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Journal of Water Process Engineering xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Journal of Water Process Engineering

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

Combined energy and removal efficiency of electrochemical

wastewater treatment for leather industry
E. Esra Gerek, Seval Yılmaz, A. Savaş Koparal, Ö. Nezih Gerek ∗
Anadolu University, Faculty of Engineering, Eskişehir, Turkey

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

Article history: Wastewater treatment and low energy consumption are two important environmental issues. In this
Received 8 November 2016 work, a challenging treatment problem of leather industry wastewater is chosen as a case study to
Received in revised form 6 March 2017 combine the issue of energy and treatment efficiency using a common denominator of oxygen demand.
Accepted 21 March 2017
Tannery wastewater is known for its highly contaminated structure. Due to the acidic nature of the efflu-
Available online xxx
ent, conventional methods do not perform well for tannery wastes, so an electrochemical process is a
reasonable approach for the problem. Since electrochemical reactors use electricity, the energy efficiency
Keywords:
of such plants should be simultaneously considered for overall sustainability. The electricity produc-
Leather industry wastewater
Wastewater treatment
tion partially results in carbon footprints and consumption of oxygen. In this work, the electrochemical
Electric energy efficiency treatment results were assessed through total chromium removal and chemical oxygen demand (COD)
COD removal reduction. As expected, the electrochemical process parameters (reactor types, electrode variations, elec-
trical current density, etc.) as well as the process duration affect the treatment performance. Meanwhile,
these parameters also affect energy consumption. Although the energy consumption has been previously
researched, (i) “the oxygen equivalent of the required energy” and (ii) “oxygen demand reduction of the
wastewater” were not considered simultaneously before. In this work, the used energy is represented in
terms of consumed oxygen at the current electric generation profile (in Turkey and in USA). It is argued
that, as the consumed energy increases, the consumed oxygen also increases, causing a separate pollution
(in terms of COD and other indirect effects). The combined production/consumption profiles as well as
energy efficient parameter settings are investigated by experiments. It is observed that the combined
oxygen demand (i.e. reduced on the treatment side and increased at the power generation side) starts
exhibiting an overall increase at early treatment stages. For example, at an electrical current setting of
20 mA/cm2 and pH of 7, using electro-coagulation with aluminum electrodes, treatment reaches to 82%
COD removal (from 1024 mg/L to 180.71 mg/L) at 8.33 kWh/m3 , corresponding to consuming 3.23 g/L
oxygen at average energy production settings in Turkey. The oxygen consumption using electro-Fenton
exhibits similar results. The necessity of renewable energy utilization or an earlier treatment termination
is concluded.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction adopted by several treatment applications, including tanneries.

Due to the high amount of contaminating chemicals and bio-
logical residues during its production process, leather industry
wastewater must be treated effectively. There has been a deep
interest in various treatment techniques for tannery wastewater,
particularly via electrochemical methods [1–14]. Recently, uti-
lization of geopolymers and other materials with adsorption and
filtering properties has become a popular approach. Yet, electro-
chemical treatment stays to be a popular method that has been
Consequently, the literature of electrochemical wastewater treat-
ment is quite large.
Although electro-Fenton is a common practice in various
wastewater treatment cases [33–35], its application to tannery
wastewater is relatively few. The physics behind electro-Fenton
process can be reviewed from the works in [13,14,24]. Particu-
larly, the significance of pH value and contaminant concentration
was thoroughly analyzed in [31] for electro-Fenton treatment of
wastewater. The Fenton process depends on the reaction of Fe+2 ion
with H2 O2 , which produces hydroxyl radicals. Detailed chemical

∗ Corresponding author.
E-mail address: ongerek@anadolu.edu.tr (Ö.N. Gerek).

