Journal of Environmental Chemical Engineering 9 (2021) 104782

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Journal of Environmental Chemical Engineering

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Treatment of textile industry wastewater by electro-Fenton process using

graphite electrodes in batch and continuous mode
Ayşe Kuleyin , Ayşem Gök , Feryal Akbal *
Ondokuz Mayıs University, Engineering Faculty, Environmental Engineering Department, Samsun, 55200, Turkey

A R T I C L E I N F O A B S T R A C T

Associate Editor: Teik Thye Lim In this study, the effectiveness of electro-Fenton (EF) technology for the advanced treatment of biologically
treated textile wastewater using graphite electrodes was investigated. The performance of the EF process was
Keywords: evaluated in terms of colour, COD and TOC removal. In batch system, the influence of process parameters such as
Textile wastewater wastewater pH, current intensity, reaction time, and Fe2+ concentration was investigated. Optimum operating
Electro-Fenton
conditions were determined as pH 3.0, current intensity of 0.55A, Fe2+ concentration of 2 mM. The use of EF
Graphite electrode
process as a post treatment technology for the biologically treated textile wastewater has led to significant
Energy consumption
reduction in colour, COD, and TOC content of textile wastewater. In continuous system, 89 % colour, 93 % COD
and 58 % TOC removal efficiencies were attained at pH 3, current intensity 1.65 A, Fe2+ of 2 mM and flow rate
25 mL.min− 1. The corresponding average energy consumption, electrical energy efficiency and current efficiency
were estimated as 16 kWhm− 3, 17 kWhm− 3order− 1 and 0.300. The results showed that EF process with graphite
anode and cathode is promising technology improving the wastewater quality for potential reuse.

1. Introduction
The textile dyeing and finishing industry is an important water
consuming industrial sector. As the effluents from textile industry have
strong colour and high chemical oxygen demand (COD), it is difficult
satisfactory treatment of these effluents. Although several traditional
technologies are applied to remove dyes in the wastewater, these tech­
nologies have some limitations [1]. Many complex wastewaters cannot
be treated effectively by conventional biological treatment processes
owing to the presence of refractory compounds. These compounds
which remain in the wastewater after biological treatment contribute
decomposed in the bulk solution through oxidation reaction with elec­
trochemically produced oxidants such as hypochlorite, chlorine and
hydrogen peroxide [8,9].
EF technology represents a combination of the electrochemical
process and the Fenton oxidation. In EF process, the major mechanisms
in the pollutant degradation are Fenton reaction in the solution (Eq. (1))
and direct oxidation on the anode surface (Eq. (4)) [10]. In EF process,
hydrogen peroxide (H2O2) is generated continuously in the solution
during electrolysis by the reduction of oxygen at cathode in acidic
conditions (Eq. (2)). Electrochemically produced H2O2 and ferrous ions
(Fe2+) added into the solution generates the hydroxyl radicals (OH ) by
•

refractory COD in the wastewater. In recent years, electrochemical the classical Fenton reaction (Eq. (1)) [11,12]. The OH is a powerful
•

technologies attract great interest in the treatment of wastewaters. This
technologies was found to be successful for the removal of various
pollutants from industrial wastewaters [2–4].
In electrochemical oxidation process, removal of pollutants occurs
through direct or indirect oxidation process. In direct oxidation process,
the pollutants adsorbed on the anode surface decomposed by the elec­
tron transfer between anode surface and pollutants without involvement
of oxidizing agent [5,6]. Most aromatic pollutants cannot be mineralized
by anodic oxidation alone because of the formation of refractory car­
boxylic acids [7]. In indirect oxidation process, the pollutants are
oxidant, has a high oxidation potential and reacts non-selectively with
the organic pollutants to ensure their complete mineralization [13,14].
Generation of H2O2 in-situ reduces the treatment cost and eliminates the
drawbacks associated with the production, transportation and storage.
Furthermore, in this process regeneration of Fe2+ ions by
electro-reduction of Fe3+ at the cathode (Eq. (3)) reduces the production
of iron sludge. As a result, E-Fenton process is considered a favourable
alternative to conventional Fenton process for the decontamination of
wastewater [15].
Fe2+ + H2O2 → Fe3+ + OH‾ + HO (1)
•

