Journal of Water Process Engineering 31 (2019) 100834

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Journal of Water Process Engineering

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Treatment of slaughterhouse wastewater with the electrochemical oxidation T

process: Role of operating parameters on treatment efficiency and energy
consumption
⁎
Dilara Ozturka, , Alper Erdem Yilmazb
a
Department of Environmental Engineering, Faculty of Engineering, Van Yuzuncu Yil University, Turkey
b
Department of Environmental Engineering, Faculty of Engineering, Ataturk University, Turkey

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, investigation of the applicability and efficiency of electrochemical oxidation (EO) processes for
Electrochemical oxidation slaughterhouse wastewater was targeted by evaluating the treatment efficiency and energy consumption values
Slaughterhouse wastewater together. The effect of operating parameters such as type of supporting electrolyte (SE) (Na2SO4, NaNO3 and
Energy consumption NaCl), concentration of SE (0.01-0.1 M), initial wastewater pH (3–9), current density (CD) (4.73–14.20 mA/cm2)
and dilution rate of wastewater (1/1-1/4) on removal of chemical oxygen demand (COD), total organic carbon
(TOC), total nitrogen (TN), total suspended solids (TSS) and color were investigated. The most effective elec-
trolyte type was observed as NaCl. With the use of 0.025 M NaCl and 25 °C reaction temperature, at fixed 4.73
mA/cm2 CD and pH of 7.03 for 4 h reaction time, the optimum conditions for both energy consumption and
removal efficiency for treatment of SWW were obtained. At optimum conditions, TSS, TOC, COD, TN and color
removal efficiencies were found as; 99.5%, 88.0%, 92.2%, 93.5% and 99.9%, respectively, and the energy
consumption under these conditions were 153.57 kWh/m3 and 14.12 kWh/kg COD. The energy cost was cal-
culated as 1.69 $/kg COD. Also, results distinctly show that almost full mineralization of organics is obtained
after 4 h treatment. Unluckily, taking into account the large volumes of effluent produced per slaughtering cycle,
the need for long treatment times is impractical, yet if the reactor is developed to include hydrodynamic con-
ditions or combined with another treatment process which is shorter than the EO treatment time a novel setup
may be possible.

1. Introduction pharmaceuticals, pathogenic and non-pathogenic microorganisms and

It is critical to secure the environment against the growing human
population and rapid industrialization. Industrial wastewaters may
contain assorted organic or inorganic contaminants. Slaughterhouses
are a section of an expansive industry, because meat is included in the
basic diet of humans. Meat consumption continues to increase with an
acceleration in the last decades [1]. The slaughterhouse sector produces
a significant amount of wastewater from both production and non-
production units, owing to the slaughtering of animals and cleaning of
the slaughterhouse plants [2]. Wastewater contains substantial biode-
gradable organic compounds like biochemical oxygen demand (BOD)
and chemical oxygen demand (COD), nitrogen, phosphorus, oil and
grease due to suspended solids and colloidal matters such as fat, blood,
protein and cellulose [3,4]. Also, these wastewaters contain trace
amounts of drug residues because of antibiotics, vaccines and other
detergent. If such wastewater is discharged into the receiving en-
vironment without treatment, it can reduce the dissolved oxygen level
and thus negatively affect biological life [5,6]. For this reason, it is
necessary to treat wastewater before discharge into aquatic media.
Commonly, slaughterhouse wastewater (SWW) treatment ap-
proaches use biological processes such as activated sludge [7,8], sta-
bilization ponds [9], anaerobic reactors [10] and combined processes
[11,12]. Though these frameworks are successful, they generally re-
quire lengthy hydraulic retention time, expansive areas and huge
amounts of created sludge [13,14]. SWW’s may involve deleterious and
non-biodegradable organic matter, biological treatment may be in-
adequate. SWW generally contains blood; as is known, electrolytes and
ions in blood induce electrical conductivity. This makes the treatment
of SWW’s with electrochemical processes advantageous. To treat the
SWW’s many electrochemical methods were investigated. Studies

⁎
Corresponding author.
E-mail addresses: dozturk@yyu.edu.tr (D. Ozturk), aerdemy@atauni.edu.tr (A.E. Yilmaz).

