Separation and Purification Technology 159 (2016) 108115

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Separation and Purification Technology

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

Removal of organics from bilge water by batch electrocoagulation

process
P. Aswathy a, R. Gandhimathi a,, S.T. Ramesh a, P.V. Nidheesh b,c
a
Department of Civil Engineering, National Institute of Technology, Tiruchirappalli, Tamil Nadu, India
b
Department of Civil Engineering, National Institute of Technology, Calicut, Kerala, India
c
Department of Civil Engineering, Vimal Jyothi Engineering College, Chemperi, Kannur, Kerala, India

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

Article history: A batch electrocoagulation study was conducted using aluminium electrodes to check the treatability of
Received 25 June 2015 synthetic bilge water. The studies were conducted to investigate the effect of various operational param-
Received in revised form 9 December 2015 eters on the treatment efficiency. At a pH of 7, applied voltage of 10 V, spacing of 1 cm and effective elec-
Accepted 1 January 2016
trode area of 45 cm2, a maximum soluble COD (CODS) removal efficiency of 85% was obtained after an
Available online 2 January 2016
electrolysis time of 120 min. The second order rate constant was derived and a maximum rate constant
of 3
106 L/mg-min was observed at optimum experimental conditions. CODS experimental measure-
Keywords:
ments give an acceptable fit for both Langmuir model and Freundlich isotherm models. A comparative
Bilge water
Electrocoagulation
study between electrocoagulation and chemical coagulation was performed and chemical coagulation
Soluble COD showed only 59.3% removal efficiency. The sludge formed after the electrocoagulation process was char-
Sludge characterization acterized for mineral composition and functional groups. XRD and FTIR results represent the formation of
aluminium hydroxide during electro coagulation process and the presence of hydrocarbons and heavy
metals in the sludge indicates the removal of these pollutants from bilge water by electrocoagulation pro-
cess. Among different electrode combinations of aluminium and iron, AlAAl combination showed max-
imum removal efficiency. A case study on real bilge water was conducted and a maximum removal of
89.84% was obtained at optimum conditions using aluminium electrodes.
2016 Elsevier B.V. All rights reserved.

1. Introduction
In recent years the increase in sea transportation has brought
along marine problems. The major pollutants in the aquatic envi-
ronment are oily wastes. According to the report prepared by
EPA on cruise ship discharge assessment [1], bilge water is the
mixture of seawater, oily fluids, lubricants, cleaning fluids, and
other similar wastes. These get accumulated in the lowest part of
the vessel from a variety of different sources. The sources of bilge
water throughout the spaces of a vessel are the main and auxiliary
engines, boilers, evaporators and related auxiliary systems, equip-
ment and related components, machines and other operations.
Metals present in bilge and ballast water cannot be removed
through treatment or environmental degradation. If these metals
are ingested, they can cause various human health problems such
as lead poisoning and cancer [2]. The structure and functions of
marine communities and ecosystems can be disrupted by the oil
present in bilge water. The chemical contaminants in oil ultimately
Corresponding author.
E-mail address: rgmathii@nitt.edu (R. Gandhimathi).
impacts the survival rates of the affected species by poisoning mar-
ine life, disrupting feeding, causing chronic diseases, reproductive
failures and deformities [1].
The electrocoagulation (EC) technology being more flexible,
compact and fairly less expensive, promises better treatment of
bilge water. EC is an economical and robust technology, a technical
solution to numerous environmental pollution problems and has
widely grown over the last few decades. The conductivity of bilge
water is high due to the high chloride concentration and this
makes it appropriate to treat by EC and it demands only low energy
consumption and less chemical usage. An increased current inten-
sity combined with decreased voltage and energy costs is obtained
due to high conductivity [3].
This study investigates the applicability of electrocoagulation
process to remove the organics from bilge water and the efficiency
was calculated in terms of organics removal. The effect of different
operational parameters was studied. The sludge generated after
electrocoagulation process was characterized. The kinetic study,
adsorption isotherm study and mass transfer study were carried
out. A comparison between electrocoagulation and chemical coag-
ulation was done and also the performance of different electrode

