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Comparative study of electrochemical

wastewater treatment processes for bilge water
as oily wastewater: A kinetic approach

Article in Journal of electroanalytical chemistry June 2015

DOI: 10.1016/j.jelechem.2015.04.005

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 Journal of Electroanalytical Chemistry 747 (2015) 104111

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Journal of Electroanalytical Chemistry

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

Comparative study of electrochemical wastewater treatment processes

for bilge water as oily wastewater: A kinetic approach
Kubra Ulucan , Ugur Kurt
Yildiz Technical University, Civil Engineering Faculty Environmental Engineering Department, Istanbul, Turkey

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

Article history: In this study treatability of bilge water was investigated by electrochemical processes: electrocoag-
Received 23 September 2014 ulation/electrootation process and also the electro-fenton process as an indirect electrooxidation pro-
Received in revised form 30 March 2015 cess. As the seawater is mixed into bilge water, the chloride content and the conductivity of bilge
Accepted 4 April 2015
water are quite high, which is a great advantage in terms of electrochemical wastewater treatment.
Available online 6 April 2015
Treatability of bilge water by electrocoagulation/electrootation process is investigated by using alu-
minum and iron electrodes in accordance with pH, time, temperature and current density. When the alu-
Keywords:
minum and iron electrodes are compared in electrocoagulationelectrootation process, the results
Bilge water
Oily water
clearly showed that the aluminum electrodes were more efcient and as well as in a short period of time
Electrofenton as 10 min. Chemical oxygen demand and oilgrease removal values obtained as 64.8% and 57% from Al
Electrocoagulation and 36.2% and 12.5% from Fe, respectively. On the other hand by electro-fenton process, it was seen that
Electrootation higher removal efciencies were obtained in comparison to the electrocoagulation method, with the COD
Pseudo-rst-order and oilgrease removal being equal to 71% and 69%, respectively. The discharge standards specied by
Pseudo-second-order MARPOL were obtained by the electro-fenton process. When processes are analyzed in economically
way, the electricity cost of electrocoagulation process by aluminum, iron and electro-fenton process
was 0.54 $/m3, 0.53 $/m3, 0.51 $/m3, respectively. In addition, pseudo-second-order kinetic model was
tted for both COD and Oil&Grease removal in electrocoagulation process.
2015 Published by Elsevier B.V.

1. Introduction
Maritime transportation has recently gained great importance
due to the increasing demand for energy and raw material world-
wide. The international conventions regarding the prevention of
marine pollution led by the ships rst appeared in the mid-20th
century. The rst international convention is the International
Convention on Preventing Sea Pollution caused by Oil and
Petroleum-derived products (OILPOL, 1954). However, due to mar-
itime accidents, it was soon understood that these measures were
not sufcient, and the International Convention on Preventing
Pollution from Ships (MARPOL, 73/78) was introduced in 1973 by
the International Maritime Organization (IMO). Today, the sea pol-
lution problem has become an increasingly important issue not
only for coastal countries, but also for all societies. Ships discharge
their wastes (bilge waters, ballast waters, domestic waters, sludge,
slop, etc...) randomly into the seas, hence causing pollution.
Corresponding author.
E-mail addresses: kulucan@yildiz.edu.tr (K. Ulucan), ukurt@yildiz.edu.tr
(U. Kurt).
Bilge waters are of great importance among all liquid wastes
including petroleum and petroleum-derived products. The bilge
waters that are stored at the bottom of the ships are greasy
wastewaters, including a number of pollutants with various char-
acteristics. The oil and grease leaking from the engine room are
also stored in the bilge, which in turn increases the oil concentra-
tions of bilge waters. Generally, bilge waters can be briey dened
as saline and greasy wastewaters. The oil and grease are mixed
with the sea water, which affects many marine species. The vul-
nerability of plankton, which are a basic food source in the seas,
to oil and grease based pollutions have been experimentally pro-
ven [1]. When plankton are harmed by oil and grease, the adverse
effects will take hold of all the other links in the food chain, and
eventually will affect all marine species.
Classical methods widely used for the aim of the treatment of
bilge waters are chemical or physical processes such as otation,
separation by centrifuge, ltration, and coagulation. Because the
major part of the oil in bilge waters is emulsied, the physical
methods may fail to satisfy the targeted treatment levels. Caplan
et al. [2] and Woytowich et al. [3] both stated that they failed to
remove emulsied oil droplets smaller than 20 lm by means of
conventional oil/water separation systems. For bilge water