https://doi.org/10.1016/j.jwpe.2019.100834
Received 13 January 2019; Received in revised form 4 April 2019; Accepted 13 April 2019
Available online 22 April 2019
2214-7144/ © 2019 Elsevier Ltd. All rights reserved.
D. Ozturk and A.E. Yilmaz
mainly focus on the EC technique and combined or hybrid processes
and fewer examine the single EO process.
Ün et al. [15] investigated hybrid processes for the treatment of
cattle-SWW using aluminum and iron electrodes. They evaluated the
impacts of CD, initial pH, and SE (Na2SO4) concentration on the effi-
ciency of the system. In the case of aluminum electrodes, polyaluminum
chloride (PAC) was utilized as the coagulant aid. COD removal of 94.4%
was obtained by adding 0.75 g/L PAC. With the use of an iron electrode,
EC was conducted simultaneously with the Fenton process. According
to the results, 81.1% COD removal was achieved by adding 9% H2O2.
Poultry slaughterhouse wastewater (PSW) treatment using the
Electro-Fenton process was investigated by Davarnejad and Nasiri [16].
The effect of pH, reaction time, volume ratio of H2O2/PSW (mL/L), CD,
H2O2/Fe2+ molar ratio was investigated on the color and COD removal.
They found the optimum conditions were reaction time of 55.60 min,
H2O2/Fe2+ molar ratio of 3.73, pH of 4.38, CD of 74.07 mA/cm2, and
volume ratio of H2O2/PSW of 1.63 mL/L for 92.3% COD removal and
pH of 3.39, reaction time of 49.22 min, H2O2/Fe2+ molar ratio of 3.62,
CD of 67.90 mA/cm2, and volume ratio of H2O2/PSW of 1.44 mL/L for
88.0% color removal.
Another study was completed by Eryuruk et al. [17] about treat-
ment of poultry SWW’s with electrochemical methods. The impact of
CD, SE (Na2SO4) concentration, feed rate of wastewater, pH and the
polyelectrolyte substance were investigated in a continuous flow
system. Also, they investigated the peroxy-electrocoagulation by using
H2O2 with several concentrations to reach maximum efficiency. When
wastewater was exposed to the peroxy-electrocoagulation, COD re-
moval efficiency of 95.4% was obtained.
Treatment of poultry SWW by EC was investigated batchwise by
Kobya et al. [18] The most elevated COD removal efficiency was 93%
with aluminum, and maximum oil–grease removal of 98% was obtained
with iron electrodes. As can be seen, SWW’s were treated successfully
using EC.
Post-treatment of SWW using EO was investigated by Awang et al.
[19] The effects of CD, reaction time and influent COD on color, COD
and BOD removal efficiencies and pH were investigated in a batch
system. Sodium sulfate (Na2SO4) was selected as SE and aluminum
electrodes were used. The optimum conditions were 220 mg/L influent
COD, 30 mA/cm2 CD and reaction time of 55 min. Under these condi-
tions, removal of color, BOD and COD were 96.8%, 81.3%, 85.0%,
respectively. Using aluminum electrodes with electrochemical post-
treatment of SWW was successful for color, BOD and COD removal.
Another study carried out by Abdelhay et al. [20] about anodic
oxidation of SWW on boron-doped diamond examined the effect of
process variables. The effect of process variables, CD, initial wastewater
pH, SE nature and concentration of electro-coagulant on the removal of
color, turbidity and COD removal was investigated. As a result, raising
the CD had a positive effect on all pollutants. Sodium sulfate (Na2SO4)
was less effective than NaCl for COD removal. Complete removal of
COD was completed in the presence of NaCl (1%) as SE. The turbidity in
wastewater was reduced by 98% with the simultaneous use of FeCl3 and
Na2SO4 owing to EC.
EC is frequently applied due to its low energy consumption and high
removal efficiency; nevertheless, these processes cause secondary
waste. Additionally, in EC, electrodes dissolve over time and need to be
replaced with new ones. Therefore, it is useful to test the processes that
are as effective as the EC process but which do not create secondary
waste. EO of organic compounds is an advanced oxidation process
(AOP), which permits total mineralization of organic matter [21]. The
organic and deleterious contaminants in wastewaters decompose
mainly via a direct anodic process or via indirect anodic oxidation by
the production of oxidants like hydroxyl radicals and ozone in EO [22].
Oxidation of the organic pollutants occurs on the anodes by active
oxygen, like hydroxyl radicals (•OH), with the direct oxidation route.
Indirect oxidation begins in the presence of chlorine ions as creation of
chlorine or hypochlorite oxidizes the inorganic/organic matters [23].
2
Journal of Water Process Engineering 31 (2019) 100834
EO has many advantages in comparison with conventional and
other AOP treatment methods. They involve no subsidiary waste gen-
eration, such as expended sorbents, sullied retentate, ferric hydroxide
waste or waste activated sludge that occurs with adsorption, filtration,
Fenton reactions and biological processes, respectively. EO has the
advantage of easy inspection via operation and does not require extra
chemicals to control the process. EO is applicable for the treatment of
industrial wastewaters owing to good electric conductivity of the
wastewaters [21]. Also, EO is appropriate for colored and blurred
wastewater, which is difficult to clarify with photo-degradation and
catalysis [21]. But, as in other processes, EO has inconveniences. These
are abrasion, passivation and polarization of electrodes and high energy
consumption. When electrochemical technologies are compared with
other technologies, they consume much more energy but are more ef-
ficient and more compact. It is critical to emphasize that electro-
chemical reactors work with dc current, which can be obtained from
renewable energy sources like photovoltaic cells (PV) [24].
In the EO process, use of SE energy consumption is reduced while
the efficiency of the treatment is increased. Polarization of the anodes
and cathodes occurs with low mass conduction and the gases aggregate
on the surface of electrode and this gives rise to the exhaustion of
electro-active species in the border coat of the electrode [21]. Abrasion
of the electrodes is another problem caused by oxidation reactions of
the anode and the formation of abrasive products on the surface of
electrode, for instance Cl2(g). This issue can be solved by improving
new electrode materials, or by choosing optimal anode materials.
Various electrodes are used in EO of organic pollutants in wastewaters
such as graphite electrodes, metal electrodes, mixed metal oxide elec-
trodes (MMO), boron-doped diamond (BDD) electrodes, etc. [25–27]
because of their long service life, abrasion resistance and high potential
to produce oxygen and hydroxyl radicals by electrochemical reactions.
Taking into consideration that electrochemical processes are com-
pact and simple to automate [28], the improvement of small-sized
electrochemical wastewater treatment systems to treat SWW might
become an alternative to be explored.
As far as the authors are aware, there are many studies about
electrochemical treatments of SWW's and there are fewer studies about
the use of single EO processes on SWW’s, but there are no published
studies investigating the combination of many parameters’ efficiency
using Ti/Pt anodes on cattle-SWW's treatment in a single EO process.
The authors also intend to contribute to the literature by predicting
the feasibility and efficiency of a single EO operation with active anodes
(Ti/Pt) on an industrial scale for SWW's.
2. Material and method
2.1. Materials and characterization of wastewater
The wastewater used in this work was collected from a cattle
slaughterhouse (Van, Turkey). The sample was taken from the main
effluent outlet and stored at 4 °C before use in experiments and further
studies. The chemical analysis of SWW is shown in Table 1 giving the
maximum and minimum values of the samples taken during 6 months.
All chemicals utilized in this study were purchased from E. Merck with
a purity of 99.4%. Mesh type Ti/Pt and Ti electrodes were selected as
anode and cathode, respectively. Because of highest electrocatalytic
activity towards organic oxidation [29], Ti/Pt electrodes were chosen
as anode.
2.2. Experimental setup
The experimental apparatus is shown in Fig. 1. A glass jacketed
reactor, for the circulation of the coolant liquid (antifreeze), was used
in experiments. Wastewater of 700 mL was used in the batch studies.
During the study using three (3) Ti/Pt mesh type anodes and three (3)
Ti mesh type cathodes, the total areas of the electrodes were calculated
D. Ozturk and A.E. Yilmaz Journal of Water Process Engineering 31 (2019) 100834

