Effect
Figure of electrolysis
6. Effect timetime
of electrolysis on mixed wastewater
on mixed CODCOD
wastewater removal rate (anode
removal material:
rate (anode Fe, cathode
material: Fe,
Figure Stainless
material:
cathode 6.material:
Effect of electrolysis
steel, current
Stainless time on 19.23
steel,density:
current density: 19.232mA/cm
mixedmA/cm
wastewater
, pH:COD
7.1). removal
2, pH: 7.1). rate (anode material: Fe,
cathode material: Stainless steel, current density: 19.23 mA/cm2, pH: 7.1).
3.2.3.2.
Effect
Effectof of
Additives
AdditivesononCOD CODRemoval
RemovalRate Rate of of Mixed Wastewater
Mixed Wastewater
3.2. Effect of Additives on COD Removal Rate of Mixed Wastewater
Under
Under the same
the samecurrent
currentdensity,
density,ananincrease
increaseofofsupporting
supporting electrolyte
electrolyte concentration
concentration can canleadleadtoto a
decrease Under
a decrease ofthe
of the same current resistance
interelectrode
the interelectrode density, anand
resistance increase
andthus thusof supporting
reduce
reduce energyelectrolyte
energy consumption.
consumption.concentration
Ghernaout
Ghernaout can lead
reported
reported to
thata decrease
thatthe addition
the of theof
addition interelectrode
ofaa supporting
supporting resistance
electrolyte
electrolyte and canthus
canalsoreduce
also energy
affect
affect thethe consumption.
removal
removal raterate
of COD Ghernaout
of COD reported
[23].
[23]. Hence, Hence,
the
that
theeffect the
effect ofofaddition
supporting
supporting of aelectrolyte
supporting
electrolyte electrolyte can
concentration
concentration onon also
ECEC affect thewas
efficiency
efficiency removal
was rate
further
further of COD
studied
studied in [23]. Hence,
in this
this study,
study, the
and and
NaNaeffect
2SO of supporting
4 was electrolyte
chosenasasthe concentration
thesupporting
supportingelectrolyte on EC efficiency
electrolyte because of its was
its low further
lowcost.
cost.The studied
TheNa 2SO in this study,
4 concentration and
of of
2 SO 4 was chosen Na 2 SO 4 concentration
Na
1.0,1.0, SO
21.1,
1.1, 1.2,was
4 1.2,
and chosen
and 1.3 ascorresponded
1.3g/L
g/L the supportingto
corresponded electrolyte
to the current
the current because of itsof
densities
densities low
of cost.
8.24,
8.24, The19.23,
13.74,
13.74, Na 2SO
19.23, 4 concentration
and
and 24.73 mA/cm
24.73 mA/cm of2, 2
,
1.0, 1.1, 1.2,
respectively. and
The 1.3 g/L
results corresponded
of the effect ofto
Na theSO current densities
addition on the of
COD8.24, 13.74,
removal
respectively. The results of the effect of Na2 SO4 addition on the COD removal rate are shown in Figure 7.
2 4 19.23,
rate and
are 24.73
shown mA/cm
in Figure
2,

respectively.
7. The removal Therates
results of the
with the effect of Na2SO
addition 42addition on thelower
COD removal ratewithout
are shown Na2inSOFigure
The removal rates with the addition of Na2of SONa SO4 are much than those
4 are much lower than those without Na2 SO4 . No positive
4. No
7. The
positive removal rates
effectremoval with
on COD efficiencythe addition
removal efficiency of Na SO
is observed are much lower
by the addition than those without Na SO 4. No
of Na2ofSO Na,2SO 4, which is consistent
2 4 2
effect on COD is observed by the addition 4 which is consistent with
positive
with previouseffect on COD
reports removal efficiency is observed by the addition of Na SO , which is consistent
The[24].
lowThe low removal efficiency can be attributed to the of increase of the
2 4
previous reports [24]. removal efficiency can be attributed to the increase the passivation
with previous
passivation layerreports
caused[24]. The
by the low removal
addition of Na2SO efficiency
4 [25]. can be attributed to the increase of the
layer caused by the addition of Na2 SO4 [25].
passivation layer caused by the addition of Na2SO4 [25].
100
without Na2SO4
100
with Na
without Na22SO
SO44
90
with Na2SO4
90
of COD/%