http://dx.doi.org/10.1016/j.jelechem.2015.04.005
1572-6657/ 2015 Published by Elsevier B.V.
 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111
treatment there are also a limited number of studies in which
ultraltration [4], UF/membrane distillation [5,6] air-stripping
and photocatalysis [7], air otation [8], electrocoagulation [3]
methods are applied.
The most rapidly developing and most commonly used pro-
cesses that are considered to be used in the future among advanced
wastewater treatment processes is the electrochemical wastewa-
ter treatment process. Besides electrochemical treatment of
domestic wastewater is applied successfully, it is proved to be
effective in treatment of phenol, aniline, olive oil, cyanide and
industrial wastewaters from leather tanning, textile, paint industry
[917].
Electrochemical processes include electrocoagulation, elec-
trootation, and direct and indirect electro-oxidation processes.
In electrocoagulation process anode electrodes (aluminum and
iron electrodes) dissolves as Al+3 and Fe+2 ions as coagulant, which
form metal hydroxides with high adsorption capacity in water.
Electrical charged metal ions can form high-gravity ocks by bind-
ing emulsied materials, suspended solids and colloidal materials:
3
Anode rxns : Al ! Al 3e
Fe ! Fe2 2e
 
Cathode rxn : 2H2 O 2e ! H2 2OH
3 
Al 3OH ! AlOH3
Fe2 2OH ! FeOH2
In addition, H2 gas produced in cathode generates large surface
areas for the adsorption of ocks and precipitates, and removes
them by oating (electrootation process). Generally in electro-
chemical oxidation process, the desired oxidation is provided by
H2O2 and OH radicals formed via produced gases (O2 and H2) by
insoluble electrodes (Ti, Ru, Pt, BDD, etc.). Electrooxidation pro-
cesses divided to direct electrooxidation and indirect electroox-
idation. In direct electrooxidation, OH radicals are formed on
electrode surface (Ti, Pt, BDD, etc.), but in indirect electrooxidation
process (electrofenton), OH radicals are formed when oxidative
chemical (H2O2 etc.) is added to system:
Fe2 H2 O2 ! Fe3  OH OH pH  3
There are a limited number of studies regarding the treatment
of bilge waters through electrochemical processes. The studies
focusing on the wastewaters with oilgrease content showed that
oil and grease in these wastewaters are removed by absorption
into metal-hydroxides formed as a result of the electrocoagulation,
or with electrootation by means of gases produced as a result of
electrocoagulation. For the electrocoagulation-based treatment of
such wastewaters, aluminum and iron electrodes were typically
used, and it was shown that aluminum electrodes led to better
results in terms of the efciency of the treatment of wastewaters
with a certain oil concentration [1820]. This study, on the other
hand, aims to investigate the efciency of electrochemical pro-
cesses for the treatment of bilge waters. It also examined how elec-
trocoagulation, electrootation, and electro-fenton processes affect
the COD and oilgrease removal.
2. Materials and method
2.1. Wastewater
The bilge wastewater used for this study was supplied by
Haydarpasa Waste Receiving Facilities. The bilge waters taken by
tankers are rst brought into the balance tank and stored so that
oil and water are separated from one another under gravitational
forces and with the aid of a heating procedure. Wastewaters taken
from the bottom of this tank are brought into the balance reservoir
105
Table 1
Characteristics of bilge water.
Parameters Concentration
pH 6.86
Conductivity, mS/cm 31.1
Turbidity, NTU 35.5
TSS, mg/L 111
Chloride, mg/L 11860
COD, mg/L 2247
BOD, mg/L 490
Oil&Grease, mg/L 93
of a chemical treatment unit and are sent to the treatment facility
by means of pumps. The bilge waters used in this study for testing
purposes were taken from the balance reservoir, just prior to being
sent in for chemical treatment. Characteristics of wastewater can
be seen in Table 1.
2.2. Reactor and operation
1
2 The reactor used in electrocoagulation and electrofenton pro-
cesses was made of Plexiglas and was 60 mm  60 mm  170 mm
3
in size (width x breadth x length), while the aluminum and iron
4 electrodes were 50 mm  200 mm (breadth  length). The dis-
5 tance between the electrodes was 60 mm. The batch system reac-
tor volume for each study was 500 ml. Mixing within the reactor
was accomplished by the gasses produced in electrootation sys-
tem. The power supply used at the reactor was a DC supply, GW
Instek model GPS-3030 DD.
2.3. Experimental procedure
Treatability of bilge water by electrocoagulation/electroota-
tion process was investigated by using aluminum and iron elec-
trodes in accordance with pH, time, temperature and current
density. The experiments were carried out with 500 ml bilge water.
Initial conditions to reach optimum conditions were xed between
6 pH: 4.510, time: 5120 min., temp.: 460 C and current density:
2.525 mA/cm2 (1 A current equals to 7.5 mA/cm2 in 6.5 V).
For electro-Fenton processes as different from the foregoing
conditions, H2O2 dosages between 1250 and 6250 mg/L and pH:
2, 3, 4 and original pH values were arranged. Current density was
about 6.8 mA/cm2 (1 A) and voltage was about 6.2.
After the electrolysis, nal pH values were documented, anionic
polyelectrolyte with a concentration of 0.2 mg/L was added to the
samples in order to facilitate the coagulation process and to accel-
erate clarity.
In electrofenton process study, hydrogen peroxide (H2O2)
should be disintegrated to determine the COD concentrations of
samples. It has to be certain that the sample is not containing
H2O2 before COD analysis. Otherwise, H2O2 will give positive
attempt to results as in Eq. (7):
Cr2 O2
7 3H2 O2 8H
2Cr3 3O2 7H2 O 7
In order to remove H2O2, which can react with dichromate in
COD analysis, permanganometrical method is used [11,21].
Permanganometric method can be used to determine oxidant
forms such as H2O2, O2, etc. This method is a well-known method
to analysis H2O2 and it is sometimes called as Ghormley Method
[11,21]. For this aim, the pH values of the samples were increased
to a value higher than 10 by NaOH solution (0.2 N). After pH
adjustment, 1 ml of efuent sample was taken homogenously in
order to analysis H2O2 by permanganometric method. Addition of
NaOH solution is continued until the efuent sample is not
106 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111