http://dx.doi.org/10.1016/j.seppur.2016.01.001
1383-5866/ 2016 Elsevier B.V. All rights reserved.
 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115
combinations of iron and aluminium on electrocoagulation was
checked. The applicability of electrocoagulation process on real
bilge water was tested.
2. Materials and methods
2.1. Synthetic bilge water preparation
A synthetic bilge water (SBW), a highly stable and homoge-
neous oil-in-water emulsion was prepared by mixing deionized
water, polysorbate (Tween 40) as emulsifying agent, motor oil
SAE 30, acrylic paint, sodium chloride, and metallic salts (Zn2+,
Cu2+ and Ni2+). A Flash mixer (Remi motor, Rjendra Elec. Ind. Ltd)
was used for the homogeneous mixing of all components. Andrade
[4] reported that the Tween 40 dose for the highest possible
emulsified oil concentration is 5000 mg/L and the same concentra-
tion was considered for the present study. After 24 h of prepara-
tion, the free oil fraction was separated from the prepared
synthetic wastewater, which kept under quiescent conditions in
the lab. Then, the resulting stable oil-in-water emulsion extracted
from the bottom of the sample container and analyzed to deter-
mine the emulsified-oil fraction. A maximum of 1280 mg/L out of
5000 mg/L of oil was remained emulsified in the SBW after adding
2500 mg/L of Tween 40 to this mixture, representing an
emulsified-oil fraction equal to 0.26. The SBW composition
included this amount of motor and emulsifying agent, plus acrylic
paint to add coloured colloidal particles, and metallic salts for con-
ductivity, thus simulating actual bilge water. The resulting SBW
composition and its initial characteristics are given in Tables 1
and 2, respectively. The pH of the synthetic bilge water was mea-
sured using Ion Analyzer (Thermo) and electrical conductivity of
the synthetic bilge water by conductivity metre (Eutech). Turbidity
was measured using turbidity metre. Total solids, total suspended
solids and total dissolved solids are analyzed based on gravimetric
method as per standard methods [5]. The sludge content was mea-
sured using the imhoff cone and quantified. Soluble COD (CODS)
was chosen as the principal parameter to define effluent treatment
as analysis of other components, namely, O&G, and C10C50
hydrocarbons was laborious. In order to get the soluble fraction,
the sample was filtered through 0.45 lm glass filter paper using
Vaccum pump. Hach 200 was used as the digester for the measure-
ment of COD by closed reflux method.
2.2. Experimental
An acrylic reactor of size 10 cm
10 cm
15 cm and was used
for the entire batch electrocoagulation of SBW. A working volume
of 1.0 L was considered for the entire experiments. The required
initial pH of the working solution was adjusted by 1 N HCl and
1 N NaOH. Aluminium plates of thickness 0.4 cm were used as
electrodes (both anode and cathode) and were placed vertical
and parallel to each other. The total effective electrode area and
the spacing between electrodes were fixed as 30 cm2 and 3 cm,
respectively. The anode and cathode were connected to a DC sup-
Table 1
Synthetic bilge water composition [4].
Constituent Concentration (mg/L)
Total oil (SAE 30) 5000
Tween 40 2500
Sodium chloride 600
Acrylic paint 200
Copper chloride dehydrate 5 generated together with H2 at high pH values [8]. So, for acidic pH
Zinc chloride 2.5
Nickel chloride hexahydrate 1.5
109
Table 2
Characteristics of synthetic bilge water.
Parameter Values
pH 7
Conductivity 1026 lS/cm
Turbidity 2870 NTU
Total COD 21,120 mg/L
Soluble COD 17,600 mg/L
Total solids 7260 mg/L
Total dissolved solids 2670 mg/L
Total suspended solids 4590 mg/L
Total fixed solids 580 mg/L
Total volatile solids 6680 mg/L
ply unit (30 V/5 A), in which required voltage was fixed. All the
reactor setup was kept above a magnetic stirrer for giving proper
agitation and a constant speed of 300 rpm was kept during the
electrocoagulation process. To remove the oxide and/or passivation
layer from the electrodes, the electrode surfaces were grinded with
sandpaper and rinsed with 1 N HCl before each experiment. An ali-
quot of 5 ml from the middle of the EC cell was collected using pip-
ette for every 15 min up to 120 min and filtered (2.5 lm) to
remove flocs. Then the sample was allowed to settle for 30 min.
After settling the sample was analyzed for soluble COD removal.
The soluble COD removal efficiency (Yt, %) was calculated from
equation,
C 0  C t
Yt
100 1
C0
where C0 is the initial soluble COD of synthetic bilge water before
electrocoagulation (mg/L), and Ct is the soluble COD of synthetic
bilge water after t min of electrocoagulation (mg/L).
The amount of the sludge produced was calculated after drying
and ignited at 105 C for 24 h and 550 C for 15 min, respectively.
Obtained sludge was also characterized using FT-IR and X-ray
diffraction techniques.
3. Results and discussions
3.1. Effect of solution pH
The effect of solution pH on COD removal efficiency of electroco-
agulation process was investigated in the initial pH range from 3 to
10 and the results are depicted in Fig. 1. It was found that the alu-
minium electrodes have higher efficiency near to neutral pH. At a
pH of 7, the removal efficiency of electrocoagulation process was
optimum with a removal efficiency of 77.6%, after 120 min of elec-
trolysis. The low efficiency at lower pH values is mainly due to the
lesser amount of aluminium insoluble precipitates generation in
the electrolytic system. At lower pH values, aluminium species will
be predominated in the form of Al3+ and Al(OH)+2. Also, the hydroxide
ions formed at the cathode were neutralized by the protons, results
in lesser amount of aluminium hydroxide formation [6]. Therefore,
the effective coagulation of pollutant not occurred at highly acidic
ranges. When pH is between 4 and 9, the Al3+ and OH ions gener-
ated by the electrodes react to form various monomeric species such
as Al(OH)+2, Al(OH)2+ 3+
2 , and polymeric species such as Al6(OH)15, Al7(-
OH)4+ 5+
17, Al13(OH)34 that finally transform into insoluble amorphous Al
(OH)3(s) through complex polymerization/precipitation kinetics [7].
These insoluble precipitates are responsible for the effective coagu-
lation at these pH values. When pH is higher than 10, the monomeric
Al(OH) 4 anion concentration increases at the expense of Al(OH)3(s).
In addition, the cathode may be chemically attacked by OH ions
different aluminium monomeric species or protons will be adsorbed
[9], whereas for aluminium at alkaline pHs both monomeric
110 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115