80
of COD/%

80
70
raterate

70
60
Removal

60
Removal

50
50
40
40
30
8 12 16 20 24 28
30
8 12 16 20 -2 24 28
Current density/mA·cm
Current density/mA·cm-2
Figure 7. Effect of addition of Na2SO4 on mixed wastewater COD removal rate (anode material: Fe,
Figure
7. 7.material:
cathode EffectofofStainless
Effect additionsteel,
addition of Na
of Na 2SO7.1,
pH: 4 onelectrolysis
mixed wastewater
time: 70COD removal
min). rate (anode material: Fe,
Figure 2 SO4 on mixed wastewater COD removal rate (anode material:
cathode material: Stainless steel, pH: 7.1, electrolysis time: 70 min).
Fe, cathode material: Stainless steel, pH: 7.1, electrolysis time: 70 min).
Activated carbon is widely used to adsorb organic compounds in wastewater [26]. In order to
studyActivated
the effect carbon is widely
of activated used
carbon to adsorb
on the organicefficiency
COD removal compounds withinEC,
wastewater [26].
wastewater In order
samples to
were
study the effect of activated carbon on the COD removal efficiency with EC, wastewater samples were
Water 2020, 12, 595 8 of 12

Water 2020, 12,

Activated 595
carbonis widely used to adsorb organic compounds in wastewater [26]. In order to8study
of 12

the effect of activated carbon on the COD removal efficiency with EC, wastewater samples were treated
treated by GAC adsorption, EC/GAC adsorption (EC plus GAC in one reactor), and EC + GAC
by GAC adsorption, EC/GAC adsorption (EC plus GAC in one reactor), and EC + GAC adsorption (EC
adsorption (EC followed by GAC in different reactors) process, and their results are summarized in
followed by GAC in different reactors) process, and their results are summarized in Figure 8.
Figure 8.

Figure
Figure 8. Effect
8. Effect of granular
of granular activated
activated carbon
carbon (GAC)
(GAC) treatmentononmixed
treatment mixedwastewater
wastewater COD
COD removal
removal
rate (anode
rate (anode material:
material: Fe, cathode
Fe, cathode material:
material: Stainless
Stainless steel,current
steel, currentdensity:
density:19.27 mA/cm22,, pH:
19.27 mA/cm pH: 7.1,
7.1,
electrolysis time: 70
electrolysis time: 70 min). min).