* Corresponding author.
E-mail address: fakbal@omu.edu.tr (F. Akbal).

https://doi.org/10.1016/j.jece.2020.104782
Received 6 September 2020; Received in revised form 26 October 2020; Accepted 16 November 2020
Available online 20 November 2020
2213-3437/© 2020 Elsevier Ltd. All rights reserved.
A. Kuleyin et al.
O2 + 2H+ + 2e‾ → H2O2 (2)
Fe3+ + e‾ → Fe2+ (3)
+
(4)
•
M + H2O → M(OH ) + H + e‾
EF process attracts attention owing to its high degradation efficiency
for recalcitrant organic pollutants, rapid pollutant removal rate and
environmental compatibility. EF process has been applied as a feasible
technology for the treatment of textile wastewaters [16–18]. In EF
process, electrode materials such as platinum and boron-doped diamond
were used for the degradation of various organic pollutants [19,20].
However, high price of these electrodes increases cost of treatment [13].
Carbon-based materials were also commonly used as electrode such as
graphite felt [21], activated carbon fiber [22], carbon sponge [23], and
carbon felt [24]. Graphite plate can also be used as cost effective elec­
trode material for EF applications.
The objective of this work is to investigate the advanced treatment of
biologically treated textile wastewater by EF oxidation using graphite
plate anode and cathode in batch and continuous operations. EF process
was evaluated as a polishing step for complete decomposition and colour
removal allowing the recovery and reuse of textile wastewater. In batch
operation, the effect of wastewater pH, concentration of Fe2+, current
intensity and electrolysis time on colour, COD and total organic carbon
(TOC) removal was investigated. In continuous operation, the effect of
flow rate on the efficiency of EF technology was investigated.
2. Materials and methods
2.1. Wastewater characterization
The textile wastewater was provided from textile industry producing
synthetic yarn and fabric (Çorlu, Turkey). Textile wastewater contains
most of the acid, reactive and disperse dyes that are used in the textile
industry. The wastewaters of textile industry are treated by conventional
biological wastewater treatment plant. Wastewater samples were taken
from effluent of secondary clarifier. Before EF experiments, wastewater
samples were filtered by sand column to remove suspended particles.
The physicochemical characterization of textile wastewater is given in
Table 1.
2.2. EF process
Batch experiments were performed using cylindrical EF reactor made
from glass and has a working volume of 0.5 L (Fig. 1a). Graphite plates
(99.8 %) with dimensions of 4.5cm*6cm*0.3 cm and surface area of 54
cm− 2 were used as anode and cathode. The distance between electrodes
was 3 cm. The direct current was applied by a digital power supply (GP-
4303D, 0–30 V, 0–3A), during experiments. The pH of textile waste­
water was adjusted with 0.1 N H2SO4 solution at the beginning of ex­
periments. Iron was added as FeSO4.7H2O at different concentrations to
wastewater. Continuous air supply was provided by a pump with air
diffuser. The textile wastewater in the EF reactor was stirred using
magnetic stirrer (MTOPS MS300HS). After a specified time, samples
were taken from the electrochemical reactor the pH of wastewater was
raised by the addition of Ca(OH)2 to allow the precipitation of iron as
solid Fe(OH)3. Then, the samples were centrifuged at 8000 rpm for 12
Table 1
Characteristics of textile wastewater.
Parameter Unit Range Average
pH – 7.07− 8.77 7.82 ± 0.48
EC (μS. cm− 1) 1602− 2862 2276 ± 431
Colour (Pt-Co) 120–245 167 ± 37
COD (mg.L− 1) 84–115 94 ± 9
TOC (mg.L− 1) 18− 39 30 ± 6.5