Fig. 1. Effect of pH on the removal of soluble COD and variation of effluent pH at an applied voltage of 8 V, spacing of 3 cm and area of 30 cm2.

negative species as Al(OH) 4 or hydroxyl ions would be adsorbed on

the precipitate.
The pH of the solution after the electrocoagulation process was
also noted and the results are shown in Fig. 1. From the figure, it
can be observed that the pH of the solution increased after the
electrolysis for the initial pHs from 3 to 7. This enhancement in
solution pH is mainly attributed the increase in hydroxyl ion con-
centration by water reduction at the cathode surface as in Eq. (2)
[10]. But, the effluent pH of SBW having initial pH 10 was
decreased to 8.7 after the electrolysis. This reduction in solution
pH is mainly due to the oxidation of hydroxyl ions at the anode
surface during the electrolysis [11]. Similar results have been
observed by Nidheesh and Gandhimathi [12] for the treatment of
textile wastewater using peroxicoagulation process. Initially the
solution pH increased from 9 and reached to 10 after 10 min of
electrolysis. Further electrolysis of the same wastewater resulted
in the reduction of pH to 9.2.
2H2 O 2e ! H2 2OH 2

3.2. Effect of applied voltage Fig. 2. Effect of applied voltage on the removal of soluble COD at a pH of 7, spacing
of 3 cm and area of 30 cm2.