The The
Figure Figure 8 shows
8 shows thatthatthethe
COD COD removal
removal rate
rate using
using GACalone
GAC aloneisislowlow(only
(only 25.7%)
25.7%) when thethe
GAC dosage reaches 6.47 g/L, indicating that GAC adsorption has little effect
GAC dosage reaches 6.47 g/L, indicating that GAC adsorption has little effect on the residual reagents on the residual reagents
in mineral
in mineral processing
processing wastewater.
wastewater. WhenWhen wastewaterisistreated
wastewater treatedby bythetheECECprocess
process alone,
alone, the
the COD
COD
removal rate is 77.62%. Compared with EC or GAC alone, both the
removal rate is 77.62%. Compared with EC or GAC alone, both the EC/GAC and EC + GAC processes EC/GAC and EC + GAC processes
can improve
can improve COD COD removal.
removal. However,
However, it worth
it is is worth notingthat
noting thatthe
theCODCODremoval
removal rate
rate of
of EC/GAC
EC/GAC is is
higher than that of EC + GAC. At a dosage of 2.94 g/L GAC, the
higher than that of EC + GAC. At a dosage of 2.94 g/L GAC, the COD decreases from 424.9 to 74.9COD decreases from 424.9 to 74.9
and
and 83.3 mg/L, corresponding to removal rates of 82.37% for EC/GAC and 80.4% for EC/GAC,
83.3 mg/L, corresponding to removal rates of 82.37% for EC/GAC and 80.4% for EC/GAC, respectively.
respectively. Therefore, the EC/GAC process was adopted in the subsequent experiments.
Therefore, the EC/GAC process was adopted in the subsequent experiments.
It can be concluded that the adsorption of GAC alone cannot be used as an effective treatment
It can be concluded that the adsorption of GAC alone cannot be used as an effective treatment
method for sulfide mineral flotation wastewater. In the EC/GAC system, GAC acts as a moving
method for sulfide mineral flotation wastewater. In the EC/GAC system, GAC acts as a moving
particle electrode to accelerate electron transfer rate and hence improve the processing efficiency
particle electrode to accelerate electron transfer rate and hence improve the processing efficiency [27,28].
[27,28]. The main reason is that it is essentially a three-dimensional electrochemical process which is
The main reason
not stable [29].is that it is essentially a three-dimensional electrochemical process which is not
stable [29].The sludge produced is around 5.8 kg/m3 of wastewater under the optimal processing
conditions. Itproduced
The sludge is aroundas
can be considered kg/m3 of resource
5.8a valuable wastewater under
because of the optimal
its high processing
Fe content conditions.
of about 45.5%.
It canFurther
be considered
research on as the
a valuable resourceutilization
sludge recycling because of itssoon
will highbeFereported
contentseparately.
of about 45.5%. Further
research on the sludge the
Furthermore, recycling
effect ofutilization will soon be
H2O2 concentration on reported separately.
EC efficiency was studied, and the results can
Furthermore, the effect of
be seen in the Supplementary2Materials H O 2 concentration on EC efficiency
(Figure S1 and Figure S2). was studied, and the results can
be seen in the Supplementary Materials (Figure S1 and Figure S2).
3.3. Effect of EC Treatment on COD Removal Rate of Different Types of Wastewater
3.3. Effect of EC Treatment on COD Removal Rate of Different Types of Wastewater
Through the above experiments, the optimum treatment conditions of mixed wastewater were
Through (iron
obtained the above
anode,experiments,
pH 7.1, 70 min the electrolysis
optimum treatment
time, 19.23 conditions of mixed
mA/cm2 current wastewater
density, and 4.1were
g/L
activated
obtained (ironcarbon).
anode, UnderpH 7.1, these optimum
70 min conditions,
electrolysis time,Pb-Zn mA/cm2wastewater,
19.23flotation pyrite and
current density, concentrate
4.1 g/L
wastewater,
activated carbon). pyrite
Under tailing
these wastewater,
optimum and mixed wastewater
conditions, were treated,
Pb-Zn flotation respectively.
wastewater, The results
pyrite concentrate
are shown in Figure 9.
wastewater, pyrite tailing wastewater, and mixed wastewater were treated, respectively. The results
are shown in Figure 9.
Water 2020, 12, 595 9 of 12
Water 2020, 12, 595 9 of 12

800 100
COD removal rate
COD before treatment
700 COD after treatment

80
603.2
600

removal rate of COD/%

COD/mgL-1 500
60
434.7 424.9
400

40
300
245.3

200
20
100 85.9 90.2
72.9
50.7

0 0
Pb-Zn flotation Pyrite concentrate Pyrite tailings mixed
wastewater wastewater wastewater wastewater

Figure 9.
Figure 9. Effect
Effect of
of EC
EC treatment
treatmenton
onthe
theCOD
CODvalues
valuesand
andCOD
CODremoval rates
removal ofof
rates four different
four types
different of
types
wastewaters.
of wastewaters.