Table 1 method 180. Before color analysis, the pH values of the samples were
Chemical analysis of SWW. set to 7.6 as recommended by the NCASI method [36] and filtered by
Parameters Units means of 0.4 mm filter paper. Deionized water was used as a blank. TN
readings were completed with the nitrogen (total) cell test method
Nitrate (NO3−)(mg/L) 18.55 – 35.86 (based on peroxydisulfate oxidation / 2,6-dimethylphenol) by using a
Sulfite (SO3−)(mg/L) 15.31 – 89.28
spectrophotometer (Spectroquant-prove 300) according to the method
Phosphate (PO4−3) (mg/L) 72.25 – 190.48
−
Chlorine (Cl )(mg/L) 239.93 – 422.69
of 108. TOC was measured with a TOC analyzer (Shimadzu TOC-L at
Total carbon (TC) (mg/L) 4535 – 10494.62 680 °C). The Lovibond water testing photometer system MD100 was
Total organic carbon (TOC) (mg/L) 4429 – 10250 used for TSS measurements. The photometric specification of sus-
Inorganic carbon (IC) (mg/L) 105.70 – 244.62 pended solids is based upon a gravimetric method. This is ordinarily
Total nitrogen (TN) (mg/L) 800 – 1546
based on evaporation of the filter remnant of a filtered water specimen
Ammonium nitrogen (NH4-N) (mg/L) 20 – 38
Total COD (mg/L) 17626 – 23268 in a stove at 103–105 °C and weighing of the dried remnant. For higher
Dissolved COD (mg/L) 13658 – 18029 accuracy we performed a gravimetric determination of samples. The
Particulate COD (mg/L) 3968 – 5239 results of the photometric method are consistent with the results of the
Biochemical oxygen demand (BOD) 2810 – 3743
gravimetric method with a margin of error of ± 1%. The energy con-
Oil & grease 50 – 407
Total Suspended Solids (TSS) (mg/L) 475 – 1800
sumption was calculated using Eq. 1.
Electrical conductivity (EC) (mS/cm) 1.36 – 3.04
kWh VxIxt
pH 7.03 – 8.23 Energy Consumption ⎛ 3 ⎞ =
⎝ m ⎠ v (1)