containing H2O2. After removing H2O2 excess by adjusting pH val- 80

ues, COD Analysis was performed in accordance with Standard
70

COD Removal Rate, %

Method 5220-B.
Analytical grade sulfuric acid, sodium hydroxide and hydrogen
peroxide as used chemicals were supplied from Merck. All analyses
were performed in accordance with Standard Methods for the
Examination of Water and Wastewater. In COD analysis, Method
5220-B, in O&G analysis Method 5520, in TSS analyses Method
2540-D were used. To measure conductivity, Hach Lange HQ 40D
conductivity meter is used. In electrofenton process investigation,
COD analysis was carried out after the absence of H2O2 by per-
manganometrical method [11,21].
2.4. Electrocoagulation Kinetics
As an electrochemical wastewater treatment process, elec-
trocoagulation is a process based on dissolving Al+3 and Fe+2/Fe+3
ions from anode electrodes as coagulant, which forms metal
hydroxides with high adsorption capacity in water, via aluminum
and iron electrodes. Removal mechanism can be modeled by
adsorption kinetics. The adsorption capacity,
C 0  C t V
qt
m out with an iron electrode. The COD removal obtained using iron
where, qt is the amount of pollutant adsorbed on gram of produced
oc(mg/g), V is the volume of reactor (L), m is the weight of dis-
solved electrode (g), C0 and Ct are the initial concentration and con-
centration of pollutant at any time (t) (mg/L), respectively. The
weight of dissolved electrode can be estimated stoichiometrically
according to Faradays Law [2225].
Pseudo-rst-order, pseudo-second-order kinetic models were
applied in order to present removal mechanism of electrocoag-
ulation process. Pseudo-rst-order kinetic model can be linearized
as follows,
lnqe1  qt ln qe  k1 t 9 Temperature is one of the most inuential mechanisms in oil
where, qe and qt are the adsorption capacity at equilibrium and at
given time, k1 is constant rate of adsorption(g/mg/min). Similarly,
pseudo-second-order kinetic model can be linearized as follows,
t 1 1 ture in winter, to 10 C60 C. These experiments were carried out
t 10
qt k2 q2e qe
where, k2 is constant rate of adsorption for pseudo-second-order-ki-
netic model (g/mg/min).
3. Results and discussion
60
50
40
30
20
Aluminum
10 Iron
0
3 4 5 6 7 8 9 10 11 12
pH
Fig. 1. COD removal rates in accordance with pH.
The COD efciency levels shown in Fig. 1 show that COD
efciencies do not vary considerably for aluminum electrodes used
between pH values equal to 6.5 and 8.5, while the optimum pH
range is 78 for iron electrodes. One can also conclude that in
the experiments carried out using aluminum electrodes, pH is
8 more inuential on COD removal efciency level that those carried
electrodes for pH values equal to 6.86 (original pH of bilge water)
and 8 were 36% and 41.5%, respectively, while it is as equal to 64%
with aluminum electrodes. This is considered to be due to the fact
that aluminum hydroxides have a better oil absorption capacity in
comparison to iron hydroxides, as previously underlined in a study
carried out using synthetic water with a certain oil concentration
[18]. In order to avoid additional costs due to pH adjustment, the
original pH value of raw water equal to 6.86 was selected as the
optimum pH level in the following testing sets.
3.1.2. Temperature adjustment
and grease removal. A test set was designed to identify the effect
of temperature increase on COD and oilgrease removal. The
COD and oilgrease removal were tested at a range of bilge water
temperature values ranging from 4 C, which is the water tempera-
at the original wastewater pH (pH 6.86), at a current density equal
to 7.5 mA/cm2 for 10 min.
The results obtained from experiments carried out using both
aluminum and iron electrodes can be seen in Fig. 2. The COD and
the oil and grease removal values at 4 C using aluminum electrodes
were 29% and 23%, respectively; these values were 64% and 68% at a

3.1. Electrocoagulation process

80

Treatability of bilge water by electrocoagulation/electroota- 70

tion process is investigated by using aluminum and iron electrodes.
Removal Rates, %