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Journal of Environmental Chemical Engineering 9 (2021) 104782
min. After centrifugation, the samples were mixed with MnO2 for 30 min
to remove residual H2O2. All samples were filtered with 0.45 mm syringe
filters before analyses.
Continuous experiments, were carried out in cylindrical EF reactor
with a working volume of 1500 mL equipped with graphite anode and
cathode with dimensions of 8cm*10cm*0.3 cm and surface area of 160
cm2 (Fig. 1b). The electrodes were connected to a digital DC power
supply (0–30 V, 0–3.0 A) and current intensity was adjusted to the
specified value before electrolysis was started. The pH of textile waste­
water was adjusted and optimum amount of Fe2+ was added to waste­
water at the beginning of experiments. The textile wastewaters in the EF
reactor was agitated with a magnetic stirrer and continuous aeration
was applied during the experiment. Peristaltic pump with two channels
was used for feeding and withdrawal of wastewater at specified flow
rates. At different time intervals, samples were taken from the outlet of
electrochemical reactor. The same analytical procedures used in the
batch experiments were applied to the samples.
2.3. Analytic methods
Colour measurements were performed using a Hach Lange DR 6000
model spectrophotometer. The overall mineralization of textile waste­
water was determined by the COD and TOC analyses. The COD analyses
were performed by the closed reflux colorimetric method. The samples
were digested by strongly acid solution of potassium dichromate
(K2Cr2O7) in the presence of silver sulfate (Ag2SO4) as catalyst and
mercury sulfate (HgSO4) at 148 ◦ C for 2 h in a thermoreactor. Then the
absorbance was measured by using a Hach Lange DR 6000 model
spectrophotometer at 420 nm. TOC was determined using a TOC ana­
lyser (Lotix TOC Analyser, Teledyne Tekmar). In TOC analysis, the
samples were ignited at 680 C on platinum-based catalyst, and the
carbon dioxide formed was swept by pure oxygen as the carrier gas
through a nondispersive infrared (NDIR) detector. Both COD and TOC
measurements were performed at least three times and average values
were considered.
In experimental studies, the removal efficiency of colour, COD and
TOC was calculated as in Eq. (5).
( )
R(%) =
C0 − Ct
∗ 100 (5)
Ct
C0 shows Colour, COD and TOC concentration in wastewater before EF
process (mg.L− 1); Ct shows Colour, COD and TOC concentration in
wastewater remaining in the wastewater after EF process (mg.L− 1).
2.4. Energy consumption
The electrical energy consumption is the principal economical
parameter affecting the operational cost of electrochemical processes.
The electrical energy consumption for different experimental conditions
was calculated using Eq. (6).
V.I.t
W= (6)
v
where, W represents the energy consumption (kWhm− 3), I is the applied
current (A), V is the potential difference in the system (Volt), t is the
electrolysis time (hours) and ν is the total wastewater volume in the
reactor (L).
The technical feasibility of electrochemical oxidation process is
generally evaluated in terms of COD removal. The removed COD can be
converted to the quantity of electrical current that causes a reduction in
pollutant concentration by using current efficiency. Current efficiency
express the ratio of the electricity consumed by the respective electrode
reaction to the electricity passed across the circuit. Current efficiency
based on COD removal (CE) was calculated as in Eq. (7).
A. Kuleyin et al. Journal of Environmental Chemical Engineering 9 (2021) 104782

Fig. 1. Batch and continuous EF reactor.