http://dx.doi.org/10.1016/j.jwpe.2017.03.007
2214-7144/© 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007
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reaction explanations and the mechanism can be found in [33–35].
The simple reaction list can be summarized as follows:
O2 + 2H+ + 2e− → H2 O2 (hydrogenperoxideproduction)
+3 − +2
Fe + e → Fe
• OH −
Fe + 2 + H2 O2 → Fe + 3 + + OH
+3 +2 +
Fe + H2 O2 → Fe + • OOH +H
Eventually, the strong hydroxyl radicals provide the system
with the necessary bonding for organic and inorganic chemicals,
which eventually reduces the chemical oxygen demand as well
as various heavy metals. The advantage of electro-Fenton is its
ability to gradually produce hydroxyl radicals. The success of this
approach was previously proven in several treatment cases includ-
ing Chromium removal [36], humic acid removal [37], winery
wastewater treatment [35], organic wastewater treatment [38],
olive oil mill wastewater treatment [39], etc.
Contrary to the relatively limited utilization of electro-Fenton
treatment for tannery wastewater, electrocoagulation is very com-
monly encountered. It has been successfully used for removing
COD, BOD, oil and chromium in tannery wastewater [3]. Electro-
coagulation does not require large doses of coagulants (due to
electrical oxidation and reduction phases), and it is operationally
as simple as the electro-Fenton method. It is also reported to be
efficient in removing very fine colloidal particles [3]. The main
chemical reactions that occur at aluminum electrodes during elec-
trocoagulation process can be listed as:
At the anode, aluminum oxidation occurs,
Al(s) → Al3+ (aq) + 3e−
At the cathode, water reduction occurs,
3H2 O(l) + 3e− → 3/2H2(g) + 3OH− (aq)
At acidic conditions,
Al3+ (aq) + 3H2 O(l) → Al(OH)3(s) + 3H+ (aq)
At alkaline conditons,
Al 3+
(aq) + 3OH− (aq) → Al(OH)3(s)
These reactions indicate that electrochemical coagulation cells
are supplied to the metal present in water. In electrocoagulation
processes, pH of wastewater (electrolyte) directly affects metal
hydroxide compounds’ solubility. At low pH, aluminum anode gen-
erates cationic monomeric species such as Al3+ and Al(OH)3 .
The removal mechanisms of chromium by electrocoagulation
or electro-Fenton are nested processes. Active Cr(iv) reduces to
Cr3+ via different equations depending on pH levels, and the oxi-
dation process. The complete set of the above removal reactions
can be found in [23,24]. Detailed explanations about various appli-
cations of electrocoagulation (standalone or combined with other
techniques) can be found in [1–12]. All the listed works agree that,
despite the large economic input of leather industry, direct disposal
of its wastewater is intolerable for the environment, particularly
for the water quality standards. In [25], it was reported that, as
of 2013, the tannery industry produces over 300 million tons of
yearly wastewater and 64,320 tons of yearly sludge in the world.
This number is expected to increase with production growth.
Beyond the COD and heavy metal removal performances,
the electrical energy consumption of electrochemical treatment
processes had also been investigated in the literature. In most
cases, the electrical energy consumption is reported at the end
of the process. The optimal duration of the process was first
investigated in [1,5]. In [15], a detailed review about electro-
coagulation in wastewater treatment was presented for various
wastewater types under a wide range of parametric conditions.
Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007
The acceptable ranges of treatment results were reported to
vary between 0.5 and 80 kWh/kg removal (depending on the
application and removal parameters), or, 0.5–30 kWh/m3 wastew-
(1)
ater treatment. For organic wastewaters (such as wastes of
(2) food industry) [16], reports 0.2–640 kWh/kg(COD) energy con-
sumption rates, depending on the applied electrical current and
(3)
waste type. For similar organic wastewaters [20], reports an
(4) energy consumption of 7.4 kWh/kg(COD) [21], reports energy
consumption of 1.75 kWh/m3 , [22] reports a consumption of
0.50 kWh/g(ammonia). For dye manufacturing wastewaters, the
required energy was reported as 51–320 kWh/kg(COD) in [17]. The
oil refinery wastewater treatment was reported to require around
a huge 200 kWh/L energy consumption [18], 13 kWh/g(COD) [19],
46 kWh/m3 [22]. In all these studies (including our own experi-
ments), the electricity consumptions are calculated according to
the measured electric parameters, duration, treatment volume, and
contaminant reduction as given in [23].
The common points in the works that consider energy consump-
tion are that they
• Calculate the energy consumption at the end of the treatment
process and give a single figure to represent the energy efficiency
(either in kWh/volume of treated wastewater, or in kWh/mass of
eliminated contamination indicator, i.e., COD).
• Give the consumed energy in kWh, but do not consider what
could be the footprint of the reported energy consumption in
terms of carbon emission or oxygen demand.
The work herein proposes a novel methodology to constitute an
(5) alternative and efficient way to look at the electrochemical treat-
ment by
(6) • Continuously monitoring the energy consumption during the
whole treatment process, and by
• Converting the electrical energy consumption to the compatible
(7) measure of oxygen demand, which enables us to assess equiv-
alent terms (i.e., COD). The approach is expected to tell us how
much average oxygen we demand at the energy production side
(8) in order to eliminate a unit amount of oxygen demand at the
treatment side.
Conversion of energy consumption (kWh) into the demanded
oxygen amount for the energy generation requires the knowledge
of energy generation profile in the particular country of interest.
Normally, a combination of all electric power sources will con-
tribute to the overall consumption. Each energy source has its own
oxygen consumption (or carbon emission) per-kWh. Depending on
the overall ratios of these individual energy source types, an aver-
age oxygen demand per-kWh for the country can be achieved [26].
Even for non-fossil fuel based electric generation systems (such as
hydro-electric plants, nuclear plants and renewable energy plants),
an equivalent effective carbon emission or oxygen consumption
rate has been evaluated [27,28]. The most current CO2 emission
averages per-kWh can be obtained from public reports of EIA,
WEA or IEA [29–31]. A recent electrical energy source distribution
study regarding the situation in Turkey can be found in [32]. Using
the proportions of that study with standard generation efficiency
assumptions, it was observed that one kWh of electric energy cur-
rently causes 0.534 kg of CO2 equivalent (as compared to the USA
cost of 0.600 kg). These results are also in total accordance with the
Turkish National Greenhouse Gas Emission Report (1990–2009).
Using atomic mass ratios, the oxygen demand can be calculated
as 0.388 kg(oxygen)/kWh. This number is, of course, valid in the
case that the used electricity is supplied by the mains connected
to the regular electric grid in the country. More detailed explana-
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Table 1
Upper limits of National Standards for Leather Production Facilities.