60
In order to determine optimum conditions, the experiments were
practiced in different pH (in range of pH 4.510), time (in range 50
of 5120 min), temperature (in range of 1060 C) and current
40
density (in range of 2.525 mA/cm2) as in the following sections.
30
3.1.1. pH Adjustment
20
On the basis of the pC-pH diagram obtained from aluminum COD Removal by Al
hydroxides, the best coagulation pH was equal to 6.5, as seen in 10 O&G Removal by Al
COD Removal by Fe
Fig. 1. In order to determine the best COD efciency, a set of differ- O&G Removal by Fe
0
ent experiments with varying initial pH values were carried out
0 10 20 30 40 50 60 70
(pH: 4.510). Each of these experiments was carried out at a tem- Temperature, C
perature of 20 C, at a current density equal to 7.5 mA/cm2, for
10 min. Fig. 2. COD and O&G removal rates in accordance with temperature.
 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111
temperature of 40 C. Fig. 2 shows the effect of temperature on oil
and grease removal. Although bilge water temperature values
higher than 20 C did not affect signicantly the COD removal, the
oil and grease removal at 20 C and 40 C were 53% and 68%,
respectively.
When iron electrodes were used, on the other hand, a small
increase was observed in the oilgrease and COD removal. The
COD and oilgrease removals at 4 C bilge water were 34% and
9%, respectively, while at 40 C these values rose to 39% and 16%.
In the study carried out by gtveren and Koparal [18] using syn-
thetic water with a certain oil concentration, it was shown that alu-
minum hydroxides had a higher absorption capacity. Additionally,
based on Fig. 2, one can conrm that the test carried out using alu-
minum electrode resulted in higher oil and grease removal than the
test carried out using iron electrodes, which was due to the differ-
ence between the absorption capacities.
From Fig. 2, it is also clear that the electrocoagulation and elec-
trootation experiments carried out using aluminum electrodes
resulted in higher efciency levels. Since the COD removal is opti-
mum at a temperature of 20 C, this value was selected as the opti-
mum temperature level and used as such in the following
experiments.
3.1.3. Effect of time
In order to identify the optimum time values for the electrocoag-
ulationelectrootation process-based treatment of bilge waters, a
series of experiments were carried out for 5120 min at 6.86 pH
and a temperature of 20 C and 7.5 mA/cm2 current density. The
obtained results can be seen in Fig. 3.
For aluminum electrodes, the major part of the COD and oil
grease was removed in the rst 10 min of the test, while after
60 min the removal efciency became approximately 70% for both
parameters. After 10 min of treatment, the COD and oilgrease
removal efciency were equal to 64% and 53%, respectively, while
these values were 69% and 68% after 60 min. In addition, from the
rst moments of electrocoagulationelectrootation process
onwards, oil became visible on the surface. The COD removal
increased until minute 60 when iron electrodes were used (COD
removal at minute 60 equal to 53%), while after minute 60, the
increase in the removal rate began to decrease. Regarding
the oilgrease removal, on the other hand, one can conclude that
the removal efciency rose until minute 80 (by 10% at minute 5,
while 36% at minute 80) and declined after that.
Asselin et al. [20], in their study regarding bilge waters, showed
that COD was removed in the rst 10 min to a large extent using
aluminum electrodes.
While COD and oilgrease concentrations were removed to a
large extent in the rst 10 min of the experiments carried out using
80
70
60
Removal Rates, %
50
40
30
20
COD Removal by Al
O&G Removal by Al
10 COD Removal by Fe
O&G Removal by Fe
0
0 20 40 60 80 100 120
Time, min
Fig. 3. COD and O&G removal rates in accordance with time.
107
aluminum electrodes, the same efciency level could not be
achieved even after 60 min when iron electrodes were used.
Therefore, considering the cost of electricity, 10 min was selected