COD0 − CODt
CE = nO2 .F.v. (7)
MO2 .I.t

where, n02 is the number of electrons required for the oxidation of water
(n = 4), F is the Faraday constant (96485 C.mol− 1), ν is the volume of
wastewater (m3), COD0 and CODt are COD concentrations in the
wastewater initially and the remaining after oxidation (g.L− 1), Mo2 is
the molecular weight of oxygen (32 g.mol− 1), I is the applied current
(A), t is electrolysis time (seconds) [25].
The electric energy per order (EEO) is also an important parameter to
estimate the energy efficiency of electrochemical process. EEO is defined
as the electric energy (in kWhm− 3) required for 1 order of magnitude
reduction in the contaminant concentration in a unit volume of waste­
water. Electrical energy efficiency calculation under different experi­
Fig. 2. Effect of the pH on colour, COD and TOC removal; current intensity:
mental conditions was calculated as in Eq. (8).
0.55 A; [Fe2+]: 2 mM, time: 30 min.
P∗t
EEO = (8)
vlog(CODo
CODt
) EF process was reached at pH 3.0, where the colour removal was 89 %,
COD removal was 88 % and TOC removal was 45 % at 30 min. This
where, P is the power of the electrochemical system (kW), COD0 is the result is consistent with the findings of other researchers who reported
initial COD concentration in the wastewater (g.L− 1), CODt is the COD that Fenton process has an optimal pH of about 3.0.
concentration remaining in the wastewater at time t (g.L− 1), ν is the A low pH is theoretically appropriate for hydrogen peroxide pro­
volume of wastewater (m3), t is the electrolysis time (hours) [25]. duction, because the protons in acidic solution are consumed during the
production of hydrogen peroxide from dissolved oxygen, as shown in Eq.
3. Results and discussions (2). On the other hand, a low pH also stimulates hydrogen generation
and causes the reduction in the number of active places for hydrogen
3.1. Batch operation peroxide production as shown in Eq. (9) [7].

3.1.1. Effect of wastewater pH 2H+ + 2e‾ → H2 (9)

In EF process, the wastewater pH is an important factor influencing
the oxidation efficiency and also electrochemical production of H2O2.
The traditional Fenton process is generally operated at acidic pH values
ranging between 2 and 4. At lower pH values, the iron ions form stable
complexes with H2O2, leading to catalysts deactivation. On the other
hand, at higher pH values they precipitate as ferric hydroxides, hence
the oxidation efficiency decreases. The optimal pH for traditional Fenton
was reported around pH 3 [26].
The effect of pH on EF process was investigated in the pH range of
2.5− 3.5. The colour, COD and TOC removals as a function of pH is
shown in Fig. 2. As observed in Fig. 2, the highest removal efficiency of
The decrease in removal efficiency at pH 2.5 can be attributed to the
side effects that occur in strong acid environment. It has been reported
that higher concentration of hydrogen ions competes with the generated
H2O2 (Eq. (10)) and blocks the accumulation of H2O2, and the excess
hydrogen ions will consume the dissolved oxygen to form H2O [27].
H2O2 + 2H+ + 2e‾ → 2H2O (10)
3.1.2. Effect of current intensity
The current intensity is an important operating parameter affecting

