Chemosphere 171 (2017) 332e338

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

Electrochemical oxidation of COD from real textile wastewaters:

Kinetic study and energy consumption
Jiaxiu Zou a, Xiaolan Peng a, Miao Li b, Ying Xiong a, *, Bing Wang b, Faqin Dong c,
Bin Wang c
a
State Key Laboratory Cultivation Base for Non-metal Composites and Functional Materials, Southwest University of Science & Technology, Mianyang
621010, PR China
b
School of Materials Science & Engineering, Southwest University of Science & Technology, Mianyang 621010, PR China
c
Key Laboratory of Solid Waste Treatment and Resource Recycle of Ministry of Education, Southwest University of Science & Technology, Mianyang 621010,
PR China

h i g h l i g h t s

Real textile wastewaters were electrooxidized using BDD anode.

COD oxidation could be well fitted using a modified kinetic model.

High COD removal rates were attained with adding NaCl and in acidic media.

Low energy consumption and short electrolysis time could be obtained under the optimizing conditions.

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

Article history: In the present study, the electrochemical oxidation of real wastewaters discharged by textile industry
Received 17 October 2016 was carried out using a boron-doped diamond (BDD) anode. The effect of operational variables, such as
Received in revised form applied current density (20e100 mA$cm2), NaCl concentration added to the real wastewaters (0
8 December 2016
e3 g$L1), and pH value (2.0e10.0), on the kinetics of COD oxidation and on the energy consumption was
Accepted 15 December 2016
Available online 19 December 2016
carefully investigated. The obtained experimental results could be well matched with a proposed kinetic
model, in which the indirect oxidation mediated by electrogenerated strong oxidants would be described
Handling editor: Enric Brillas through a pseudo-first-order kinetic constant k. Values of k exhibited a linear increase with increasing
applied current density and decreasing pH value, and an exponential increase with NaCl concentration.
Keywords: Furthermore, high oxidation kinetics resulted in low specific energy consumption, but this conclusion
Textile wastewaters was not suitable to the results obtained under different applied current density. Under the optimum
Electrochemical oxidation operational conditions, it only took 3 h to complete remove the COD in the real textile wastewaters and
Kinetic study the specific energy consumption could be as low as 11.12 kWh$kg1 COD. The obtained results, low
BDD anode
energy consumption and short electrolysis time, allowed to conclude that the electrochemical oxidation
Energy consumption
based on BDD anodes would have practical industrial application for the treatment of real textile
wastewater.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction concentration of dyes and other organic and/or inorganic com-

Synthetic organic dyes have been extensively used in many in-
dustries such as textile, cosmetic, paper, pharmaceuticals and food,
thus producing large volumes of wastewaters with high
* Corresponding author.
E-mail address: xiongying@swust.edu.cn (Y. Xiong).
pounds (Martínez-Huitle and Brillas, 2009; Brillas and Martínez-
Huitle, 2015; Zhao et al., 2016). The discharge of these colored
wastewaters in the environment, without meeting required stan-
dard, would result in considerable non-aesthetic pollution and
serious health-risk factors (Forgacs et al., 2004). Thus, it is neces-
sary to apply reliable and effective treatment technologies, capable
of dealing with these organic dyes, before they are entered into the
surface and groundwater. Conventional treatments, such as