as the optimum time and used as such in the following experiments.
3.1.4. Effect of current density
In order to investigate the effect of current density on the treat-
ment of bilge waters, a series of experiments were carried out for
2.525 mA/cm2 current density values at 6.86 pH, at a temperature
of 20 C for 10 min. The obtained results are shown in Fig. 4.
The experiments carried out using aluminum electrodes showed
that the COD and oilgrease removal values remained unchanged
under the current density values higher than 7.5 mA/cm2. In addi-
tion, Fig. 4 shows the oilgrease and COD removals as being parallel
to each other.
In the test carried out using an iron electrode, a rapid increase in
the COD and oilgrease removal levels was not obtained, either
(Fig. 4). The COD and oilgrease removal values were 35% and
15%, respectively, up to the current density value equal to
15 mA/cm2. The oilgrease removal with aluminum electrodes
was 55%, while it was equal to 15% when iron electrodes were
used. This is considered to be due to the higher absorption capacity
of aluminum electrodes.
When electrochemical treatment systems are compared to each
other, both COD and oilgrease removals obtained at the end of the
electrocoagulationelectrootation processes carried out using
iron electrodes were quite low. In addition, it was observed that
the level of turbidity and total suspended solids (TSS) were very
high in the efuent water.
3.2. Electro-fenton process
The electro-fenton testing aimed to identify the effect of pH
variations (in range of pH 24), reaction time (in range of 10
60 min), current (in range of 2.52 A), and H2O2 dose (in range of
12506250 mg/L) on oxidation. Considering that temperature val-
ues higher than 20 C do not cause a considerable change in the
removal efciency in electrocoagulation and electrootation pro-
cesses, as well as the fact that higher temperature values will lead
to the disintegration of H2O2, the temperature was established as
20 C for electro-fenton testing.
3.2.1. Effect of Initial pH
Because the instability of hydrogen peroxide increases as the
initial pH value of wastewaters increases, pH values are normally
selected in the range of 34 for electro-fenton processes [26].
Therefore, in this study, the initial pH values were chosen as pH
80
70
Removal Rates, %
60
50
40
30
20
COD Removal by Al
10 O&G Removal by Al
COD Removal by Fe
OO&G Removal by Fe
0
0 3 6 9 12 15 18 21 24 27 30
Current Density, mA/cm2
Fig. 4. COD and O&G removal rates in accordance with current density.
108 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111
2, pH 3, pH 4, and the original pH. The experiments were carried
out using 5000 mg/L H2O2 dose and under 1 A constant current
(6.80 mA/cm2) and 6.2 V.
While the COD removal values obtained for pH values equal to 2
and 4 are close to each other (around 70%), efciencies up to 80%
were obtained when the pH value was set at 3. In the experiments
carried out using the original pH value, on the other hand, COD
removal efciency in the range of 65% was obtained. The optimum
pH was chosen as 3 for the future experiments.
3.2.2. Effect of current density
The amount of iron ions transferred into water during the elec-
tro-fenton process affect the processs efciency. For this aim, a set
of experiments were carried out using samples with different cur-
rent values between 0.25 and 2.00 A (1.713.6 V) and with pH and
H2O2 concentration equal to 3 and 5000 mg/L, respectively. Fig. 5a
show the impact of the change in the applied current density on
the basis of time on COD removal efciency. The COD removal ef-
ciency was found to be 50% under 0.25 and 0.50 A electric current,
while the efciency value increase to 70% when the current was
increased to 1.00, 1.50, and 2 A. The removal was completed in
the rst 10 min under 1 A, while the removal efciency in the rst concentration on the electro-fenton process was investigated. The
10 min decreased when the current was increased to 1.50 A. This is
considered to be due to the fact that oxidant types (radicals like