It has been established that the applied current has a consider-

able influence on the performance of the EC process via the coag-
ulant dosage rate [13]. Current density determines both
coagulant dosage and bubble generation rates and strongly influ-
ences both solution mixing and mass transfer at the electrodes.
Thus, this parameter should have a significant impact on pollutants
removal efficiencies [14]. To evaluate this effect, a series of exper-
iments were conducted by keeping pH 7, spacing of electrodes
3 cm and area of electrodes 30 cm2 and applied voltages varying
from 5 V to 10 V. The removal efficiency variation with voltage is
shown in Fig. 2. It was observed that the increase in voltage
increases the CODS removal efficiency of EC process. An increase
in removal efficiency of 80.9% from 71.9% was observed when
the voltage was increased from 5 V to 10 V at 120 min. This
increase in efficiency of the process is mainly due to the increased
aluminium dissolution at the elevated voltages. The increase in
voltage increases the current density of the electrolytic system.
The current induced at 5 V, 8 V and 10 V were observed as
0.18 A, 0.24 A and 0.35 A respectively. This increased current
increases the dissolution of aluminium ions from the anode and
increases the coagulation efficiency at elevated voltages. If the
voltage is again increasing, there may be a competition between
water oxidation and aluminium oxidation and it will reduce the
removal efficiency [9].
3.3. Effect of electrode spacing
The influence of the distance between the electrodes on the effi-
ciency of the process could be explained by the fact that the elec-
trostatic field which depends on the distance between the
electrodes diminishes as this parameter increases [15]. The influ-
ence of electrode spacing on removal efficiency of CODS is shown
in Fig. 3. The spacing between the electrodes was varied from
1 cm to 5 cm. The results indicated that the increase in spacing
 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115
Fig. 3. Effect of spacing of electrodes on the removal of soluble COD at a pH of 7,
applied voltage of 10 V and area of 30 cm2.
between the electrodes decreases the removal efficiency of CODS
by electrocoagulation process. When the spacing is increased from
1 to 5 cm, the removal efficiency was decreased to 72.2% from
83.1% at 120 min of electrolysis. The electrical conductivity was
directly disproportional to the distance between two electrodes.
As the distance between the anode and cathode is increased, the
resistance is also increased. The decrease in electrode gap
increased the current. The current induced at 1 cm, 3 cm and
5 cm electrode gap were observed as 0.62 A, 0.35 A and 0.21 A,
respectively. The increased current at lesser electrode gaps
increases the efficiency of electrocoagulation as explained earlier.
The increase in the electrode gap between anode and cathode
increases the power consumption for the required current supply
[16]. It was also observed that the current density increases with
decrease in spacing. With increase in spacing between electrodes,
less interaction between ions and hydroxyl polymers is expected
[11].
3.4. Effect of effective area of electrodes
The effect of electrode cross-section area on the removal effi-
ciency was evaluated at 1545 cm2. The results showed that the
removal efficiency decreased by increasing the area of cross-
section of the electrodes (Fig. 4). When the area cross-section of
the electrodes increases, IR-drop decreases, and thus the cell volt-
age and the electrical energy consumed are decreased [6].
A maximum removal efficiency of 85% was obtained with
45 cm2 of electrode area at 120 min of process. The removal effi-
ciency increases from 79% to 85% when the electrode exposed area
increases from 15 to 45 cm2, as the increase in electrode area
increases the amount of Al ions exposed for coagulant activity.
There is direct relationship between removal efficiency and total
area of electrodes. So when the area of electrodes increase, the dis-
tribution of the coagulation agents density is more effective. This
can produce the related coagulation and completes the removal
of pollutants [11].
3.5. Modelling of electrocoagulation process