http://dx.doi.org/10.1016/j.chemosphere.2016.12.065
0045-6535/© 2016 Elsevier Ltd. All rights reserved.
 J. Zou et al. / Chemosphere 171 (2017) 332e338
physical adsorption, separation, chemical and microbiological
oxidation, have encountered hard difficulties to solve when facing
to these dyes effluents, thus cannot completely degrade the ma-
jority of these contaminated dyes (Robinson et al., 2001; Forgacs
et al., 2004; Santos et al., 2007; Ulson de Souza et al., 2007). Over
the past 10 years, the application of conductive BDD anode in the
abatement of synthetic or simulated dyes wastewaters have received
great attention, because of several technologically important
characteristics of BDD anode including high O2 evolution over-
voltage, an inert surface with low adsorption properties, remark-
able corrosion stability (S
aez et al., 2007; Panizza and Cerisola,
2008; Andrade et al., 2009; Palma-Goyes et al., 2010; Migliorini
et al., 2011; Petrucci and Montanaro, 2011; Aquino et al., 2012;
Abdessamad et al., 2013; Rocha et al., 2014; Garcia-Segura et al.,
2015; Fan et al., 2016; Migliorini et al., 2016). But until now, there
are only a few reports about the electrochemical treatment of real
textile wastewaters using BDD anode (Aquino et al., 2011; Zhu et al.,
2011; Martínez-Huitle et al., 2012; Tsantaki et al., 2012; Solano
et al., 2013).
Compared to the synthetic dyes effluents, real textile waste-
waters are more complex and usually contain organic dyes with
high concentration, inorganic ions such as chloride and sulfate, as
well as many other soluble compounds. During the electrochemical
oxidation of real textile wastewaters, competitive reactions may
occur at the anode surface and/or in the homogeneous phase, and
the different species obtained may interact creating complex sce-
narios that are difficult to describe, which is disadvantage to further
take the new technique into practice (Anglada et al., 2009).
Therefore, it is necessary to have a better understand on the elec-
trochemical oxidation process using consistent mathematical
models that can describe the reactions involved in the electro-
oxidation of multicomponent mixtures of various pollutants. In
the last decade, several mathematical models have been succes-
sively proposed to describe the processes occurring in the anodic
oxidation of organic compounds at BDD anode (Panizza et al., 2001;
Can~ izares et al., 2004; Mascia et al., 2010; Tissot et al., 2012; Hems
et al., 2016). These models can reproduce the experimental results
obtained from synthetic wastewaters with a wide variety of organic
substrates with great precision, but they still have to be validated
for real wastewaters with complex and unknown detailed compo-
sition. Recently, several groups have focused their attention on
clarifying the relationship between the operating variables and the
kinetic behaviors of electrochemical removal of ammonium, ni-
trites and COD from various real wastewaters, such as landfill
leachates, rubber manufacturing wastewaters and recirculating
aquaculture saline solutions (Díaz et al., 2011; Pe
rez et al., 2012;
Urtiaga et al., 2012, 2014). However, the kinetic study of electro-
chemical treatment of real textile wastewaters has been few re-
ported using BDD anode.
For these reasons, the aim of this study is to investigate the
viability of electrochemical oxidation using BDD anode as an
alternative to treat real textile wastewaters. Particular attention has
been devoted to the effect of several operating variables, such as
applied current density (j), NaCl concentration, and pH value, on
the kinetic behavior of COD oxidation. Finally, by optimizing the
operational variables, the energy consumption for the COD removal
has been also assessed.
2. Material and methods
2.1. Chemicals
All analytical reagents including NaCl, NaOH, H2SO4 (98%),
K2Cr2O7 and (NH4)2Fe(SO4)2 were bought from Sinophram Chem-
ical Reactant Co. Ltd, and used as received. Deionized water
333
(Millipore Milli-Q system, resistivity  18.2 MU$cm) was used for
the preparation of all solutions.
2.2. Characteristics of real textile effluent
The wastewater samples were provided by a local textile plant in
Santai county, Sichuan province, and directly collected at the
entrance reservoir. As-received textile wastewater was mainly
composed of dyes and various organic/inorganic additives. The
exact composition could not be obtained due to possible com-
mercial secret. It has high COD concentration (2154 mg/L) and poor
biodegradability (BOD5/CODCr ¼ 0.13). Its conductivity was 11.6 mS/
cm and the pH was around 12.6. Ion chromatography measure-
ments revealed the textile wastewaters contained chloride
(731 ppm) and sulfate ions (1690 ppm). It should be noted here that
no physical-chemical treatment were performed for the textile
wastewaters before the electrochemical oxidation.
2.3. Electrochemical oxidation experiments
The oxidation experiments were performed in a Diacell®201
commercial electrolytic cell (WaterDiam, Switzerland), which are
formed by two parallel flow-by compartments separated by a
central bipolar boron-doped diamond electrode, working as anode
for one compartment and as cathode for another one (Urtiaga et al.,
2014). The mono- and bipolar BDD electrodes supported by
monocrystalline Si substrate, with the thickness of 2 mm and the
working surface of about 70 cm2, were bought from NeoCoat SA Co.
The doping concentration of boron atoms in BDD electrodes was