3
A. Kuleyin et al.
the efficiency of the electrochemical oxidation process [28]. The applied
current creates a driving force for the reduction of oxygen at the cathode
resulting in hydrogen peroxide generation. The increase of the applied
current causes an increase in the production of hydrogen peroxide and
the concentration of hydroxyl radicals which are strong oxidants and
responsible for the degradation of organics. The increasing current also
increases the electro-regeneration of ferrous ion (Eq. (3)) and the effi­
ciency of Fenton chain reactions [26].
In this study, to determine the suitable current intensity for optimal
colour, COD and TOC removal, the experiments were performed at
current intensity of 0.35 A (6.5 mAcm− 2), 0.55 A (10 mAcm− 2) and 0.75
A (14 mAcm− 2). Fig. 3(a) shows the influence of current intensity on
colour removal efficiency. It can be seen that, colour removal efficiency
increased from 88 % to 93 % with an increase in current intensity from
0.35 A to 0.55 A. However, further increase in current intensity to 0.75 A
has insignificant effect on colour removal. Fig. 3(b) and (c) show the
effect of current on intensity on COD and TOC removal efficiency. At the
current intensity of 0.35 A, 78 % of COD and 43 % of TOC could be
removed at 60 min. The increase in current intensity to 0.55 A caused an
increase in removal of COD and TOC to 90 % and 50 %, respectively. A
further increase in current density to 0.75 A, increased COD removal to
Fig. 3. Effect of the current intensity on (a) colour (b) COD and (c) TOC
removal; initial pH:3; [Fe2+]:2 mM.
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Journal of Environmental Chemical Engineering 9 (2021) 104782
99 %, while had insignificant influence on the removal of TOC. Since the
electric energy consumption increased with the increasing current in­
tensity, the optimum current intensity of 0.55 A (current density of 10
mA.cm− 2) was selected for the subsequent experiments. In a study
investigating the COD removal from dyeing wastewater, it has been
reported that the COD removal increased by increasing current density,
due to the increase in the hydrogen peroxide production rate and con­
centration of hydroxyl radicals [16].
3.1.3. Effect of Fe concentration
Fe2+ ions act as catalyst in EF process and the concentration of Fe2+
has a significant effect on the process efficiency. Generally, the degra­
dation rate of pollutants and efficiency of EF process increase at high
iron concentrations, since Fe2+ ions have a stimulating effect on the
production of hydroxyl radicals [7].
In the EF experiments, both Fe2+ and Fe3+ was used as iron source to
investigate the effect of catalyst type. The colour, COD and TOC removal
efficiencies obtained with Fe2+ was slightly higher than that of Fe3+,
thus Fe2+ was used in subsequent experiments. Fig. 4(a) shows the effect
of the ferrous ion concentration on the colour removal efficiency. The
colour removal efficiency increased from 89 % to 93 % with an increase
in ferrous ion concentration from 1 to 2 mM. However, the increase in
ferrous ion concentration from 2 to 3 mM did not increase the colour
removal efficiency significantly.
The effect of Fe2+ concentration on COD and TOC removal was
Fig. 4. Effect of the Fe2+ concentration on (a) colour (b) COD and (c) TOC
removal; initial pH:3; current intensity:0.55 A.
A. Kuleyin et al. Journal of Environmental Chemical Engineering 9 (2021) 104782

shown in Fig. 4(b) and (c), respectively. It can be seen that, COD removal
increased from 76 % to 90 % and TOC removal increased from 48 % to
50 % as Fe2+ concentrations was increased from 1 mM to 2 mM. How­
ever, the increasing Fe2+ concentration to 3 mM, did not further increase
the COD and TOC removal.
Concerning the Fenton chemistry, it is evident that Fe2+ concentra­
tion has a remarkable effect on the production of HO and degradation of
•

2+
organic pollutants. But at high Fe concentrations, efficiency of EF
process diminishes due to excessive increment of ferrous ion concen­
tration acting as a scavenger for HO (Eq. (11)) [29]. The results of this
•

study are consistent with findings of other researchers.

Fe2+ + OH → Fe3+ + OH‾ (11)

•

2+
The COD removal increased with an increase in Fe concentration
from 1 to 2 mM, due to the increase of OH production at higher Fe2+
•

concentrations in the wastewater. When concentration of Fe2+ increased

from 1 to 2 mM, the COD removal increased from 76 to 90 %, indicating
that Fe2+ ions in the wastewater accelerated the degradation due to
formation of OH . But, further increase in Fe2+ concentration has
•

insignificant effect on COD removal. Hence, 2 mM Fe2+ was selected as

the optimum concentration for EF oxidation [27].
It was observed that the colour, COD and TOC removal was very high
at the initial period of oxidation process at all Fe2+ concentrations. At
the initial period of oxidation, high Fe2+ concentration leads to increase
in the production of hydroxyl radicals by the reaction of Fe2+ ions with
H2O2 produced at the cathode. The concentration of Fe2+ decreases over
time owing to the production of iron hydroxides which results in
decreasing efficiency of EF process. Also, the concentration of pollutants
also decreases with the elapsing time, which leads to decrease of
possible collisions between OH and pollutants. Therefore the removal
•

efficiency decreased with increasing reaction time [13].