Parameter Unit Composite Composite

sample (2 h) sample (24 h)

COD (mg/L) 300 200

SSM (mg/L) 125 –
Kjeldahl N (mg/L) 20 15
Fat-Grease (mg/L) 30 20
S−2 (mg/L) 2 1
Cr+6 (mg/L) 0.5 0.3
Tot. Chromium (mg/L) 3 2
ZSF – 4 4
pH – 6–9 6–9

tions, experimental set-up details, observations and conclusions

are presented in the rest of the paper.
Fig. 1. Parallel plate electro-Fenton treatment set up.

2. Materials and methods

2.1. Sample acquisition, treatment regularizations and
experimental set-ups
The experiments were conducted over actual tannery wastew-
ater samples that are obtained from a leather manufacturing
and processing factory in İzmir, Turkey. The samples were col-
lected in polypropylene bottles and stored in a refrigerator at
277 K until experiments (on par with ISO 5667-1, 2007; EN ISO
5667-1/AC, 2007; ISO 5667-3:2012; ISO 5667-10: 2002 standards).
The wastewater was measured to have a COD value of about
1000 mg L−1 , total chromium concentration of about 1200 mg L−1 ,
a conductivity of close to 46 mS cm−1 and an initial pH value near
to 4.
The team has worked on a detailed suit of analyses about elec-
trochemical methods that are applied to tannery wastewater under
various testing conditions, including pH, current density, electrode
type, etc. The optimum process conditions are sought after. Besides,
the achieved results were compared to the National Standards for
Leather Production Facilities, which urges the treatment plant to
have the following upper limits (Table 1).
For both of the electrochemical experiment suits (electro-
Fenton and electrocoagulation), we used H2 SO4 (Merch, Germany)
and NaOH (Merch, Germany) for adjusting the initial pH levels of
the tannery wastewater. The pH and conductivity of the wastew-
ater were measured using pH and conductivity meter (Thermo
Scientific Orion STAR A215 model, USA). The experiments were
conducted constantly at room temperature with a cylindrical glass
reactor of 500 mL on a magnetic stirrer (Falc. Instruments F60
model, Italy) working at a stirring speed of 300 rpm. A current
controlled DC power supply (Statron type 3262, 0–5 A/0–80 V,
Germany) was used for injecting electricity to the electrodes. In
order to supply uniform electrochemical reactions, pole chargers
were used and electrode polarities were occasionally switched.
The electrochemical reactor structures were also kept identi-
cal for fair comparison. Six plates of aluminum (and iron) were
used, three connected as anodes and three as cathodes. The total
(vertically) immersed area of both anode and cathode electrodes
was ∼100 cm2 at 4 cm depth with between-electrode distance of
0.3 cm. Every time an experiment ended, the electrode surfaces
were always rinsed with diluted HCl solution and distilled water.
Additionally, H2 O2 was supplied for the electro-Fenton experi-
ments. We must emphasize that the production energy costs of
hydrogen peroxide or diluted acid/base chemicals are unknown
by the researchers, therefore their effects have been ignored in
energy oxygen demand analysis. For each experiment, the batch
processes were kept to last a maximum of 50 min with 10 min sam-
pling intervals for analysis. The samples were taken 5 mL in volume.
A centrifuge system (Nüve NF 800 R, Turkey) was used at 7000 rpm
for 5 min to eliminate sludge formation. Total chromium concen-
tration was analyzed with Agilent 8800 ICP-Triple Quadrupole, USA
(ICP MS). The residual COD concentrations were determined using
a COD reactor (Merck Spectroquant TR 420, Germany) according
to Open Reflux Method (Turkish Standard, 2010). All COD analy-
ses were carried out multiple of times and average values were
recorded. Removal efficiency was calculated as the percent COD
removal as compared to the initial COD value. The experiments
were repeated three times for every fixed pH and electrical current
density setting. The pH values were adjusted to be 3.98 (original
pH of the wastewater), 7 and 9. Tested electrical current densities
were 10, 20 and 30 mA/cm2 . Considering two types of reactors, a
total of 2 × 3 × 3 × 3 = 54 experiments (with durations of 1 h for the
process and excess time for preparation, COD/chromium determi-
nation, cleaning, etc.) were conducted. Observed parameters and
results were recorded. It was observed that variation of pH (Sec.
3.1) and electrical current density (Sec. 3.2) both alter the treatment
and energy consumption performance.
2.2. Electro-Fenton experiments
The first set of electrochemical treatment experiments were
conducted via electro-Fenton process. Classically, two different
Fenton reactor types could be used; by using metal electrodes with
added H2 O2 , or by gradually adding Fe(II) and H2 O2 to the system
for reaction. In this work, we used batch processing of wastewa-
ter with ion reactors containing iron plate electrodes (the electrical
approach) while gradually adding (or electrochemically producing)
H2 O2 to the system.
In our experiments, we have used parallel plate iron electro-
Fenton reactors that are connected to an electrical power supply.
The power supply is selected to provide controlled and constant
current (mA). The plates are submerged into the wastewater tank
with a stirrer attached to the bottom. The initial pH values were
controlled by additional H2 SO4 or NaOH, according to whether
acidity or alkalinity was aimed. The experimental setup can be
illustrated as in Fig. 1.
Treatment success results and comparisons with the alterna-
tive electrochemical method (electrocoagulation with aluminum
electrodes) will be presented in Sec. 3.
2.3. Electrocoagulation experiments (aluminum electrode)
The energy efficiency analysis and operating point determi-
nation of electrochemical processes require a wide range of
experimentation with several electrode types. However, we chose
electrocoagulation with aluminum electrodes as the alternative

Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
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to the iron-plate electro-Fenton to keep the presentation com-
pact. Coagulation and electrocoagulation are, in fact, quite popular
methods in tannery wastewater treatment [1–12]. In our experi-
mental electrocoagulation processes, we used aluminum anode to
generate coagulants in situ by electrically dissolving metal from
electrodes. Therefore, a reactor structure that is very similar to
the electro-Fenton experimental set-up is used (Fig. 1). The metal
ions (cations) are consumed at anode and hydrogen gas is evolved
from cathode for pollutant removal by flotation. The reaction details
are explained in the introduction part of this paper. An issue that
deserves attention is the passivation problem of aluminium elec-
trode (because, with the use of this system, electrode surface is
covered with passive layer, therefore the efficiency decreases). In
this study, a pole changer device is incorporated to avoid passiva-
tion.
3. Experimental results
After constructing the described experimental set-ups, several
(54) runs of experiments were conducted. Treatment and energy
consumption results for electrocoagulation and electro-Fenton,
together with the observed effects of pH and electrical current den-
sity are reported in this section. In order to keep the manuscript
compact, the effect of pH is presented at the overall best current
density of 20 mA/cm2 , and the effect of current density is presented
at a fixed pH value of 7. The experimental repetitions are aver-
aged and the measurement variances are reported. The graphs are
plotted at the mean measurement points.
It must be noted that this paper also proposes consideration
of a novel oxygen demand-equivalent of consumed energy. The
overall oxygen demand idea, its decrease/increase model, and the
corresponding observations are presented separately in Sec. 4.
3.1. Effects of pH on efficiency
The acid/alkaline value of the wastewater is naturally expected
to affect the electrolysis and removal efficiency through various
mechanisms [23]. First of all, it affects the stability of the formed
hydroxide formations. Besides, it can modify the charge particles
along the surface and therefore affect the removal of colloidal
organics from the solution [23]. For both ferrous and aluminum
ion solutions, hydrolysis and electrolysis would differently target
a predominant pH value. Hence, the initial pH value of the process
is expected to alter the removal efficiency (in terms of both total
Cr removal and COD removal). In our experiments, apart from the
original acidic pH of the tannery wastewater (pH = 3.97), two other
initial pH values (neutral pH = 7 and slightly alkaline pH = 9) were
selected in order to observe their effects on treatment. Obviously,
the pH value varies as the treatment process is performed in time.
However, each experiment was repeated with the same initial pH
settings.
The effect of pH alteration was tested using electrocoagula-
tion and electro-Fenton with analogous electrode structures at an
electrical current density of 20.00 mA/cm2 . Once a reasonable pH
setting is obtained, that value is fixed and the electrical current den-
sity was varied as 10.00, 20.00 and 30.00 mA/cm2 to see its effect
in Subsection 3.2. The total chromium removal and COD removal
performances (in time) of electrocoagulation by using aluminum
electrode are displayed in Fig. 2a and b, respectively.
For the chromium density measurements, the standard devi-
ation of 3-experiment repetitions at the end of the processes
were calculated as 3.2 in electrocoagulation, and 2.3 in electro-
Fenton. For the COD measurements, the standard deviation of
3-experiment repetitions at the end of the processes were 14
in electrocoagulation and 11 for electro-Fenton. Comparing these
Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007
deviations with the average measurements, a consistent set of