Where; V (Volt) is potential difference, I (ampere) is current intensity, t

as 1056 cm². All electrodes had rectangular shape with dimensions of
(hour) is time, and v (m3 ) is SWW volume. During the process, the
40 mm x 200 mm. The distance between the electrodes was the least
amount of electrochemical energy consumption and per kg of removed
possible (3 mm), because decreasing the space between the electrodes
COD was calculated using Eq. 2 [37].
reduces energy consumption [30]. Electrodes were connected in par-
allel. Ti/Pt and Ti electrodes are reported in the literature for use in kW − h ⎞ VxIxt
E ⎛⎜ ⎟ =
several studies about wastewater treatments [31–33]. In order to pro- ⎝ kg COD ⎠ ΔCxVR (2)
vide the required electric current during the trials, a TTI/QPX1200S
model digital controlled direct current (DC) power supply (0–60 V, where, V is the average of applied voltage (V), I is the applied current
0–50 A) was used. WTW multi340i multimeter was utilized to adjust the (A), t is the time of reaction (h), Δ C is the difference between the input
pH, conductivity and temperature values of the SWW at the beginning and output COD to the reactor (mg/L), and VR is the SWW volume (L).
of the reaction and to read these values momentarily during the reac- Removal efficiency was calculated by Eq.3.
tion. The initial SWW pH was adjusted with nitric acid (0.1 M) or so- (C0 − Ct )
dium hydroxide (0.1 M). Due to the nature of the EO process, there is an Removal efficiency (%) = x100
C0 (3)
increase in heat during the reaction, so a temperature-controlled liquid
circulator (Labo C200-H13) was used to keep the SWW at a constant Where; C0 and Ct are pollutant concentration before and after the re-
temperature. All experiments were performed at atmospheric pressure action with time t, respectively.
and constant temperature (25 °C). The electrolysis time in the EO pro-
cess is highly effective both on the removal of pollutants from the 3. Results and discussion
system and on energy consumption. Several preliminary tests were
performed before deciding the reaction time. As a result of the ex- 3.1. Effect of initial pH of SWW
periments, it was observed that the EO rate of all pollutants was slow.
This may be due to the properties of the anode material used. For this The pH of wastewater could have both a positive and a negative
reason, the reaction time was chosen as 4 h to observe satisfactory re- effect on the mineralization of organics as it affects the stability of
moval efficiency and provide the discharge standards. various hydroxide species that form. The impact of initial pH on COD,
TOC, TN, TSS and color removal was firstly examined. In this way, pH
2.3. Analytical methods values of 3, 5, natural pH (7.03), 8 and 9 were investigated at fixed
4.73 mA/cm2 CD without using SE and fixed reaction temperature of
COD was measured with the closed reflux colorimetric method ac- 25 °C and reaction time of 4 h (Fig. 2).
cording to the standard methods for measurement [34]. Color mea- The removal efficiency for all pollutants increased when the initial
surements were carried out using the platinum–cobalt standard method pH value of the wastewater increased from 3 to 7.03. While the removal
[35] with a spectrophotometer (spectroquant-prove300) according to efficiencies at pH 7.03 and 8 were close to each other, the effluent

Fig. 1. Experimental Setup (refrigerant fluid circulator (1), (2) glass jacketed reactor, (3)Ti/Pt mesh type anodes and Ti mesh type cathodes, (4) direct current (DC)
power supply).