3.2. Continuous operation

3.2.1. Effect of flow rate

Flow rate is expected to have a significant effect on the treatment
efficiency, as it directly affects the residence time. To investigate the
effect of flow rate, EF experiments were carried out at flow rate of 25 and
50 mL.min− 1 with Fe2+ concentration of 2 mM and current intensity of
1.65A (current density of 10 mA.cm-2). When the flow rate was 25, and
50 mL.min− 1, the residence time in EF reactor was 60 and 30 min,
respectively.
As shown in Fig. 5(a), the colour removal efficiency increased when
the flow rate decreased. The colour removal efficiency was 76 % and 89
% on average when the flow rate was 50 and 25 mL.min− 1. Fig. 5(b) and
(c) demonstrate the effect of flow rate on COD and TOC removal effi­
ciency. As the flow rate decreased from 50 to 25 mL.min− 1, the COD
removal efficiency increased from 67 % to 93 % and TOC removal ef­
ficiency increased from 42 % to 58 %. This can be explained by the fact
that low flow rate increases the residence time. In the study investi­
gating the azo dye removal at different flow rates in a continuous EF
system, it was reported that the steady-state dye removal efficiency
decreased with increasing flow rate due to the decrease of hydraulic
retention time [27]. In another study investigating the decolorization of
Lissamine Green B, Methyl Orange and Reactive Black 5 dyes in
continuous EF bubble reactor, it was reported that higher colour
removal was achieved when the residence time was increased [30].
3.3. Sludge production
The amount of sludge produced slightly increased from 0.377 g.L− 1
to 0.400 g.L− 1 by increasing current intensity from 0.35 A to 0.55 A. The
further increase in current intensity increased the sludge production
significantly. Similarly, the sludge production was nearly same up to
Fe2+ concentration of 2 mM and then increased significantly by
Fig. 5. Effect of the flow rate on (a) colour (b) COD and (c) TOC removal;
initial pH:3; [Fe2+]:2 mM, current intensity:1.65A.
increasing Fe2+ concentration (Fig. 6(a)). At optimum conditions (pH
3.0, current intensity 0.55 A and Fe2+ concentration 2 mM), EF process
was found to produce 0.400 g of sludge per liter of treated wastewater.
The composition of sludge produced during EF process was shown in
Fig. 6(b). It can be seen that EF sludge is composed of mainly O (45.7 %),
Fe (16.2 %), Ca (10.2 %), S (10.1 %), and Na (4.6 %) and contains minor
amounts of Cl, Si, Cu, N, and Zn elements.
3.4. Kinetics of EF process
The kinetic study was performed for COD as a representative
parameter for organic substances due to the complex nature of the
wastewater. The experimental data obtained at the different operating
conditions were used to determine the order of the reaction. The first-
order and second-order kinetic models were used to describe the COD
removal kinetics (Eqs. (12) and (13) respectively [31,32]:
First-order kinetics:
lnCt = lnC0 − K1 .t (12)
Second-order kinetics:
1 1
− = K2 .t (13)
Ct C0

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A. Kuleyin et al. Journal of Environmental Chemical Engineering 9 (2021) 104782

Fig. 6. (a) Sludge production at different operating conditions in EF process, (b) composition of sludge produced.