The removalrates
The COD removal ratesfor
forthe
theabove
above four
four types
types of wastewaters
of wastewaters are are 80.24%,
80.24%, 79.33%,
79.33%, 85.05%,
85.05%, and
and 82.84%, respectively. The results indicate that the higher the COD value of wastewater
82.84%, respectively. The results indicate that the higher the COD value of wastewater is, the better is, the
better efficiency
efficiency the corresponding
the corresponding EC experiment
EC experiment obtains.obtains. Thetailing
The pyrite pyrite wastewater
tailing wastewater
with thewith the
highest
highest COD has
COD value valuethehas the highest
highest CODCOD removal
removal rate,rate, followed
followed byby mixedwastewater,
mixed wastewater,Pb-Zn
Pb-Zn flotation
flotation
wastewater,
wastewater,andandpyrite
pyriteconcentrate
concentratewastewater.
wastewater.

3.4. Effect of
3.4. Effect of Water
Water Type
Type on
on the
the Grade
Grade and
and Recovery
RecoveryofofPb/Zn
Pb/ZnSulfide
SulfideMineral
MineralFlotation
Flotation
The
The above
above experimental
experimental results
results confirmed
confirmed that
that EC
EC is
is an
an effective
effective technique
technique for
for COD
COD removal
removal of
of
the
the sulfide
sulfidemineral
mineralflotation wastewater.
flotation To To
wastewater. further investigate
further the possibility
investigate of reusing
the possibility the EC-treated
of reusing the EC-
water
treatedaswater
the feed water,
as the feedflotation experiments
water, flotation were carried
experiments wereout, and their
carried results
out, and areresults
their shownarein shown
Tables
S1–S3, respectively. The comparison of the Pb/Zn grades and recovery rates using different
in Tables S1–S3, respectively. The comparison of the Pb/Zn grades and recovery rates using different types of
water during
types of waterflotation is presented
during flotation in Figurein
is presented 10.Figure 10.

(%)
(a) Pb Grade
80 Pb Recovery
71.73

60 57.62
51.91

40 36.06
30.54
25.01

20

0
fresh water wastwater water after teatment

Figure 10. Cont.

Water 2020, 12, 595 10 of 12
Water 2020, 12, 595 10 of 12

(%) Zn Grade
(b)
80 Zn Recovery
68.61
65.33
59.99
60 56.96 56.96 56.33

40

20

0
fresh water wastwater water after teatment

Figure 10. The

The grade
grade and
and recovery
recovery of
of Pb (a) and Zn (b) sulfide flotation concentrates
concentrates using
using different
types of water.

recovery using different

The Pb recovery different types of water
water obeys
obeys the
the following
following order:
order: Treated
Treated water
water (36.06%)
(36.06%)
> fresh water
> fresh (30.54%) >>wastewater
water (30.54%) wastewater(25.01%),
(25.01%), whereas
whereas the
the order
order ofof Pb
Pb grades
grades is:is: Fresh
Freshwater
water(71.73%)
(71.73%)
>
> wastewater (57.62%) >>treated
wastewater (57.62%) treatedwater
water (51.91%).
(51.91%). The
Theexperimental
experimental results
results indicate
indicate that
that flotation
flotation using
treated water can significantly improve the Pb recovery,
recovery,while
whilethethePbPbgrade
gradeisisreduced.
reduced.
concentrate, a similar Zn grade
In terms of Zn concentrate, grade is
is obtained
obtained with
with different
different types of waters (around
Zn recovery obeys the following order: Fresh water (68.61%) >
The Zn
56%). The treated water (65.33%) >>
> treated
wastewater (59.99%). Compared
Compared with the the untreated
untreated wastewater,
wastewater, EC-treated water is more conducive
for the increase of Zn recovery without affecting
affecting the
the Zn
Zn grade.
grade.