3
D. Ozturk and A.E. Yilmaz
Fig. 2. Effect of initial pH on the removal of TSS, TOC, COD, TN and color.
efficiency decreased abruptly when the pH increased to 9. Moreover,
TSS and color removal efficiencies did not change much at pH values
other than pH 9. This indicates that the degradation with Ti/Pt per-
formed well in wide ranges of pH, which means pH adjustment is not
required (if pH of 9 is not exceeded) and thus treatment costs will be
reduced in practical applications.
Initial pH of SWW was a very substantial parameter for the treat-
ment of SWW by EO. It can be seen from the results that the removal
efficiency for all selected pollutants in the SWW was highest at neutral
pH (7.03), and quite low in very acidic (3) and basic (9) conditions. The
removal yield was less in acidic conditions owing to OH− instability
and noticeably more in alkali solution owing to formation of OCl- ion
indicating that the basic or neutral pH situations were more favorable.
Under acidic conditions to produce HOCl, the OCl- and H + ions un-
dergo the reverse reaction of combining with each other (Eq. 4) [38].
So, OCl− ions prefer the reverse reaction rather than oxidizing the
pollutants due to its instability. Also, acidic conditions considerably
reduce the concentration of notable oxidative radicals of •OH produced
on anodes [39].
HOCl↔[H++OCl−]
On the other hand, active chlorine at high pH is found as hypo-
chlorite, which is a less potent oxidant of organic species than hypo-
chlorite acid [40].
The removal efficiencies depend on the initial pH value as well as
the pH values during the process (Fig.3).
As shown in Fig. 3, the effluent at all pH generally increased during
the first 90 min of reaction, and then began to slightly decrease or re-
main stable until 240 min. The pH rises owing to the release of more
OH− ions than protons in the solution due to reactions on the cathode
and anode. In cases where EO is dominant, a tendency for pH to remain
constant or slightly increase is observed. After 90 min pH decreases,
Fig. 3. The variation of pH values during the reaction.
Journal of Water Process Engineering 31 (2019) 100834
Fig. 4. Effect of current density on the removal of TSS, TOC, COD, TN and
color.
which could be due to the formation of HOCl−. At this point, the pH of
the media is either more acidic or basic, depending on whether HOCl−
or OCl− is dominant at these points. The degradation of organic com-
pounds can occur at different pHs. The maximum removal efficiency at
initial pH (7.03) can be explained with this approach. So, it can be said
that the removal efficiency of the EO process is not only related to in-
itial wastewater pH, but also to the variation in pH during EO.
3.2. Effect of current density
The impact of CD on the COD, TOC, TN, TSS and color removal was
examined at 4.73, 9.47, and 14.20 mA/cm2 CDs at initial pH of 7.03
and reaction temperature of 25 °C, without using SE and reaction time
of 4 h. According to the results, as CD increased all remaining pollution
parameters decreased (Fig. 4).
For this situation it can be said that the increase in CD greatly
speeded up the removal of pollutants due to the production of more
electrons [41], but at higher CD, generation of additional electrons may
(4) contribute to unwanted side-reactions such as parasitic loss reactions
causing the consumption of hypochlorite concentration [42,43]. Results
for 4.73, 9.47; and 14.20 mA/cm2 on COD, TOC, TN, TSS and color
removal for each CD are; 78.2, 71.5, 78.7, 89.6 and 88.1%; 91.4, 94.5,
97.6, 98.8 and 99.2%; and 96.1, 96.2, 98.2, 99.8 and 99.2%, respec-
tively. As seen, the concentrations of COD and TOC decreased to 96.1%
and 96.2, thus confirming the degradation of organic compounds ex-
isting in the SWW by the low amount of electrically-produced oxidative
species and chemisorbed oxygen on the anode surface.
It is clear from the results that even at lower CD’s, the removal ef-
ficiency was good for all pollutants. This situation suggests that oxi-
dation is based on the characteristic of the electrode, and that it might
be executed by both direct (oxidation of pollutants by electrons trans-
ferred to the electrode surface) and indirect oxidation (oxidation with
electrogenerated hydroxyl radicals (•OH) formed from water discharge
at the anode surface (M) (Eq. 5) [44]. The activity of the •OH radicals is
strongly related to their interaction with the electrode surface (M).
M+H2O→ M(•OH) +H++ e− (5)
Although the removal of pollutants is largely dependent on the
applied CD, the type and characteristic of the anode material used is
also very effective. Ti/Pt electrodes are categorized as active material
[45,46]. According to the literature [47–49], low amounts of reactive M
(•OH) are formed by oxidation at Ti/Pt electrodes (Eq. 5) because the
strong M‐•OH interaction and low O2 evolution overpotential facilitates
oxidation to yield the weaker MOx (chemisorbed oxygen on anode
surface) species [62]. The MOx species favoring partial conversion of
the pollutants (P) (Eq. 6).
P + MOx→ M + POx (6)
4
D. Ozturk and A.E. Yilmaz Journal of Water Process Engineering 31 (2019) 100834

Finally, they are oxidized with low M(•OH) radicals until thorough
oxidation (CO2 and H2O) is achieved (Eq. 7).
M(•OH)
POx CO2 + H2 O
→ (7)

This situation lengthens the time of electrolysis, as previously re-

viewed by other authors [48,50].