where K1 and K2 are the first-order and second-order rate constants. The
results of the kinetic study showed that the first-order kinetic model
better fit the data with higher correlation coefficients. The calculated
rate constants (K1 and K2) and correlation coefficients (R2) are presented
in Table 2. As can be seen, the first-order rate constants slightly
increased with increasing the Fe2+ concentration and current intensity.
3.5. Energy consumption of EF process
Energy consumption is the most important issue for electrochemical
concentration and reaction time on the energy consumption was
determined in batch EF system. Regarding the influence of current in­
tensity, as shown in Table 3, an increase in current intensity results in
higher energy consumption (W), from 9.1 kWhm− 3 for 0.35 A to 27
kWhm− 3 for 0.75 A at 60 min. It can also be observed form Table 3 that
the electrical energy efficiency (EEO) increased from 13.27 to 16.46
kWhm− 3order− 1 when current intensity increased from 0.35 A to 0.75 A.
On the other hand, current efficiency (CE) was 0.318 at current intensity
of 0.35 A and decreased to 0.189 with increasing current density to 0.75
A. This can be explained by the fact that concentration of degradable
compounds in the wastewater decreases and OH cannot degrade the
•

treatment of wastewater. The effect of applied current intensity, Fe2+

Table 2
Reaction rate constants for COD removal by EF process.
First Order Second Order

K1 t½ R2 K2 t½ R2
(min− 1) (min) (L. mol− 1s− 1) (min)

Current Intensity
0.35A 0.0234 29.62 0.9581 0.0006 19.60 0.9530
0.55A 0.0414 16.74 0.9460 0,0023 5.11 0.9716
0.75A 0.0890 7.78 0.9064 0,0644 0.18 0.5356
Fe2þ Concentration
1mM 0.0239 29.00 0.9349 0.0007 16.80 0.9560
2 mM 0.0366 18.93 0.8979 0.0018 6.53 0.9818
3mM 0.0398 17.41 0.9015 0.0023 5.11 0.9893

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A. Kuleyin et al. Journal of Environmental Chemical Engineering 9 (2021) 104782

Table 3 min− 1, respectively.

Energy consumption at different operating conditions.
t (min) W (kWhm− 3) CE (%) EEO(kWhm− 3) 3.6. Biodegradability assessment
Current Intensity
0.35 A 15 1.8 0.793 5.690 The biodegradability of wastewater after EF oxidation were evalu­
30 3.9 0.450 10.658 ated by using average oxidation state (AOS) and carbon oxidation state
45 5.8 0.369 11.331 (COS) parameters. AOS and COS were calculated by following equations
60 9.1 0.318 13.270
0.55 A 15 4.1 0.668 8.534
[33]:
30 7.7 0.419 10.180 COD
45 9.9 0.311 9.363 COS = 4 − 1.5 ∗ ( ) (14)
60 13.2 0.237 11.834
TOC0
0.75 A 15 6.8 0.602 14.550
30 13.5 0.335 18.999 COD
AOS = 4 − 1.5 ∗ ( ) (15)
45 20.3 0.240 20.521 TOC
60 27.0 0.189 16.463
Fe Concentration where, COD and TOC are the chemical oxygen demand (mg.L− 1) and the
1 mM 15 4.4 0.500 15.333 total organic carbon (mg.L− 1) after EF treatment and TOC0 is initial TOC
30 8.8 0.298 23.661
(mg.L− 1) of textile wastewater. AOS and COS range between +4 for
45 13.2 0.258 22.111
60 16.5 0.197 26.439 carbon dioxide and –4 for methane, indicating the most oxidized and the
2 mM 15 4.4 0.705 8.863 most reduced state of carbon [34].
30 8.8 0.423 11.861 Textile wastewater has an AOS and COS value of –1.48 indicating
45 13.2 0.315 12.381 reduced state of the textile wastewater. Both AOS and COS values
60 16.5 0.238 14.954
3 mM 15 4.4 0.766 7.521
increased with increasing reaction time. After 60 min EF treatment at
30 8.8 0.436 10.968 optimum conditions (current intensity of 0.55 A and Fe2+ concentration
45 13.2 0.307 13.869 of 2 mM), AOS and COS increased up to 3.10 and 3.53, respectively
60 18.7 0.239 16.748 (Fig. 8). Variation of AOS and COS indices from negative to positive
values indicates the enhanced biodegradability of wastewater [35]. The
produced compounds efficiently. refractory organics in the textile wastewater were further oxidized to
Fig. 7(a) and (b) shows the energy consumption, current efficiency biodegradable compounds. The AOS and COS values for continuous
and electrical energy efficiency in continuous EF system for flow rates of system operated at flow rates of 25 mL.min− 1 and 50 mL.min− 1 were
25 and 50 mL.min− 1, respectively. As can be seen, the energy con­ shown in Fig. 9. As can be seen from the figure that AOS and COS values
sumption and current efficiency decreased when flow rate increased. were higher at flow rate of 25 mL.min− 1. At lower flow rate, higher
The average energy consumption, EEO and CE were estimated as 16 retention time in the EF reactor resulted in higher oxidation of organic
kWhm− 3, 17 kWhm− 3order− 1 and 0.300 for flow rate of 25 mL.min− 1 compounds in the textile wastewater.
and 8.8 kWhm− 3, 19 kWhm− 3order− 1 and 0.220 for flow rate of 50 mL.
4. Conclusion