OH, HO2) react with Fe(II), and hence slow down the oxidation
of the pollutants as a result of greater transferred iron amounts
under 1.50 A electric current than under a 1 A electric current.
Under 2 A, the removal efciency increased again. The reason for
this is Fe(II)/Fe(III) ions transferred into the reaction medium trig-
gers a Fe(OH)3 coagulation mechanism, resulting in an increase in
the efciency levels. Fig. 5.b shows the COD and oilgrease removal
results obtained from the experiments carried out using samples
taken at the 20th minute for each current density value.
The COD and oilgrease removal values obtained for low cur-
rent density levels are quite low, while these values obtained
under 6.8 mA/cm2 (1 A) current density were 73% and 69%, respec-
tively. Furthermore, a considerable change was not observed in the
removal levels with increasing current density values. Based on
this observation, the current to be applied in future experiments
was chosen as 1 A (6.8 mA/cm2).
3.2.3. Effect of initial H2O2 concentration
The experiments carried out to determine optimum current
density showed that the H2O2 concentration consumed at a
0,25 A
1,00 A
2,00 A
a b
Fig. 5. Effect of current density in electrofenton process (a) on COD removal rate. (b) On COD and O&G removal rate.
1250 mg/L
2500 mg/L
3750 mg/L
5000 mg/L
6250 mg/L
Fig. 6. Efux H2O2 concentrations by time.
1.00 A electric current and 5000 mg H2O2/L was 1020 mg/L at the
end of 20 min. Therefore, one can conclude that a H2O2 concentra-
tion equal to 1020 mg/L is required in order to obtain COD removal
efciency in the range of 73%. In this study, the effect of initial H2O2
initial concentration was established as 1250, 2500, 3750, 5000,
and 6250 mg/L by means of calculation method, and COD removal
efciency values obtained for pH3 bilge water were investigated on
the basis of time.
The change in efux H2O2 concentrations over time can be seen
in Fig. 6. Even though the initial H2O2 concentration values used for
this study were 1250, 2500, 3750, 5000, and 6250 mg/L, the H2O2
concentrations calculated at the end of the analysis were 1020,
2295, 3400, 4250 and 5313 mg/L.
Additionally, in another test that was carried out using a repli-
cate samples (using distillated water, in the mentioned concentra-
tions above and at pH 3), H2O2 concentrations were determined
using permanganometric method, and values calculated as 1250,
2500, 3750, 5000, and 6250 mg/L were equal to 1050, 2350, 3500,
4400, and 5400 mg/L. This situation showed that, hydrogen perox-
ide have started to disintegrate as soon as it was added to the sam-
ples with a pH level equal to 3. Fig. 6 also shows that as the H2O2
concentration decreased, the total reaction duration decreased, as
well. Even though the initial concentration values changed, the
H2O2 consumption levels were close to each other. Fig. 7a show
the effect of initial H2O2 concentration values on COD removal on
the basis of time. In the previous test, 1020 mg/L H2O2 was
0,50 A
1,50 A COD
O&G
 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111 109