3.3. Effect of supporting electrolyte type and concentration

The effect of SE type on the COD, TOC, TN, TSS and color removal
was examined at fixed 4.73 mA/cm2 CD, natural initial SWW pH (7.03)
and temperature of 25 °C using different SE’s (NaCl, NaNO3 and
Na2SO4) at 0.1 M SE concentration and reaction time of 4 h. Sorting
NaCl, NaNO3 and Na2SO4 by removal efficiency, the following order
was found; NaCl > NaNO3 > Na2SO4 electrolyte. NaCl has the highest
removal efficiency which is similar to observations reported in the lit-
erature [51,52]. The highest yield was seen in this SE owing to the
formation of strong oxidizing species such as chlorine radical, hypo-
chlorous acid (HClO−) and hypochlorite ion (ClO−) [53]. NaNO3 and
Na2SO4 electrolytes were not as effective as NaCl. This situation was
explained by Fil et al. [54] as being due to Na2SO4 and NaNO3 elec-
trolytes not including chloride ions in their molecular structures and
they may change into a more stable media that is broken down by direct
electrolysis. Also, the reason for lower efficiency of the process in
NaNO3 and Na2SO4 media compared to NaCl is because both are inert
electrolytes unlike NaCl which produces active chlorine species
[55,56].
Using SE leads to an increase in the removal efficiency for all pol-
lutants. Numerical results are illustrated in Table 2 and the removal
efficiency graph is shown in Fig. 5(a).
To investigate the effect of SE concentration on removal efficiency,
NaCl was chosen as SE with different concentrations (0.01, 0.025, 0.05, Fig. 5. Effect of supporting electrolyte type (a) and concentration (b) on the
0.1 M) at fixed 4.73 mA/cm2 CD, natural initial SWW pH (7.03), tem- removal of TSS, TOC, COD, TN and color.
perature of 25 °C for 4 h reaction time. The removal efficiency at SE
concentration of 0.1 M was COD (96.2%), color (100%), TN (94.2%), As an alternative, chlorine is quickly hydrolyzed and forms hypo-
TOC (93.9%) and TSS (100%); at 0.05 M SE concentration removal chlorous acid and chloride ions;
efficiency was observed as COD (94.6%), color (99.9%), TN (93.8%),
TOC (92.0%) and TSS (100%); at 0.025 M SE concentration results were Cl2(aq)+H2O↔HClO + Cl−+H+ (10)
observed as COD (92.2%), color (99.9%), TN (93.5%), TOC (88.0%) Hypochlorous acid is in equilibrium with the hypochlorite ion;
and TSS (99.5%); and at 0.01 M SE concentration the removal efficiency
for COD (88.2%), color(99.5%), TN (80.0%), TOC (85.0%) and TSS HClO↔ ClO− +H+ (11)
(98.9%) was observed.
The prepotent species is soluble chlorine up to pH near 3, HClO at
The indirect oxidation process varied with the NaCl concentration in
pH between 3 and 8, and ClO− above pH 8 [44].
SWW. It is well-recognized that electrolysis of chloride solutions in a
On the other hand, depending on the conditions of operation, the
disunited cell includes the anodic oxidation of Cl−, to provide soluble
possibility of chlorate formation may also be considered:
Cl2 [44]:
ClO−+2HClO→ClO3−+2Cl−+2H+ (12)
2Cl− →Cl2(aq)+2e− (8)
Chlorate may promote indirect removal of organics. In the course of
There is accompanying attenuation of water at the cathode, which
indirect oxidation, an elevation in NaCl concentration gives rise to
provides OH− and H2(g). If the concentration of solubilized chlorine
stepped interchange of the oxygen alteration reaction to more favorable
exceeds its solubility, supersaturation results in the creation of Cl2(g)
potentials, when checked against electrolysis applied in the lack of SE.
blisters [44]. Since the electro-produced chlorine spreads away from
Similar observations are reported in the literature [44,57,58].
the anode, trichloride ions can occur by means of reaction with chloride
As can be seen from both numerical and graphic results (Fig. 5(b)),
ions;
at 0.025 M and above the removal efficiency for all pollutants did not
Cl2(aq)+Cl−↔Cl3− (9) change much. Also, the use of 0.01 and 0.025 M NaCl reduced the en-
ergy consumption and results are close to each other; in the same way
Table 2 the use of 0.05 M and 0.1 M NaCl produced almost the same results. To
Effect of supporting electrolyte type on removal efficiency. decide the optimum electrolyte concentration, it is important to know
whether the discharge standards are achieved when the concentration
Type of SE TSS (%) TOC (%) COD (%) TN (%) Color (%)
is applied. With the use of 0.025 M, discharge limits [2] of SWW’s are
Without SE 89.6 71.5 78.2 78.7 88.1 provided for the effluent concentration of COD (120 mg/L), TN (10 mg/
NaCl 100 93.5 96.2 94.2 100 L) and TSS (0 mg/L). So, it can be concluded that the concentration of
NaNO3 93.5 87.0 89.3 86.2 92.9
0.025 is sufficient to achieve the discharge limits. Consequently, the
Na2SO4 92.0 75.1 82.3 84.2 89.3
addition of chloride had a considerable effect on the treatment of SWW

5
D. Ozturk and A.E. Yilmaz Journal of Water Process Engineering 31 (2019) 100834

Fig. 7. Effect of the initial pH on the energy consumption related to COD re-
Fig. 6. Effect of diluting rate on the removal of TSS, TOC, COD, TN and color. moval.