about 5000 ppm, and the sp3/sp2 ratio was about 200. The elec-
trode distance was kept to be 1 mm. A feed tank with water-cooled
system and the capacity of 10 L was used to store the textile
wastewaters that were circulated by a centrifugal pump with a
constant flow-rate of 400 L/h. Before the electrochemical oxidation
of textile wastewaters, the anodic polarization procedure of Si/BDD
electrodes was carried out in the diluted H2SO4 solution by
applying 60 mA/cm2 for 30 min. It should be stressed that in each
electrochemical oxidation the volume of textile wastewater was
kept at 5 L. The main operational variables included applied current
density j, NaCl concentration added into the wastewaters, and pH
value. At given time intervals, liquid samples were withdrawn from
the feed tank. The electrochemical effectiveness in the oxidation of
real textile wastewaters was assessed by the COD removal of the
collected sample.
2.4. Analytical methods
The COD values were determined by the standard dichromate
method on 10 mL samples. After refluxed at 150  C for 2 h and then
returned to ambient temperature, ammonium ferrous sulfate
((NH4)2FeSO4) solution was used to titrate the residual dichromate
ions. The pH and conductivity were detected with the pH-201 pH
meter and the DDS-307 conductivity meter.
3. Results and discussion
Electrochemical oxidation of organics at BDD anode has been
achieved through three possible mechanisms: direct electron
transfer from the anode to organics, oxidation mediated by hy-
droxyl radicals (
OH) occurring in a thin layer close to the anodic
surface, and oxidation mediated by electrogenerated strong
oxidizing species such as active chlorine, hydrogen peroxide and
peroxidisulfate, often appearing in the homogeneous phase
(named as indirect oxidation) (Scialdone and Galia, 2011; Araújo
et al., 2015). In the model proposed by Comninellis et al., kinetics
334 J. Zou et al. / Chemosphere 171 (2017) 332e338
of COD oxidation could be predicted if only direct and/or
OH-
mediated oxidation were considered (Panizza et al., 2001; Tissot
et al., 2012). But in the presence of inorganic ions in the waste-
waters, electrogenerated strong oxidants would also contribute to
the overall oxidation processes, thus resulting in more complex
mechanism for COD oxidation. In recent years, several different
mathematical models, developed by modifying the Comninellis'
mathematical model, were proposed to quantify the complex
chemical and/or electrochemical oxidation processes (Can ~ izares
et al., 2004; Mascia et al., 2010; Díaz et al., 2011; Pe
rez et al.,
2012; Urtiaga et al., 2012, 2014; Hems et al., 2016). For the case of
real wastewaters, Urtiaga and coworkers demonstrated that COD
evolution could be described by the introduction of pseudo-first-
order kinetic constant k to link to the activity of the electro-
generated strong oxidants, when the oxidation is under the mass-
transport limitation (Urtiaga et al., 2012, 2014). The detailed COD
evolution is represented by the following Equation:
d½COD
V ¼ A$km $COD  k$V$COD
dt
where km is the mass transport coefficient and is measured to be
about 2.0  105 m/s in our electrolytic cell, A is the electrode area,
V is the volume of feed wastewaters, and k is a pseudo-first-order
kinetic constant that will strongly depend on the same variables
as the concentration of electrogenerated oxidants does, such as j,
NaCl concentration and pH value. In general, the more contribution
of indirect oxidation mediated by the strong oxidants to the COD
oxidation, the higher the obtained pseudo-first-order kinetic con-
stant k, meaning faster oxidation kinetics (Anglada et al., 2009; Díaz
et al., 2011; Urtiaga et al., 2012, 2014).
3.1. Effect of j on the kinetics of COD oxidation
Fig. 1a shows the effect of j on the change in COD removal during
the electro-oxidation of real textile wastewaters. At a low j
(20 mA$cm2), the COD decreases linearly at the beginning of
electrolysis, indicating that under this conditions the oxidation of
COD is under current control, and then exhibits an exponential
decay with respect to time, suggesting that the oxidation of COD is
under mass-transport control. The change is well in agreement
with the theoretical model proposed by Comninellis et al. (Panizza
et al., 2001; Tissot et al., 2012). Only about 46% COD is removed
from the real textile wastewaters after 6 h of electrolysis. When j
increases to be 40 mA$cm2, the COD removal as a function of time
can be fitted using Eq. (1) with great precision and increases to be
about 61%. Further increase in j results in greater COD removal, for
Fig. 1. (a) Influence of j on the COD removal. (The square scatter plots represent obtained experimental data, and the solid lines are the corresponding fitted results. Black:
20 mA$cm2, Red: 40 mA$cm2, Blue: 60 mA$cm2, Magenta: 100 mA$cm2) (b) the linear relationship between k value obtained and applied current density. (c) the pH variation
with respect to the electrolysis times. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
example, 78% for the case of 60 mA$cm2 and 88% for the case of
100 mA$cm2. In both cases, the COD removal presents an obvious
exponential change with the electrolysis time. Table 1 summarizes
the results obtained from fitting the experimental data to the
proposed kinetic model, Eq. (1). The pseudo-first-order kinetic
constant k almost increases linearly with increasing j, as depicted in
Fig. 1b, as expressed by Eq. (2).
 