4. Conclusions
4. Conclusions
This study
This study provides
provides the
the latest
latest evidence
evidence that
that EC
EC isis aa promising
promising method
method forfor treating
treating and
and recycling
recycling
mineral processing wastewater. Different factors were investigated to obtain
mineral processing wastewater. Different factors were investigated to obtain optimal experimental optimal experimental
conditions, i.e., 2
conditions, i.e., iron
ironanode,
anode,pHpH7.1,
7.1,19.23
19.23mA/cm
mA/cmcurrent
2 current density, 70 70
density, minminelectrolysis time,
electrolysis andand
time, 4.1 g/L
4.1
activated
g/L carbon.
activated carbon. Under thethe
Under optimal
optimal conditions,
conditions,thetheCOD
CODofofthe
themixed
mixedwastewater
wastewater decreases from
decreases from
424.9 to
424.9 to 72.9
72.9 mg/L.
mg/L. TheThe addition
addition of
of aa supporting
supporting electrolyte
electrolyte like
like Na
Na22SO can be
SO44 can be harmful
harmful toto the
the removal
removal
of COD. The COD removal rate of wastewater with the highest COD
of COD. The COD removal rate of wastewater with the highest COD value is highest. Moreover,value is highest. Moreover,
flotation results
flotation results show
show that
that the
the recoveries
recoveries ofof both
both Pb
Pb and
and ZnZn using
using EC-treated water are
EC-treated water are higher than
higher than
those of directly using wastewater or fresh water. The results imply that the EC technique
those of directly using wastewater or fresh water. The results imply that the EC technique can provide can provide
aa new
new direction
directionfor forrecycling
recyclingmineral
mineral processing
processing wastewater.
wastewater. This
This study
study provides
provides novel
novel insights
insights into
into dealing with wastewater in the mining industry, and is meaningful
dealing with wastewater in the mining industry, and is meaningful in both environmental and in both environmental and
economical ways.
economical ways.
Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4441/12/2/595/s1:
Supplementary Materials: The following are available online at www.mdpi.com/xxx/s1: Figure S1: Variation of
Figure S1: Variation of COD removal rate with dosage of H2 O2 (Anode material: Fe, Cathode material: Stainless
COD removaldensity:
steel, Current rate with dosage
19.23 mA/cmof H O2 (Anode
2 ,2pH: material:time:
3.0, Electrolysis Fe, Cathode
70 min), material:
Figure S2:Stainless
Effect of steel,
H2 O2Current density:
on the boundary
19.23 mA/cm2, pH: 3.0, Electrolysis time: 70 min), Figure S2: Effect of H O on the boundary between
between mud and water, Table S1: Flotation tests results with fresh water, Table S2: Flotation tests results with
2 2 mud and
water,
mixed Table S1: Flotation
wastewater, tests
Table S3: results with
Flotation tests fresh
resultswater, Table S2:
with treated Flotation tests results with mixed wastewater,
water.
Table
Author S3:Contributions:
Flotation tests Conceptualization,
results with treatedZ.G.water.
and W.S.; methodology, W.S.; formal analysis, Z.G.; investigation,
G.J.; dataContributions:
Author curation, G.J. and S.R.; writing—original
Conceptualization, Z.G. draft
and preparation, G.J.; writing—review
W.S.; methodology, W.S.; formaland editing, Z.G.;
analysis, Y.G.;
supervision, Z.G.; project administration, W.S.; funding acquisition, Z.G. All authors have read and agreed to the
investigation, G.J.;of
published version data
the curation, G.J. and S.R.; writing—original draft preparation, G.J.; writing—review and
manuscript.
editing, Y.G.; supervision, Z.G.; project administration, W.S.; funding acquisition, Z.G. All authors have read
agreedThe
Funding:
and authors
to the acknowledge
published financial
version of support from the National Natural Science Foundation of China
the manuscript.
(51634009, 51774328, and 51404300), the Young Elite Scientists Sponsorship Program by CAST (2017QNRC001),
Funding: The authors acknowledge financial support from the National Natural Science Foundation of China
(51634009, 51774328, and 51404300), the Young Elite Scientists Sponsorship Program by CAST (2017QNRC001),
Water 2020, 12, 595 11 of 12