1250 mg/L 2500 mg/L

COD
3250 mg/L 5000 mg/L
O&G
6250 mg/L

a b
Fig. 7. Effect of H2O2 concentrations in electrofenton process (a) on COD Removal Rate. (b) On COD and O&G removal rate.

Table 2 concentration is more inuential on COD removal than the initial

Parameter values for kinetic modeling.
H2O2 concentration. The COD removal values obtained for
Pseudo-rst- Pseudo-second- 5000 mg/L and 6250 mg/L initial H2O2 concentration values do
order kinetic order kinetic not vary considerably; therefore, the optimum initial H2O2 concen-
COD Correlation 0.8828 0.9301 tration value was selected as 5000 mg/L.
coefcient The COD and oilgrease removal efciency values obtained in
Constant rate of 0.182 0.056
the rst 20 min for different H2O2 concentrations can be seen in
adsorption
Fig. 7b. The oilgrease removal efciency value obtained for the
Oil&Grease Correlation 0.9378 0.9313
1250 mg/L H2O2 concentration was 41%, while for 6250 mg/L, this
coefcient
Constant rate of 0.148 1.447 value increased to 69%. Fig. 7b shows that oilgrease and COD
adsorption removal efciencies are parallel to each other. With the electro-
fenton process, 428 mg/L COD and 14 mg/L oilgrease was
obtained after 60 min using a 5000 mg/L H2O2 concentration.
consumed to be able to provide a COD removal efciency in the
range of 73% in the rst 20 min with the initial H2O2 concentration 3.3. Kinetic study
equal to 5000 mg/L.
As can be seen from Fig. 7, the COD removal efciency obtained Pseudo-rst-order and pseudo-second-order kinetic models
for an initial H2O2 concentration equal to 1250 mg/L could not were investigated to consider experimental data obtained in elec-
exceed 50%. This clearly shows that the consumed H2O2 trocoagulation process. Correlation coefcients and constant rates

Table 3
Comparison of electrochemical processes.