k ¼ 1:61  105  j  3:15  103 R2 ¼ 0:997 (2)
It should be kept in mind that real textile wastewaters contains a
great variety of inorganic ions that can be lead to the formation of
strong oxidizing species, such as active chlorine and perox-
idisulfate. The linear increase of k with j suggests that at higher
current density, indicate oxidation process would make more
contributions to the COD due to the enhancement of the formation
of electrogenerated oxidants (Urtiaga et al., 2012; Martínez-Huitle
et al., 2015). Furthermore, the pH variation of the textile waste-
(1)
waters was also recorded with the electrolysis time, as shown in
Fig. 1c. In all of current density, the pH value decreases gradually,
meaning the continuous production of Hþ ions in the electrolysis
process. An increase of j leads to a more obvious reduction of pH,
which is in well accordance with the COD evolution in Fig. 1a. In
theory, there are several electrochemical and/or chemical processes
that can result in the production of Hþ ions: (1) the formation of

OH from water discharge at the anode surface and subsequently
the oxidation of organics in the diffusion layer; (2) the production
of strong oxidizing species through the oxidation of inorganic ions
at the anode surface, and then its oxidation reactions with organics
in the bulk solution, (3) other parasitic side reactions such as ox-
ygen evolution reaction (Martínez-Huitle et al., 2015). At lower j, Hþ
ions are mainly originated from the process (1), and the COD in the
wastewater is basically oxidized by
OH obtained, thus resulting in a
slower COD oxidation and smaller pH reduction. In contrast, at
higher j, the above-mentioned three processes can be co-existed
during the whole of electrolysis, thus leading to larger pH
Table 1
Pseudo-fisrt-order kinetic constant k and energy consumption Esc for COD oxidation
at different j.
j (mA$cm2) k  103 (min1) R2 Esc (kWh$kg1 COD)
20 0.05a 0.999 16.12
40 3.50 0.998 33.44
60 6.19 0.995 46.50
100 13.02 0.983 80.04
a
The k value only corresponds to the mass-transport-limited regime (exponen-
tial decay).
 J. Zou et al. / Chemosphere 171 (2017) 332e338 335

reduction. But, in the later stage of electrolysis, the latter two Table 2
processes would be strengthened, and on the contrary the first Pseudo-fisrt-order kinetic constant k and energy consumption Esc for COD oxidation
at different NaCl concentrations.
process would be suppressed, because of the low mass transport
efficiency of organics to anode surface in the wastewaters con- NaCl (g$L1)a k  103 (min1) R2 Esc (kWh$kg1 COD)
taining low organic concentration, which would be the possible 0 6.19 0.995 46.50
reason for the faster COD oxidation. 1 7.06 0.995 40.27
2 8.92 0.993 36.32
3 15.22 0.989 32.76
3.2. Effect of added NaCl concentration on the kinetics of COD
a
oxidation The concentration value refers to NaCl content added into real textile waste-
waters and do not include the NaCl existed in the wastewaters.