the Young Elite Scientists Sponsorship Program by Hunan province of China (2018RS3011), the Natural Science
Foundation of Hunan Province of China (2018JJ2520), and the National 111 Project (B14034).
Acknowledgments: The authors are grateful to the financial support from the National Natural Science
Foundation of China (51634009, 51774328, and 51404300), the Young Elite Scientists Sponsorship Program by
CAST (2017QNRC001), the Young Elite Scientists Sponsorship Program by Hunan province of China (2018RS3011),
the Natural Science Foundation of Hunan Province of China (2018JJ2520), and the National 111 Project (B14034).
All authors appreciate the School of Minerals Processing and Bioengineering, Central South University, Changsha,
China for providing the facilities.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Farrokhpay, S.; Zanin, M. An investigation into the effect of water quality on froth stability. Adv. Powder
Technol. 2012, 23, 493–497. [CrossRef]
2. Zhao, S.; Pan, J.Z. Overview on the Treatment Technology of Wastewater from Copper Mineral Processing
(WCMP). Adv. Mater. Res. 2013, 750, 1369–1372.
3. Sitorus, F.; Cilliers, J.J.; Brito-Parada, P.R. Multi-criteria decision making for the choice problem in mining
and mineral processing: Applications and trends. Expert Syst. Appl. 2019, 121, 393–417. [CrossRef]
4. Kobya, M.; Can, O.T.; Bayramoglu, M. Treatment of textile wastewaters by electrocoagulation using iron and
aluminum electrodes. J. Hazard. Mater. 2003, 99, 163–178. [CrossRef]
5. Beck, E.C.; Giannini, A.P.; Ramirez, E.R. Electrocoagulation clarifies food wastewater. Food Technol. 1974, 22,
18–19.
6. Bazrafshan, E. Application of electrocoagulation process for dairy wastewater treatment. J. Chem. 2012, 2013,
1–8. [CrossRef]
7. Wang, S.; Wang, Q. Experimental studies on pretreatment process of brackish water using electrocoagulation
(EC) method. Desalination 1987, 66, 353–364. [CrossRef]
8. Vik, E.A.; Carlson, D.A.; Eikum, A.S.; Gjessing, E.T. Electrocoagulation of potable water. Water Res. 1984, 18,
1355–1360. [CrossRef]
9. Eryuruk, K.; Un, U.T.; Ogutveren, U.B. Electrochemical treatment of wastewaters from poultry slaughtering
and processing by using iron electrodes. J. Clean. Prod. 2019, 121, 1089–1095. [CrossRef]
10. Moreno-Casillas, H.A.; Cocke, D.L.; Gomes, J.A.G.; Morkovsky, P.; Parga, J.R.; Peterson, E. Electrocoagulation
mechanism for COD removal. Sep. Purif. Technol. 2007, 56, 204–211. [CrossRef]
11. Mollah, M.Y.; Morkovsky, P.; Gomes, J.A.; Kesmez, M.; Parga, J.; Cocke, D.L. Fundamentals, present and
future perspectives of electrocoagulation. J. Hazard. Mater. 2004, 114, 199–210. [CrossRef] [PubMed]
12. Johnson, P.N. Ferric chloride and alum as single and dual coagulants. Acta Sci. Circumst. 1983, 75, 232–239.
[CrossRef]
13. Makarov, V.M.; Kalaeva, S.Z.; Zakharova, I.N.; Nevzorov, I.A.; Maltseva, M.S.; Shipilin, A.M.;
Krzhizhanovskaya, M.G. Magnetic and X-ray studies of nanodispersed magnetite synthesized from chrome
containing galvanic sludge. J. Nano- Electron. Phys. 2015, 7, 4–12.
14. Wei, X.; Cao, J.; Holub, R.F.; Hopke, P.K.; Zhao, S. TEM study of geogas-transported nanoparticles from
the Fankou lead–zinc deposit, Guangdong Province, South China. J. Geochem. Explor. 2013, 128, 124–135.
[CrossRef]
15. Yang, S.; Verdaguer-Casadevall, A.; Arnarson, L.; Silvioli, L.; Čolić, V.; Frydendal, R.; Rossmeisl, J.;
Chorkendorff, I.; Stephens, I.E. Toward the decentralized electrochemical production of H2 O2 : a focus on the
catalysis. Acs Catal. 2018, 8, 4064–4081. [CrossRef]
16. Arslan-Alaton, İ.; Kabdaşlı, I.; Vardar, B.; Tünay, O. Electrocoagulation of simulated reactive dyebath effluent
with aluminum and stainless steel electrodes. J. Hazard. Mater. 2009, 164, 1586–1594. [CrossRef]
17. Ghalwa, A.; Nasser, M.; Farhat, N. Removal of abamectin pesticide by electrocoagulation process using
stainless steel and iron electrodes. J. Env. Anal. Chem. 2015, 2, 134. [CrossRef]
18. Garg, K.K.; Prasad, B. Treatment of toxic pollutants of purified terephthalic acid waste water: A review.
Environ. Technol. Innov. 2017, 8, 191–217. [CrossRef]
19. Lu, J.; Li, Y.; Yin, M.; Ma, X.; Lin, S. Removing heavy metal ions with continuous aluminum electrocoagulation:
A study on back mixing and utilization rate of electro-generated Al ions. Chem. Eng. J. 2015, 267, 86–92.
[CrossRef]
Water 2020, 12, 595 12 of 12