Parameters Electrocoagulation/electrootation Electrofenton

Aluminum Iron Iron
Reaction time (min) 10 10 10
Applied current (A) 1.0 1.0 1.0
Applied current density (mA/cm2) 7.5 7.5 6.8
Initial voltage (V) 6.5 6.5 6.2
Dinal voltage (V) 6 6.2 6
Inuent pH 6.86 6.86 3
Efuent pH 6.95 6.90 4.86
Conductivity (mS/cm) 29.8 29.5 28.4
Sludge produced (ml/500 ml) 40 55 35
Turbidity, ntu 24.4 276 23.7
Inuent COD concentration(mg/L) 2247 2247 2247
Efuent COD concentration (mg/L) 792 1433 656
Removal rate of COD (%) 64.8 36.2 71
Inuent Oil&Grease concentration (mg/L) 93 93 93
Efuent Oil&Grease concentration (mg/L) 40 81.4 29
Removal rate of Oil&Grease (%) 57 12.5 68.8
Inuent BOD concentration (mg/L) 490 490 490
Efuent BOD concentration (mg/L) 167 200 <10
Removal rate of BOD, % 66 59 >98
Inuent TSS concentration (mg/L) 111 111 111
Efuent TSS concentration (mg/L) 13 213 10
Removal rate of TSS, % 88 0 >90
Electricity consumption (kWh/m3) 2.17 2.13 2.07
110 K. Ulucan, U. Kurt / Journal of Electroanalytical Chemistry 747 (2015) 104111
of kinetic models were given in Table 2. The results showed that
COD removal mechanism is more tted to pseudo-second-order
kinetic model, and O&G removal mechanism is more tted to
pseudo-rst-order kinetic model. By this information it can be said
that, COD removal are mostly related to oil and grease adsorption
on aluminum hydroxides.
3.4. Comparison of the systems
Table 3 summarizes all the experiments carried out with the
aim of identifying the treatability of bilge waters using electro-
chemical methods.
When the electrochemical treatment methods are compared to
each other, it was also seen that the electrocoagulationelec-
trootation processes carried out using iron electrodes resulted
in very low COD and oilgrease removal efciencies. In addition,
these processes resulted in higher levels of efuent turbidity and
TSS in comparison to other processes. Turbidity and TSS was higher
due to the Fe(II) oxidation after process. When the results obtained
for 10 min of operation time for both electro-fenton and elec-
trocoagulation processes are compared to each other, it was seen
that the electro-fenton process resulted in higher efciency levels
(the COD removal efciency values obtained using electrocoag-
ulation and electro-fenton processes were 64.8% and 71%, respec-
tively, while these values were 57% and 68.8% for oilgrease
removal efciency). When the electro-fenton process was applied,
the increase observed in oilgrease removal efciency has also
increased the COD removal. In addition, because biochemical oxy-
gen demand (BOD) was completely removed, it can be conclude
that all bio-degradable organic pollutants were totally removed.
When the processes are compared in terms of sludge production,
the sludge produced at the end of the electro-fenton process was
relatively less and more stable than that caused by other processes.
Kurt et al. [10] also showed that for the same current density value,
the electro-fenton process resulted in a more stable sludge produc-
tion in comparison to that obtained using iron electrodes.
In order to analysis the process in economically way, electricity
consumption for all three processes was done. The power source
used for electrocoagulation process by aluminum electrodes was
1.0 A with 6.5 V of current. Correspondingly, electricity consump-
tion was 1.0 A  6.5 V  10 min = 1.0833 Wh for 0.5 l wastewater
and required energy amount will be 2.17 kWh/m3 wastewater
(Table 3). When energy consumption in Turkey was 0.25 US $/
kWh [9], the cost of electrocoagulation process by aluminum elec-
trodes will be 0.54 $/m3 wastewater and for electrocoagulation
process by iron electrodes and electro-fenton processes it will be
0.53 and 0.51 $/m3, respectively.
4. Conclusion
At the end of 10 min, which was determined as the optimum
duration for electrochemical treatment processes, the COD and
oilgrease removal efciency values obtained using the electro-
fenton process were 71% (81% for 60 min.) and 68.8%, respectively,
while the electrocoagulation process carried out using aluminum
electrodes resulted in 64.8% COD and 57% oilgrease removal ef-
ciency. In the electro-fenton process, hydrolyzed oil acids partially
oxidized in low pH range (pH 3) resulted in an increase in oil
grease and COD removal levels. On the other hand, when the treat-
ment sludge was examined, it was seen that the sludge formed at
the end of the electro-fenton process was more stable and lower in
volume.
Among all processes examined in this study, the standard dis-
charge values were reached after 60 min with 5000 mg/L hydrogen
peroxide concentration (428 mg/L COD and 14 mg/L oilgrease)
only at the end of the electro-fenton process.
On the other hand, it should also be recalled that the results
reported here are specic to the bilge water tested in this study.
The characteristics of bilge waters may vary considerably. In this
study, actual bilge waters were tested. Because of the high conduc-
tivity of these waters, different electrochemical methods were
used and their performances were investigated. The obtained
results are promising and open to further advancement. It is
obvious that two-phase systems designed to include electrocoag-
ulation and electro-fenton processes will result in more successful
results. In addition, the performance of direct electro-oxidation-
based treatment of bilge waters (Ti/BDD electrodes, etc...), and
detailing of energy potentials of treatment outputs are important
points requiring further research.
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