results were achieved.
Several observations can be made according to these results. For
electrocoagulation, the acidic medium of the original wastewater
pH seems to adversely affect the treatment, whereas, for electro-
Fenton, the original pH does not seem to harm the treatment
efficiency. On the contrary, the COD removal slightly suffers from
high alkalinity in electro-Fenton. Interestingly, it is difficult to argue
a persistent rule of thumb for pH preference. However, due to the
reasonable overall performance, we selected a neutral pH value
of 7 for the rest of the reported experiments for consistency. It
must be noted that these results are not per kWh that is con-
sumed throughout the process. The same graphs will be drawn
over a horizontal axis of energy consumption (kWh/m3 ) in Sec.
3, where, the oxygen demand (or carbon emission) effect of the
consumed electric energy could be incorporated over the graph.
In this section, the final energy consumptions could be discussed
as follows. Using electrocoagulation, the total energy consumption
was 7.75 kWh/m3 at pH = 3.97 and 8.33 kWh/m3 at pH = 7. These
values can also be converted to kWh/kg(COD) as 6.5 kWh/kg(COD)
at pH = 3.97 and 7 kWh/kg(COD) at pH = 7. Compared to the aver-
age energy consumption (15–40 kWh/m3 ) during electrochemical
treatment of food industry wastewater [16] or higher for oil and
dye manufacturing wastewaters [17–22], these energy consump-
tion levels are, in fact, quite low. Besides, these levels are completely
on par with the average of the literature [1–12].
Interestingly, although pH = 7 performs better in terms of total
chromium or COD removal within the same tame period, it spends
more electric energy. Therefore, a question of “which case is more
overall efficient?” arises. As a comparison, although COD removal
of electro-Fenton is visibly more effective than electrocoagulation,
it causes a high electric energy consumption of 10.46 kWh/m3 at
pH = 3.97, whereas the consumption significantly drops down to
6.93 kWh/m3 at pH = 7, making this pH value even a more desirable
setting. These energy consumption levels are also less than or equal
to the levels reported in [14,16,19] for other treatment applications
of electro-Fenton.
3.2. Effects of electric current density on removal efficiency
In both electrocoagulation and electro-Fenton, the current den-
sity (mA/cm2 ) has an obvious effect on treatment efficiency. In this
subsection, the initial pH values were fixed at a value of 7 and the
current densities were varied as 10.00, 20.00 and 30.00 mA/cm2 .
Following the graphs in Figs. 4 and 5, it can be seen that a cur-
rent density of 20.00 mA/cm2 is an overall reasonable setting
for best performance (therefore, in fact, the experiments in Sub-
section 3.1 were carried out with that current density value).
Although the higher current density of 30.00 mA/cm2 also provides
plausible treatment performance, the corresponding energy con-
sumption jumps to 12,5 kWh/m3 (from 8 kWh/m3 for 20 mA/cm2 )
in electrocoagulation and to 14.56 kWh/m3 (from 6.92 kWh/m3 for
20 mA/cm2 ) in electro-Fenton, which causes the favoring for the
electrical current density of 20.00 mA/cm2 . The energy consump-
tion for these experiments depends on the instantaneous resistance
of the aqueous solution as:
E = I × R2 × t (9)
Therefore, although the current value can be fixed, the conduc-
tance (or, conversely, the resistance) is a parameter dependent on
contamination and it also varies during treatment. Eventually, it is
difficult to estimate the consumed energy value. Instead, we have
monitored the consumption (through both voltage and current
recordings) during our experiments for analysis purposes.
As discussed in Sec. 3.1, the final energy consumption lev-
els are around 7–14 kWh/m3 , which are comparable or less than
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Fig. 2. (a) Total chromium and (b) COD removal of electrocoagulation in time at various pH settings (20.00 mA/cm2 ).