From the perspective of cost-saving, electrochemical COD

oxidation performed under the current control condition is the
most favorable. But under this condition, long electrolysis time is
necessary as a result of slow oxidation kinetics, which results in
increasing investment costs related with the purchase of a higher
number of cells would probably hinder the industrial imple-
mentation of the process. Therefore, a possible strategy to resolve
conflicts between energy consumption and electrolysis time con-
sists of making full use of the indirect oxidation mediated by the
formed strong oxidants to obtain faster oxidation kinetics, under
the mass-transport condition (Urtiaga et al., 2014). Given that, the
focus in the following works is to investigate how to improve the
contribution of indirect oxidation to the kinetics of COD oxidation
by adjusting the operational variables at a constant j of
60 mA$cm2.
Of all the electrogenerated oxidants, active chlorine, a term that
encompasses Cl2(aq), HClO and ClO, is the most frequently studied
one (Bonfatti et al., 2000; Martínez-Huitle et al., 2008). In our work,
to obtain exact influence of indirect oxidation mediated by active
chlorine, different amount of NaCl was firstly dissolved in the real
textile wastewaters, after that, the COD removal was investigated as
a function of the time at j ¼ 60 mA$cm2. As observed from Fig. 2a,
when an increase of NaCl concentration is attained, COD removal
efficiency is notably improved, indicating a lower charge consumed
for the same COD removal. More specifically, after 6 h of electrol-
ysis, more than 99% of COD removal is achieved when the added
NaCl concentration reaches to 3 g$L1. Meanwhile, in all cases, the
evolution of COD with electrolysis times can be fitted using Eq. (1)
satisfactorily. Values of the pseudo-first-order kinetic constant k,
corresponding to the different NaCl concentration, are shown in
Fig. 2b and Table 2. It can be observed from Fig. 2b that there is an
exponential relationship between the obtained k and the NaCl
concentration, as expressed in Eq. (3).
4
k ¼ 3:26  10 $expð1:12  ½NaClÞ þ 5:94
 
3
 10 R2 ¼ 0:998
Also, Fig. 2c shows the pH variation as a function of electrolysis
time, under different NaCl concentration. With prolonging the
electrolysis time, the pH of textile wastewaters reduces gradually,
same with the effect of j. On the other hand, the difference is that
the pH variation is almost independent of the NaCl concentrations.
It is obvious that under a constant j increasing NaCl concentration
can result in more active chlorine produced, and subsequently
promote the indirect oxidation process occurring in the bulk so-
lution, which is also the expected result (Solano et al., 2013).
Simultaneously, an increase in NaCl concentrations can suppress
the water discharge to form
OH and subsequent organics oxidation
in the very close of anode surface considering the fact that there is a
competition between the water and chloride oxidations. Further-
more, they can also minimize the parasitic oxygen evolution reac-
tion. As a result, taking all those affecting factors into account, it can
be concluded that the production Hþ ions mainly depends on the
total electrical charges applied, and is almost independent of the
NaCl concentrations.
3.3. Effect of pH value on the kinetics of COD oxidation
The pH value is an important operational parameter in elec-
trochemical oxidation of organics because in most cases the COD
removal efficiency is maximal at an optimum pH value. Therefore,
in the following experiments, we tried to maintain the pH to be a
Table 3
Pseudo-fisrt-order kinetic constant k and energy consumption Esc for COD oxidation
at pH value.
pHa k  103 (min1) R2 Esc (kWh$kg1 COD)
10.0 3.48 0.998 50.71
7.0 6.56 0.992 35.91
2.0 12.44 0.987 25.42
(3) a
In these experiments, the pH value can be adjusted through the addition of
H2SO4 and NaOH, and it remains the same during the whole of the electrolytic
process.

Fig. 2. (a) Influence of added NaCl concentration on the COD removal. (The square scatter plots represent obtained experimental data, and the solid lines are the corresponding fitted
results. Black: 0 g$L1, Red: 1 g$L1, Blue: 2 g$L1, Magenta: 3 g$L1) (b) the exponential relationship between k value obtained and added NaCl concentration. (c) the pH variation
with respect to the electrolysis times. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
336 J. Zou et al. / Chemosphere 171 (2017) 332e338
predetermined value (shown in Table 3) using H2SO4 and/or NaOH
during the whole of electrolysis process. Fig. 3a gives the obtained
relationships between the COD removal with electrolysis times and
the pH value of textile wastewaters, with a constant current density
of 60 mA$cm2 and without the addition of NaCl. A faster COD
decay can be observed with decreasing pH from 10.0 to 2.0, thus
suggesting the acidic media is conducive to the oxidation of COD. In
particular, more than 95% of COD can be removed at pH 2.0 after 6 h
of electrolysis. This is in well accordance with previous reports
about the electrochemical oxidation of simple and complex mole-
cules (Costa et al., 2009; Scialdone et al., 2009; Aquino et al., 2013).
At the same time, the COD removal with respect to electrolysis time
also follows an exponential decay tread. It is interesting in Fig. 3b
and Table 3 that obtained k presents a linear reduction with
increasing pH value, as expressed in Eq. (4).
 