The CODS reduction velocity can be obtained using a kinetic
model. This model provides preliminary data for evaluation of
the kinetic constants. Chou [17] compared the first and second
111
Fig. 4. Effect of electrode area on the removal of soluble COD at a pH of 7, applied
voltage of 10 V and spacing of 1 cm.
order kinetics for the removal of polyvinyl alcohol and observed
that EC process was best described using pseudo-second-order
kinetics. Vasudevan et al. [18] observed the similar results for
the removal of iron from water medium. The adsorption system
for the removal of fluoride by electrocoagulation process is also
belongs to the second-order kinetic model [19]. Vasudevan et al.
[20] and Vasudevan and Lakshmi [21] analyzed the kinetics of elec-
trocoagulation under both AC and DC supplies. The authors
observed that the electrocoagulation follows second order kinetics
even under DC power supply. Since, all the papers reported that
electrocoagulation process follows second order kinetics; the pre-
sent study also assumed that the process undergoes a second order
reaction rate. The CODS reduction kinetics was evaluated using sec-
ond order equations through various conditions of pH, applied
voltage, spacing of electrodes and effective area of electrodes for
an electrolysis time of 120 min. The rate of electrocoagulation
can be expressed by the following equation [22]:
dCODS
kCODS 2 3
dt
where CODS represents the soluble COD (mg/L), t represents reten-
tion time (min) and k represents the rate constant (L/mg min). A
plot between Time versus 1/C (C = Final CODS) was made. The con-
formity between experimental data and the model values was
expressed by the correlation values (R2).
It is obtained that the second order model best fits the decrease
in CODS with time. A maximum rate constant of 3
106 L/mg-
min was observed at optimum experimental conditions. A rela-
tively high R2 value indicates that the model successfully describes
the kinetics of the EC system. The electrophoretic migration of par-
ticles toward the anode is described by a second order rate equa-
tion which also represents the electrocoagulation rate [23]. The
kinetic model proposed by Matteson et al. [24] is in agreement
with the present results. According to their model the superficial
charge of the colloidal particles are neutralized by the ions gener-
ated during the electro-dissolution of the anode. Also the efficiency
of the process does not depend on the Al generation rate but only
on the electrophoretic velocity of colloidal particles toward the
anode.
Generation of metal flocs through electrochemical process and
the adsorption of the effluents on the surface of the flocs through
physio-chemical process are the two separate processes revealed
112 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115
to have been taking place in a critical analysis of the electrocoagu-
lation of organic pollutants [25]. The hydrous aluminium is bound
to the pollutant which is assumed to act as a ligand to form a
gelatinous precipitate [17]. Faradays law can be used to estimate
the electrode consumption, and a stoichiometric determination
of the amount of generated floc is possible. An adsorption phe-
nomenon can be used to model the pollutant removal because
for a given time the amount of coagulant can be estimated. Lang-
muir and Freundlich equations are the two most commonly
employed adsorption equilibrium models.
The applicability of the isotherm equations was compared
based on the correlation coefficients (R2) in the present study.
The values of all parameters of the adsorption isotherm models,
along with the linear regression co-efficient R2 for the present
experimental conditions, were obtained and listed in Table 3.
Mass transport is very important in separation process. In the
case of an electrolytic system, mass transport rate can be related
to the physical parameters such as electrode length, current den-
sity, electrode potential, electrochemical cell voltage, the ratio of
electrode area and electrolyte volume including the solution prop-
erties, and electrolysis time as well. The mass transfer coefficient
for stirred batch electrochemical reactor (SBER) could be estimated
by [26]
 