Fig. 3. (a) Total chromium and (b) COD removal of electro-Fenton in time at various pH settings (20.00 mA/cm2 ).

Fig. 4. (a) Total chromium and (b) COD removal of electrocoagulation in time at various current densities (pH = 7).

the reported electric energy consumption reports throughout the
literature [1–12,15–23]. Particularly, wastewaters with organic
contamination, such as food industry and agriculture, and wastew-
aters of oil and dye producers require up to ten folds of the energy
consumption levels reported here.
4. Energy consumption/equivalent oxygen demand for
consumed energy
Although most of the electrochemical treatment reports men-
tion about the consumed energy (and even its economic/fiscal value
[40–42]) at the end of the process, the oxygen demand – equiv-
alent approach to the consumed energy is a novel contribution
of this work. Since the proposed scheme uses electricity for the
treatment of wastewater, a proportional amount of CO2 is emit-
ted to the atmosphere for each kWh energy used. Proportionally, a
fraction of oxygen is consumed from the atmosphere. It is, there-
fore, necessary to monitor how much energy is consumed for each
unit of COD reduction and simultaneously convert the energy to an
oxygen-equivalent. For example, if the process requires M kWh for
elimination of 1 kg of COD, and if the utilized electricity causes an
oxygen consumption of N kg per generated kWh, then logic requires

Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
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Fig. 5. (a) Total chromium and (b) COD removal of electro-Fenton in time at various current densities (pH = 7).

that N × M must be less than 1 kg of oxygen for a reasonable attempt

to treatment. Otherwise, it would mean that, for each reduced COD
at the treatment site, even more oxygen is demanded at the energy
generation side, rendering the process questionable. In order to
make this analysis, the oxygen consumption (N) per produced kWh
must be estimated. According to a recent electrical energy source
distribution study [32], the power sources can be visualized as in
Fig. 6.
Once the contribution from coal and natural gas are considered,
the equivalent CO2 emission per kWh can be obtained as 0.534 kg.
As a comparison, the same CO2 emission in USA is around 0.600 kg
(according to EIA reports). Using the molecular mass formula, it can
be easily seen that 32/44 of the CO2 mass corresponds to oxygen.
By calculation:

N = 0.534 × 32/44 = 0.388 kg/kWh = 388g/kWhofoxygen (10)

in mass per consumed energy for the treatment (in Turkey).