k ¼ 1:46  102  1:13  103  pH R2 ¼ 0:997
On the one hand, the pH can influence the competition between
water and chloride oxidation. Generally, low pH is expected to
enhance the mediated oxidation of organics by active chlorines. In
contrast, high pH is expected to favor the oxidation of water over
chloride, thus enhancing the oxidation of organics by
OH (Trasatti,
1987). On the other hand, it can also determine the relative con-
centrations of active chlorine species. To be specific, Cl2(aq) is the
predominant species up to pH near 3.0, HClO mainly exists in the
pH range from 3 to 8, and ClO at pH > 8.0 (Martínez-Huitle et al.,
2015). As reported in previous works, the mediated oxidation of
organic with these species is expected to be favored in acidic media,
because of the higher E0 of Cl2(aq) (E0 ¼ 1.36 V vs SHE) and HClO
(E0 ¼ 1.49 V vs SHE) compared with ClO (E0 ¼ 0.89 V vs SHE).
Based on above theoretical pictures, it can be concluded that higher
COD oxidation kinetics at low pH value could be attributed to the
enhancement of the concentration of active chlorine and the
oxidation ability of as-obtained active chlorine species.
3.4. Energy consumption
For pilot- or industrial-scale applications, energy consumption
is a crucial factor in estimating the viability of wastewater treat-
ment. Thus, the effect of applied current density, NaCl concentra-
tion and pH value on the energy consumption was assessed. In our
work, the specific energy consumption Esc (kWh$kg1 COD), was
calculated using Eq. (5).
Fig. 3. Influence of the pH value on the evolution of COD removal. (The square scatter plots represent obtained experimental results, and the solid lines are the corresponding
simulated results. Black: 12.6, Red: 7, Blue: 2) It should be noted that the applied current density was fixed on 60 mA$cm2. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
Ecell $I$Dt
Esc ¼ (5)
1000$V$DCOD
where Ecell is the average cell voltage (V), I is the applied current (A),
Dt is the duration of the electrolysis (h), V represents the volume of
feed wastewater (m3), and DCOD results from the removed COD
during the time Dt (kg$m3).
Regarding the influence of j, as shown in Table 1, an increase in j
results in higher Esc, from 16.12 kWh$kg1 COD for the case of
20 mA$cm2 to 80.04 kWh$kg1 COD for the case of 100 mA$cm2.
This demonstrates that the excess of energy is spent in side re-
actions at higher current density. In Table 2, it can be seen that the
calculated Esc decreases from 46.50 kWh$kg1 COD without the
addition of NaCl to 32.76 kWh$kg1 COD for the case of 3.0 g$L1
NaCl. Increasing NaCl concentrations can improve the conductivity
of wastewaters and thus to reduce the Ecell (15.5 V for NaCl 0 g$L1
(4)
and 14.0 V for NaCl 3 g$L1). On the other hand, increasing NaCl
concentration is able to achieve faster oxidation kinetics and obtain
higher current efficiency through secondary reactions with the
participation of active chlorines. Finally, from the observation of
Table 3, experimental results show that the Esc at the pH of 2.0
(25.42 kWh$kg1 COD) is only half of that at the pH of 10.0
(50.71 kWh$kg1 COD). The reason for this behavior is that low pH
can effectively suppress the oxygen evolution reaction and over-
come the mass transport limitation of organics for the case of
OH-
mediated oxidation. Furthermore, the predominant active chlorine
in acidic media is Cl2(aq), with stronger oxidation capacity than ClO
in alkaline media, thus resulting in faster oxidation kinetics.
On the basis of above-obtained information, the energy con-
sumption was expected to further reduction with the application of
optimum operational parameters that could achieve higher COD
oxidation kinetics. To prove this conjecture, an additional experi-
ment was carried out under the following conditions: jappl of
60 mA$cm2, NaCl concentration of 3 g$L1 and pH of 2.0. Fig. 4
shows the COD evolution of textile wastewater as a function of
electrolysis time. It is interesting that under these conditions, the