km Ae
X SBER 1  exp  t 4
VR
where VR is electrolyte volume (m3), Ae is the electrode area (m2), km
is mass transfer coefficient (m/s), t is reaction time (s), and XSBER is
fractional COD conversion in stirred batch electrochemical reactor
[26]. This equation is a mass balance over the reactor via Faradays
Law with the assumption that the entire electrode supports a reac-
tion under mass transport control via convective diffusion of the
reactant or product and the longitudinal dispersion of flow due to
diffusion is negligible [27].
For initial pollutant concentration (CODS) ranging from
9600 mg/L to 17,600 mg/L electrocoagulation tests were conducted
at optimum conditions. It is found that as the pollutant concentra-
tion increases the mass transfer coefficient decreases. A maximum
mass transfer coefficient of 7.5
105 m/s was obtained at an ini-
tial pollutant concentration of 9600 mg/L. For a pollutant concen-
tration of 17,600 mg/L the mass transfer coefficient obtained is
6.7
105 m/s.
The mass transfer coefficient was determined with respect to the
electrolysis time at the optimum conditions. As the electrolysis time
increases the mass transfer coefficient decreases. Mass transfer
coefficient decreases from 2.1
103 m/s to 5.9
105 m/s when
the electrolysis time increases from 15 min to 120 min. The mass
transfer coefficient km is affected by a complex IR drop in the elec-
trolyte during gas evolution at the electrodes. In the liquid phase
mass transfer process is slower than in the gas phase in electro-
chemical reactors [26]. This phenomenon results in mass transport
that is more complicated and having limitations on chemical change
rates in the reactor and at the solidliquid interface reaction layers
are formed as indicated by Pletcher and Walsh [27].
Table 3
Characteristic constants of Langmuir and Freundlich adsorption isotherm models of
aluminium anode.
Langmuir isotherm Freundlich isotherm
KL (L/mg) aL (mg/g) R2 n kf (mg/g)
4
2.2988
10 50,000 0.998 1.424 72.777
3.6. Comparison between electrocoagulation and chemical coagulation
A comparison between the CODS removal efficiencies of the
chemical and the electrochemical break-up of O/W emulsions with
hydrolyzing aluminium salts was done and determined the simi-
larities or differences that exist between both destabilization pro-
cesses. To meet this objective, the experiments were conducted to
meet similar conditions between both technologies, especially in
terms of aluminium dose and pH. Standard jar tests for synthetic
bilge water treatment were conducted on a jar test apparatus.
The synthetic bilge water of 500 mL with different pH, such as 3,
5, 7 and 10 were transferred into each of the 1000 mL glass beakers
and a four-paddled stirrer was used for mixing. Predetermined
amount of coagulant (Al2(SO4)316H2O) was dosed and then the
solutions were stirred rapidly at 150 rpm for 60 s after coagulant
addition, followed by slow stirring at 40 rpm with duration of
15 min and then 60 min of quiescent settling. After depositing,
samples were collected from 2 cm below the solution surface for
subsequent measurements of CODS. The comparison between
chemical coagulation and electrocoagulation is tabulated in
Table 4.
A similar behaviour of CODS removal was obtained for both
chemical and electrocoagulation processes. As shown in Table 4
the electrocoagulation process has a higher efficiency than the
chemical coagulation process. A maximum removal efficiency of
59% in relation with CODS removal corresponds to the aluminium
dosage of 0.1012 g/L generated in the chemical coagulation pro-
cess, while by electro dosing of aluminium the removal efficiency
reaches around 78%. The effluent contains sulphate after chemical
coagulation process. Since the coagulant dosage is high, the final
pH of the effluent decreases compared to the initial pH. As metal
coagulants are commonly acidic, coagulant addition consumes
alkalinity. For low alkalinity waters coagulant addition may con-
sume all of the available alkalinity depressing the pH values too
low for effective treatment. High alkalinity waters may require
high coagulant addition to depress the pH values favourable for
coagulation [28]. It is also found that the settling ability of the
chemically coagulated sludge was poor compared to that of elec-
trocoagulation. Organic flocs are fragile, open structures that have
a low settling velocity when it is formed during the treatment [29].
The growth rate of flocs in stirred tanks is initially determined by
the applied shear, the concentration of particles and efficiency of
collision (and hence on the degree of particle destabilization
caused by the added coagulant). The further growth of flocs as they
become larger is restricted by the applied shear due to two reasons.
Disruptive forces may be break the existing flocs [30] and as parti-
cle size increases the efficiency of collision of particles in a shear
field is lowered [31,32]. Bonds between the components of the
aggregate determine floc strength. The floc strength is also interre-
lated with floc structure, particle bond strength and the number of
individual bonds [33]. Therefore, a floc will be broken when the
bonding strength is lower than the stress on floc. The settling
velocity decreases as the shear rate increases, due to the decreasing
size of floc [34]. As the sludge formed by electrocoagulation is pri-
marily composed of metallic oxides/hydroxides it settles readily
and is easy to de-water compared to chemical coagulation. Flocs
formed by electrocoagulation can be separated faster by filtration
because electrocoagulation flocs tend to be much larger, contain
less bound water, are acid-resistant and more stable unlike chem-
ical flocs. The advantage of the electrocoagulation process is that it
can remove even the smallest colloidal particles by facilitating the
coagulation because the applied electric field sets them in faster
R2 motion. The pollutant is carried to the top of the solution by the
gas bubbles produced during electrolysis and it can be easily con-
0.997
centrated, collected and removed. The electrolytic processes in the
 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115 113