This rate can be compared with the values of energy con-
sumption that we have obtained in our experiments. Depending
on the Fenton/Coagulation process, pH values and applied cur-
rent densities, the required energy for eliminating 90% of
1 g/L (COD) was measured between 4 and 14 kWh/m3 . These
numbers can be balanced in the common denominator as
0.004–0.014 kWh/L, or 0.0044–0.0155 kWh/g(COD). Multiplying
these kWh rates with the oxygen equivalent for production (N),
we get 388 × 0.0044 = 1.72–388 × 0.0155 = 6.35. Both of these val-
ues are larger than 1, meaning that “the overall process requires
more than 1 g of oxygen to reduce 1 g of COD”!
The above observation provides a novel insight to the
phenomenon of energy consumption during electrochemical treat-
ment: if the COD decrease is considered as the treatment issue, the
process must consider simultaneous oxygen bonding during elec-
tricity generation. As a second novel contribution of this work, it
is proposed that one does not need to consider the consumption
only at the end of the process. In fact, the COD and energy con-
sumption levels must be continuously monitored and one should
not let the process to go beyond a certain duration of treatment.
The critical time threshold for treatment is when the amount of
oxygen bonding for electric consumption overshoots the marginal
decrease in oxygen demand in the treated wastewater. The concept
is described as an illustration in Fig. 7. The proposed model shows
that the COD levels must be plotted as a function of used kWh,
where a linear oxygen consumption effect may be simply added to
the oxygen function to find an optimal point in terms of oxygen
demand.
For example, in Fig. 7, the bonded oxygen (in mass) lin-
early increases as a function of produced energy at a rate of
0.534 × 32/44 = 0.388 kg/kWh in mass per consumed energy. Prac-
Fig. 6. Distribution of Turkey’s electric energy generation in 2012.
tically, the slope of this (red) line is fairly steep, and there is a
huge necessity of very quick and efficient electrochemical treat-
ment systems. If more renewable energy is produced in a country,
or if the proposed electrochemical treatment plant is located near
to a renewable energy generator, the rate slope of this red line could
be smaller, or even zero. In this work, we made the assumption that
the treatment plant uses electricity that is plugged directly to the
mains of a grid-connected building in Turkey.
Obviously, COD is not the only contamination parameter for
treatment applications. For example, in tannery wastewaters,
chromium is a highly toxic and commonly encountered chemical
that requires careful treatment. But, Figs. 2–4 and Fig. 5 (a) shows
that the chromium elimination is quickly saturated at around
10 min. If the processes were terminated at 10 min, very reasonable
chromium removals would be obtained, while the COD reduction
(per L) would be 400 mg with an oxygen demand cost (at electric
production side) as low as 1.72/6 = 286 mg, making the system an
overall efficient one.
In order to better visualize the reasonable operation range, COD
removal performances of electrocoagulation and electro-Fenton
treatment per utilized electric energy are shown in Fig. 8a and b for
various current density settings. The electricity production oxygen
demand lines per utilized kWh are overlaid (red lines) on the graphs
with a slope of 388 mg/kWh-L. In Fig. 8a, the electrocoagulation
reactor treatment characteristic shows that, although time-wise
performance at 10.00 mA/cm2 current density stays small, its per-

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for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007
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Fig. 7. Combined oxygen demand from treated wastewater (blue / decaying curve) and electricity generation (red / straight increasing line) adds up to a total COD (black /
top curve). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 8. COD removal per utilized energy using (a) electrocoagulation, and (b) electro-Fenton at various current densities (pH = 7).

formance per consumed energy (hence per consumed oxygen) is
more efficient as compared to higher currents (the lower-going
blue curve). In fact, despite their quick treatments, higher cur-
rent values seem to be more inefficient than low current densities
in terms of per-energy treatment. The graphs show that spend-
ing energies over 1–2 kWh/m3 is technically inefficient for COD
reduction.
Interestingly, the energy efficiency property of low current den-
sities is not the case in electro-Fenton. The lowest going (hence the
most energy efficient) treatment appears to be at 20.00 mA/cm2
electric current density. Again, the applicable energy consump-
tion range is not over 1–2 kWh/m3 . The difference between these
two behaviours imply that special care must be given to each
proposed electrochemical treatment method by experimenting
according to energy consumption. For comparison, the reported
energy consumptions in [1–12,15–23] are all beyond the efficient
consumption limit, causing more oxygen to be consumed for elec-
tric production during reduction of COD. These operating curves
may be expected to differ further for various electrode types, such
as BDD, Ti/IrOx etc. Consequently, conduction of test experiments
is recommended to observe these behaviours, prior to installing
actual treatment plants.
5. Conclusions and discussions
In this work, we have presented a case study of tannery
wastewater treatment in order to illustrate the energy issues in
electrochemical treatment. Since the eventual aim of wastewater
treatment is to attain a clean and sustainable environment, spe-
cial interest must be paid to utilization electrical energy for the
process. It must be noted that an important portion of classical
electricity power plants use fossil fuels for generating electricity.
Whenever we plug our reactors to the mains of a building, we
cause a certain amount of CO2 emission. Therefore, it is not only
an economical issue to spend energy. In previous studies, the eco-
nomical aspects of spending certain energies and certain materials
were carefully investigated [40–42]. However, a compatible “oxy-
gen demand” equation is proposed for the first time in this work,
where the reduction in COD at the treatment site is compared to
the amount of oxygen necessary to produce the electrical energy
at the power generation side. If this new aspect is kept in mind,
an environmentally friendly treatment plant must also consider
energy efficiency of the process through an explicit oxygen balance
equation. This balance has two perspectives:
• How much oxygen demand are we causing while trying to reduce
the chemical oxygen demand of the wastewater? At which energy
consumption level do we need to stop? And,
• What are the optimal electrochemical reactor settings (electrode
selection, pH, current density, etc.) for best treatment-per-
consumed energy (not necessarily treatment speed)?
The answer to the first perspective (i) was sought after using an
equivalent oxygen bonding amount to compensate the COD reduc-
tion at the wastewater treatment side. A novel operation curve
(Fig. 7) is proposed to illustrate the linear increase of oxygen bond-
ing as a function of utilized energy (over where, COD reduction can
be plotted as in Fig. 8). The addition of oxygen curves produces a
“first decreasing, then increasing” pattern. It is explained that the
sign change in the slope is the point where the COD removal treat-
ment must logically stop. Experimental results show that treatment
for over 10–20 min already overshoots the efficient point for COD
reduction, so the process must be terminated at about 15 min. For-
tunately, the chromium removal already reaches to a saturation at

Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007
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these process times. As a comparison, the whole electrochemical
treatment experimental results that are reported in the litera-
ture (and mentioned in the introduction) wildly overshoots the
critical efficiency point of oxygen demand (i.e. the sweet spot).
Unfortunately, since these papers only report the electrical energy
consumption, and do not provide an equivalent oxygen demand, it
had been difficult to come up with this observation. This shows that
the described efficiency analysis must be applied to other treatment
applications, too.
Obviously, the treatment of heavy metals is a very different
issue. Their removal is separately critical as compared to simple
COD removal. In such cases, it must be emphasized that the carbon
emission of the electricity generation may not be as impactful or
important as the elimination of such poisonous metals. Therefore,
the process must, of course, continue as long as necessary for the
elimination of heavy metals down the regulation limits.
As a final remark regarding the perspective (i), the proposed
analysis is valid only for an average electricity production profile of
the country. If the treatment plant installs a self-sufficient renew-
able energy generation system (consisting of solar pV panels and/or
wind turbines) at a meteorologically suitable geographical location,
then the oxygen cost for producing each kWh energy would be
practically zero. In that case, the above analysis would be unneces-
sary and the system could continue electrochemical treatment as
long as desired.
The answer to the second perspective (ii) is easily attained
through simple experiments that show treatment per kWh (i.e.,
Fig. 7). Interestingly, we were unable to observe a consistent
rule about parameter settings in electrochemical treatment (sim-
ilar situations are observed in different treatment applications in
the literature). In the aluminum-electrode electrocoagulation case,
lower electric current density values seem to perform with higher
energy efficiency (Fig. 8a), whereas that observation was not valid
in electro-Fenton with iron electrodes (Fig. 8b). A similarly mixed
set of results were available about the efficiency of the reactors
under different pH conditions. Eventually, we conclude that a thor-
ough set of experiments is necessary for checking and observing
combinations of parameters at different values (for example, test-
ing at pH = 3, 5, 7, etc. and at each pH, testing with a current density
of 10, 20, 30, etc. mA/cm2 ) because different electrodes and dif-
ferent wastewater structures may not have a common parametric
behavior. Testing these observations with different electrodes (i.e.
BDD, Ti/IrOx etc.), different reactor styles (i.e. Raschig rings, con-
tinuous process, half cells, etc.) and different wastewater cases
(i.e. agricultural, urban, etc.) may be listed as possible future study
directions of this research.
Acknowledgments
This work has been supported in parts by the Scientific and
Technological Research Council of Turkey (TUBITAK – contract no.
115Y841) and Anadolu University Research Fund (BAP – 1601F026).
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Please cite this article in press as: E.E. Gerek, et al., Combined energy and removal efficiency of electrochemical wastewater treatment
for leather industry, J. Water Process Eng. (2017), http://dx.doi.org/10.1016/j.jwpe.2017.03.007