oxidation of COD becomes faster, and only about 3 h, COD in textile
wastewater is removed completely. By the fitting of this result us-
ing Eq. (1), the highest kinetic constant k can be obtained to be
about 21.31. It is important to remark that the Esc can be as low as
11.12 kWh$kg1 COD. From these results, it can be reasonably
concluded that under this operational condition we can completely
remove the COD in real textile wastewater with low energy con-
sumptions (11.12 kWh$kg1 COD or 23.94 kWh$kg1 COD) and
short electrolysis times (3 h).
 J. Zou et al. / Chemosphere 171 (2017) 332e338
Fig. 4. COD evolution of real textile wastewaters as a function of time. Conditions:
j ¼ 60 mA$cm2, [NaCl] ¼ 3 g$L1, and pH ¼ 2.0.
Generally speaking, it is not easy to compare the results here
reported on COD removal and corresponding energy consumption
with those obtained by other authors due to the difference in
experimental conditions. As a result, our results in this work will
only simply compared with the reports about the treatment of real
textile wastewater using BDD anodes. Aquino et al. (2011) reported
that for a real textile effluent (COD0 ¼ 729 mgO2$L1) complete
removal of COD needed to consume electrical energy of about
30 kWh$m3, with the addition of 1.5 g$L1 NaCl and the j of
5 mA$cm2. But in this case, the electrolysis time was up to 17 h.
Mantzavinos and coworkers treated an actual textile effluent with a
COD content of 470 mgO2$L1 over a BDD anode. They found that
more than 80% of COD could be removed in 180 min of electrolysis,
at an applied current density of 8 mA$cm2, and its energy con-
sumption was about 75 kWh$kg1 COD (Tsantaki et al., 2012).
When electrochemical abatement was carried out for the real
textile effluent from Brazilian Textile industry with the COD value
of 1029 mgO2$L1, Martínez-Huitle et al. found that after the
addition of NaCl (10 g$L1), the complete removal of COD could be
achieved in the electrolysis time of 10 h, with the applied current
density of 40 mA$cm2, and the corresponding energy consump-
tion was about 36.96 kWh$m3 (Solano et al., 2013). From these
results and those here reported, it becomes clear that the
enhancement of indirect oxidation process mediated by electro-
generated active chlorine can help to improve the oxidation ki-
netics of COD and further reduce the energy consumption. It is vital
important to promote the real-scale application in the treatment of
textile wastewaters. Of course, as pointed out by Martínez-Huitle's
group.(Solano et al., 2013), particular attention in our future studies
must be devoted to monitor and limit the production of undesired
by-products, such as ClO 
3 , ClO4 and organochloride compounds
that have more dangerous than those in the beginning of the
treatment.
4. Conclusions
In summary, the present work reported the electrochemical
oxidation on BDD anodes could be suitable as an effective alter-
native for the treatment of real textile wastewaters. By introducing
a pseudo-first-order kinetic constant k, the contribution of several
oxidation processes to kinetics of COD removal could be clarified,
which strongly depended on the operational variables. Adding NaCl
337
into the wastewater and keeping acidic media of electrolytes could
significantly improve the oxidation efficiency of COD and further
reduce the corresponding energy consumption. But the increase of
applied current density would result in consuming electrical en-
ergy for the useless side reaction, even although it could also
accelerate the COD oxidation. On basis of these results, the opti-
mum operational conditions (60 mA$cm2, 3.0 g$L1 NaCl, pH 2.0)
were applied. Complete removal of COD from textile wastewaters
could be achieved in the electrolysis time of 3 h, with the lowest Esc
of 11.12 kWh$kg1 COD.
Acknowledgement
Financial project supported by National Key Technology
R&D Program of the Ministry of Science and Technology
(2014BAC13B05) is kindly acknowledged.
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