Table 4
Comparison between chemical coagulation and electrocoagulation.

pH Amount of Al Chemical coagulation Electrocoagulation

dissolved (g/L)
Alum dosage Final Initial sulphate conc. Conc. of sulphate in CODS removal Final CODS removal
(g/L) pH (mg/L) effluent (mg/L) efficiency (%) pH efficiency (%)
3 0.0875 1.020 2.87 293.76 136.08 18.545 6.36 64.727
5 0.1413 1.648 3.62 474.62 287.45 51.273 6.84 73.818
7 0.1614 1.880 4.01 541.44 323.44 59.272 8.05 77.636
10 0.1012 1.176 7.32 338.69 189.82 33.818 8.65 68.909

electrocoagulation cell requires only less maintenance since it is

controlled electrically with no moving parts [35].
During the electrocoagulation process, sludge was formed at the
top and bottom of the cell and was analyzed separately. The sludge
formed after electrocoagulation process was collected and dried for
finding volatile and fixed fraction. The results are given in Table 5.
The volatile fraction indicates the presence of hydrocarbon in the
sludge and fixed fraction indicates the presence of heavy metals
and other impurities.
X-ray diffractograms (Fig. 5) of electrocoagulation by-products
in the present experiment showed very broad and diffused diffrac-
tion peaks indicating that the analyzed phase possesses a short-
range order, i.e. amorphous and very poorly crystalline in nature.
The presence of AlO(OH), Al(OH)3, and Al2O3 were identified. The
heavy metals which are present in the synthetic bilge water were
precipitated as its hydroxides. XRD results shows the presence of
Ni(OH)2, Cu(OH)2 and Zn(OH)2 in the sludge obtained after electro-
coagulation process. So the removal of heavy metals is an added
advantage of the process. The electro co-precipitated sludge gener-
ated was analyzed using FTIR spectrometer and the results are
shown in Fig. 6. Peaks at 2852, 2863, 2914, 2938 cm1 are corre-
sponding to CAH stretching mode of saturated CAC bonds, show-
ing the presence of hydrocarbons in the sludge [36]. Peaks at
1751 and 2357 cm1 are corresponding to stretching vibration of
C@O [37]. OAH bending and AlAOAH bending vibrations were
obtained at peak corresponding to 1457 cm1 [38]. Peak at
1369 cm1 shows the presence of ZnAOAH. Peak at 669 cm1
was assigned to the skeletal vibration of CAC [39].