by EO even with both low CD and low concentration of chloride.
3.4. Effect of dilution rate of SWW
To investigate the effect of dilution rate, the raw SWW was diluted
with tap water to 1/1 (raw wastewater), 1/2, 1/3, 1/4 and 1/5 and
experiments were conducted at fixed 4.73 mA/cm2 CD, natural SWW
pH (7.03), temperature of 25 °C, and 4 h reaction time without using
any SE. All pollutant removal efficiencies are illustrated in Fig. 6. The
reduction in dilution factors resulted in an increase in the removal ef-
ficiency owing to the reduced pollution concentration. However, this
would not be suitable for an industrial process, as it would require the
need to purify more water due to the use of even more water. Similar
observations are available in the literature [59,60]. For all dilution
rates, results are given in Table 3.
3.5. Energy consumption
Like all treatment methods, the cost of the system is as important as
the removal efficiency for the EO process. While this study was carried
out to treat 700 mL of wastewater, the energy consumption values were
calculated for all operational parameters as the amount of energy
consumed per cubic meter of wastewater (Eq. 1) in order to create an
estimate for an industrial plant. After deciding the optimum operation
conditions, to calculate the energy consumption as the amount of en-
ergy spent per removed kg COD Eq. 3. was used.
3.5.1. Effect of initial pH on energy consumption
The influence of the initial pH on the energy consumption related to
COD removal is presented in Fig. 7. The maximum energy consumption
per m3 wastewater from maximum to minimum is as follows; pH7.03
> pH8 > pH5 > pH3 > pH9 for initial pHs. This situation is related
to the HNO3 and NaOH added to the wastewater which increased the
conductivity of the wastewater and the increase in conductivity de-
creased the potential difference applied to the system in experiments
with constant CD (4.73 mA/cm2). On the other hand, the highest re-
moval efficiency for all pollutants was observed at SWW’s natural pH
(7.03) which did not need chemicals for adjustment of pH (see Fig. 2).
In order to achieve cost advantages, high removal capability and low
energy utilization should be chosen. When the energy consumption
values are considered, it is clear that the lowest consumption value is at
pH 9, but when the cost approach is considered according to industrial
applications, it is obvious that the cost will increase depending on the
amount of base to be used to increase the original waste water pH value
to 9. In such cases, different parameters should be evaluated in order to
make a decision. More importantly, it should be decided whether the
priority goal is the removal efficiency or the cost advantage.
3.5.2. Effect of current density on energy consumption
Energy consumption was calculated for 4.73, 9.47 and 14.20 mA/
cm2 CD for operation conditions fixed as initial pH of 7.03, 25 °C
temperature, 4 h reaction time without SE. The results are shown in
Fig. 8. It is obviously seen from Fig. 8 that as the CD increases, the
potential difference applied to the system and COD removal efficiency
increases and the rise in the potential difference increases the energy
consumption. Increasing CD accelerates the EO process and reduces the
reaction time but according to Faraday's Law the increase in CD in-
creases the consumption of electrodes [61]. Above 4.73 mA/cm² energy
consumption increased significantly, so these CDs are not applicable at
real scales. This is why 4.73 mA/cm² was chosen as fixed CD for further
studies.
3.5.3. Effect of supporting electrolyte type on energy consumption
The change in the energy consumption of the system versus time is
shown graphically in Fig. 9 for NaCl, NaNO3 and Na2SO4 at fixed
concentration of 0.01 M, under operation conditions of 25 °C tempera-
ture, pH 7.03 and 4 h reaction time.
When the results are examined, it is seen that the SE type sig-
nificantly affects the energy consumption. The energy consumption for
each type of SE is lower than the energy consumption obtained from the
trials without SE. The reason for this is that the solubility of the SE used
are very high, resulting in good ionization in the solution medium and

Table 3
Effect of dilution rate on the removal efficiency.
Dilution rate TSS(%) TOC(%) COD(%) TN(%) Color(%)

1/1 (raw) 89.6 71.5 78.2 78.7 88.1

1/2 94.3 82.8 81.4 80.0 92.9
1/3 95.2 85.6 87.5 84.2 96.4
Fig. 8. Effect of current density on the energy consumption related to COD
1/4 97.7 93.9 91.6 90.6 98.0
removal.