This study aims to investigate the feasibility of EF technology for

advanced treatment of biologically treated textile wastewater. In batch
EF experiments, the optimum levels of operating parameters such as
initial pH, current intensity, Fe2+ concentration and reaction time were
determined. The effect of pH on the colour, COD and TOC removal was
studied in the pH range 2.5–3.5. The results showed that the optimum
pH value for EF processes was 3.0. The colour, COD and TOC removal
efficiencies were obtained as 89 %, 88 % and 45 % at pH 3.0 at reaction
time of 30 min. At pH values of 2.5 and 3.5, the colour, COD and TOC
removals reduced slightly. The results indicated that the current in­
tensity and Fe2+ concentration had significant influence on the perfor­
mance of EF system. The COD removal efficiency increased with
increasing of Fe2+ concentration up to 2 mM and then remained con­
stant, while the colour and TOC removal efficiencies were similar. The

Fig. 7. Energy consumption (W), energy efficiency (EEO) and current efficiency Fig. 8. Variation of AOS and COS values for batch EF system at opti­
(CE) for continuous EF system operated at (a) 25 mL.min− 1, (b) 50 mL.min− 1. mum conditions.

7
A. Kuleyin et al.
Fig. 9. Variation of AOS and COS values for continuous EF system.
optimal Fe2+ concentration for the EF process was determined as 2 mM.
The increase in current intensity lead to the increase of the colour COD
and TOC removal efficiencies. On the other hand, the energy con­
sumption increased with the increase of current intensity. The optimum
current intensity was determined as 0.55 A (10 mAcm− 2). In continuous
EF experiments, higher COD and TOC removal was achieved at flow rate
of 25 mL.min-1 compared to 50 mL.min-1. The colour, COD and TOC
removal efficiencies for continuous system were found as 89 %, 93 %
and 58 % at pH 3, current intensity 1.65 A, Fe2+ of 2 mM and flow rate
25 mL.min-1. The corresponding average energy consumption, electrical
energy efficiency and current efficiency were estimated as 16 kWhm− 3,
17 kWhm− 3order− 1 and 0.300. It was concluded that EF technology can
be used as polishing step for biologically treated textile wastewater to
improve the water quality for potential reuse.
CRediT authorship contribution statement
Ayşe Kuleyin: Conceptualization, Investigation, Validation, Visual­
ization, Formal analysis. Ayşem Gök: Methodology, Data curation.
Feryal Akbal: Conceptualization, Investigation, Funding acquisition,
Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This study was performed in the frame of the European ERANET
MED Water-13-043 project SETPROpER with the financial support of
The Scientific and Technological Research Council of Turkey (TUBITAK)
under Grant 115Y845.
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