20. Doǧan, D.; Türkdemir, H. Electrochemical oxidation of textile dye indigo. J. Chem. Technol. Biotechnol.: Int.
Res. Process, Environ. Clean Technol. 2005, 80, 916–923.
21. Zongo, I.; Maiga, A.H.; Wéthé, J.; Valentin, G.; Leclerc, J.P.; Paternotte, G.; Lapicque, F. Electrocoagulation for
the treatment of textile wastewaters with Al or Fe electrodes: Compared variations of COD levels, turbidity
and absorbance. J. Hazard. Mater. 2009, 169, 70–76. [CrossRef] [PubMed]
22. Holt, P.K.; Barton, G.W.; Mitchell, C.A. The future for electrocoagulation as a localised water treatment
technology. Chemosphere 2005, 59, 355–567. [CrossRef] [PubMed]
23. Ghernaout, D.; Ghernaout, B. On the controversial effect of sodium sulphate as supporting electrolyte on
electrocoagulation process: A review. Desalination Water Treat. 2011, 27, 243–254. [CrossRef]
24. Chen, X.; Chen, G.; Yue, P.L. Separation of pollutants from restaurant wastewater by electrocoagulation. Sep.
Sci. Technol. 2007, 42, 819–833. [CrossRef]
25. Tezcan Un, U.; Topal, S.; Ates, F. Electrocoagulation of tissue paper wastewater and an evaluation of sludge
for pyrolysis. Desalination Water Treat. 2016, 57, 28724–28733. [CrossRef]
26. Eldars, F.M.S.E.; Ibrahim, M.A.; Gabr, A.M.E. Reduction of COD in water-based paint wastewater using
three types of activated carbon. Desalination Water Treat. 2014, 52, 2975–2986. [CrossRef]
27. Zhang, C.; Jiang, Y.; Li, Y.; Hu, Z.; Zhou, L.; Zhou, M. Three-dimensional electrochemical process for
wastewater treatment: a general review. Chem. Eng. J. 2013, 228, 455–467. [CrossRef]
28. Jung, K.-W.; Hwang, M.-J.; Park, D.-S.; Ahn, K.-H. Performance evaluation and optimization of a fluidized
three-dimensional electrode reactor combining pre-exposed granular activated carbon as a moving particle
electrode for greywater treatment. Sep. Purif. Technol. 2015, 156, 414–423. [CrossRef]
29. Xiong, Y.; Strunk, P.J.; Xia, H.; Zhu, X.; Karlsson, H.T. Treatment of dye wastewater containing acid orange II
using a cell with three-phase three-dimensional electrode. Water Res. 2001, 35, 4226–4230. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).