6
D. Ozturk and A.E. Yilmaz
Fig. 9. Effect of supporting electrolyte type on energy consumption related to
COD removal.
thus increased electrical conductivity of the solutions. An increase in
the electrical conductivity of the solution causes a decrease in the po-
tential difference applied at the constant current, which results in low
energy consumption. At the end of the reaction, consumption of energy
values can be listed without SE, NaNO3, Na2SO4 and NaCl as; 243.31,
206.86, 191.80, and 174.31 kW h/m3, respectively. NaCl has minimum
energy consumption among other salts because of its high solubility and
good ionization in solution. Even at very low concentration (0.01 M
NaCl), there was 28.35% less energy consumption compared to the
experiment without SE. When deciding on the electrolyte type, the io-
nization, the capacity to reduce the potential difference, the behavior of
reducing the energy consumption and the indirect removal efficiency
on pollutant parameters should also be taken into account. Because
when applied in a real facility, tons of the electrolyte considered to be
the most suitable will be used. Considering all respects, the most sui-
table electrolyte is NaCl.
3.5.4. Effect of supporting electrolyte concentration on energy consumption
To investigate the effect of SE concentration on energy consump-
tion, NaCl was chosen as target electrolyte. Studies were carried out
with 0.01, 0.025, 0.05 and 0.1 M SE concentrations at fixed 25 °C re-
action temperature, 4.73 mA/cm2 CD, initial pH of 7.03 and 4 h reac-
tion time. Results are shown in Fig. 10.
When Fig. 10 is examined, increasing the SE concentration de-
creases the energy consumption and increases the COD removal. The
conductivity of the wastewater increases as the amount of SE added to
the system increases, and this leads to a decrease in the potential dif-
ference required to pass the same current through the system so the
consumption of energy reduces. At the end of the reaction, values of
energy consumption can be listed for concentration of 0.01 M, 0.025 M,
0.05 M and 0.1 M NaCl as; 174.31, 153.57, 143.43 and 118.86 kW h/
m3, respectively. It can be seen from Fig. 10 that the use of 0.01 and
Fig. 10. Effect of supporting electrolyte concentration on energy consumption
related to COD removal.
7
Journal of Water Process Engineering 31 (2019) 100834
Fig. 11. Effect of dilution rate on energy consumption related to COD removal.
0.025 M NaCl reduced the energy consumption and results are close to
each other; in the same way the use of 0.05 M and 0.1 M NaCl produced
almost the same results. Although the application of increasing con-
centration of SE may have a reducing impact on energy consumption,
when deciding the optimum concentration of SE it should also be noted
that the effluent must meet the discharge standards specified for that
wastewater. With the use of 0.025 M, discharge limits [2] of SWW’s are
ensured for the effluent concentration of COD (120 mg/L), TN (10 mg/
L) and TSS (0 mg/L). So, it can be concluded that the concentration of
0.025 NaCl is sufficient to achieve the discharge limits. Optimum
conditions are accepted as the use of 0.025 M NaCl and 25 °C reaction
temperature, at fixed 4.73 mA/cm2 CD and initial SWW pH of 7.03 for
4 h reaction time in terms of both energy consumptions and removal
efficiency for treatment of SWW. Also, energy consumption value for
per kg COD calculated for 0.025 M was 14.12 kW h/ kg COD.
3.5.5. Effect of dilution rate on energy consumption
To understand the real effect of dilution rate on the energy con-
sumption, this study was conducted in an environment without SE at
constant 25 °C reaction temperature, 4.73 mA/cm2 CD and 4 h reaction
time. Fig. 11 exhibits the plot of energy consumption per m3 waste-
water versus dilution rate and COD removal efficiency.
It is clearly seen from the figure that the energy consumption in-
creases with increasing dilution rate. Energy consumption values for
dilution rates of 1/1 (raw wastewater), 1/2, 1/3 and 1/4 were calcu-
lated as 243.31, 284.54, 297.06 and 320.03 kW h/m3. The increased
dilution rate decreases the pollution in the wastewater, but on the other
hand, it reduces the electrical conductivity of the SWW due to the
electrical conductivity of tap water (0.285 mS/cm in this study) being
lower than the SWW (3.04 mS/cm). Therefore, energy consumption
increased as a result of the increased resistance in the system. The di-
lution rate is a natural process that occurs as a result of washing the
equipment in the slaughterhouse plants. As tap water is mixed with
wastewater, pollutants are diluted and can be oxidized more easily by
the EO process. On the other hand, because the electrical conductivity
of the tap water is less than SWW, it causes a higher potential difference
during the EO process. As a result of this situation, the amount of en-
ergy consumed by the system increases. Therefore, minimum water
consumption during the washing operations in slaughterhouses will
result in less energy consumption for the treatment of these waste-
waters with EO.
4. Conclusions
In this study, the aim was to treat SWW with EO using a Ti/Pt mesh
anode under different operation conditions. According to the experi-
ments, it was found that the removal of the organic content of SWW by
EO with Ti/Pt mesh anode was very efficient. With respect to the re-
sults, the removal of all pollutants was observed to be maximum at
D. Ozturk and A.E. Yilmaz
SWWs natural pH (7.03). The most effective electrolyte was found to be
NaCl. The highest removal efficacy was seen with the use of 0.1 M NaCl,
but the application of this concentration on an industrial scale means
the use of tons of NaCl. Taking into consideration the discharge limits of
SWW’s and contribution to low energy consumption, the optimum
concentration was selected as 0.025 M. As the CD increased an obvious
increase was seen on removal efficiency but 4.73 mA/cm² was chosen
to minimize the consumption of energy. The dilution rate affected the
removal efficiency positively, but caused a decrease in the electrical
conductivity because of the lower conductivity of tap water compared
to SWW; hence it caused an increase in the energy consumption.
Therefore, minimum water consumption during washing operations in
slaughterhouses will result in less energy consumption for the treatment
of these wastewaters with EO. Optimum conditions for the treatment of
SWW with EO were found to be natural initial pH of 7.03, 4.73 mA/cm²
CD, using 0.025 M NaCl, without dilution, reaction time of 4 h, at re-
action temperature of 25 °C. Under these optimum conditions, TSS,
TOC, COD, TN and color removal efficiencies were found to be 99.5%,
88.0%, 92.2%, 93.5% and 99.9% respectively. Four hours of electro-
lysis were completed at 153.57 kW h/m3, 14.12 kW h/kg COD and the
energy cost under optimum removal conditions was calculated as 1.69
$/kg COD.
Also, the results clearly demonstrate that almost full mineralization
of organics was obtained after 4 h treatment. Unluckily, taking into
account the large volumes of effluent produced per slaughtering cycle,
the need for long treatment times is impractical, yet if the reactor is
developed to arrange the hydrodynamic conditions or combined with
another treatment process which shortens the EO treatment time (such
as EF), a novel setup may be possible.
Acknowledgement
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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