3.7. Performance of different electrode combination in

electrocoagulation

In electrochemical processes the electrode pair has significant

effect on the removal efficiency. The type of electrode used is a
controlling factor for the performance of electrocoagulation pro-
cess [36]. The effective performance of electrocoagulation tech-
nique in the treatment of bilge water has been investigated using
different combinations of aluminium (Al) and iron (Fe) electrodes. Fig. 5. XRD pattern of sludge produced in the electrocoagulation process.
Fig. 7 shows the effects of the electrode pair on the CODS removal
efficiency.
From Fig. 7, when electrolysis time increases from 0 min to of pollutants and sludge flotation is achieved since there is an
120 min the removal of CODS increases to 85% for the AlAAl pair, increase in the amount of metal oxidized which increases the
to 74.5% for the AlAFe pair, to 70.9% for the FeAAl pair, to 66.9% removal efficiency. Also with increasing current density, bubbles
for the FeAFe pair. density is increased and their size decreased resulting in a greater
Among all the combinations, higher current density was upwards flux [40]. Various monomeric and/or polymeric metal
observed for AlAAl combination. At high current, a faster removal hydroxides complexes are formed (Eq. (5)) by Fe3+ and/or Fe2+ ions,
depending on pH when iron electrode is used as anode. Hydrous
iron is chemically bound by the pollutant which acts as a ligand
Table 5 (L) in the surface complexation mode [41].
Results of sludge characterization study.

Sl. no. Content Amount present (%)

L-Haq OHOFes ! L-OFes H2 O 5
1 Volatile fraction of top sludge 93
2 Fixed fraction of top sludge 6.9 The solution was turned into a red brownish colour after some
3 Volatile fraction of bottom sludge 81.6 time of the electrocoagulation process due of the formation of the
4 Fixed fraction of bottom sludge 18.3
octahedral hexaaquaions, [Fe(H2O)6]3+. When the pH is greater
114 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115

Table 6
Characteristics of real bilge water.

Sl. no. Parameter Values

1 pH 7.17
2 Chloride 3249 mg/L
3 Turbidity 2560 NTU
4 Total COD 11,520 mg/L
5 Soluble COD 9,920 mg/L
6 Total solids 24,435 mg/L
7 Total dissolved solids 15,080 mg/L
8 Total suspended solids 9,355 mg/L
9 Total fixed solids 6,025 mg/L
10 Total volatile solids 18,410 mg/L

coagulation by a gelatinous suspension of Fe(OH)2 which is formed

in alkaline pH and remains in the aqueous stream as a gelatinous
suspension [43]. Due to incipient oxidation of Fe(OH)2 by air, its
normal colour green turns to greenish-black [44]. So, the effluent
obtained after electrocoagulation is coloured and it reduces the
efficiency of the treatment. Another factor is that when iron elec-
trodes are used no secondary reaction takes place in the anode,
i.e. there is no formation of oxygen. In the case of aluminium anode
both hydrogen and oxygen gases helps the removal of pollutants
[45].

3.8. Case study on real bilge water

Fig. 6. FTIR spectrum of the sludge produced in the electrocoagulation process.
The real bilge water was collected from the bilge compartment
of Kangayan fish boat at Rameswaram harbour, Tamilnadu. The
characteristics of bilge water were determined according to APHA
standard method. The experiment was conducted at optimum con-
ditions (at pH = 7, current density = 0.65 A/cm2, spacing = 1 cm and
effective area of electrodes = 45 cm2) for an electrolysis time of
120 min using aluminium electrodes. The characteristics of real
bilge water collected from the Kangayan fish boat, Rameswaram
are given in Table 6.
The real bilge water shows a neutral pH. The concentration of
chloride and dissolved solids indicates a high conductivity of bilge
water. A high CODS value and volatile solids confirms the presence
of hydrocarbons in bilge water.
The experiment was conducted at optimum conditions for an
electrolysis time of 120 min using aluminium electrodes. From
Fig. 8, a maximum CODS removal of 89.84% was obtained after an
electrolysis time of 75 min. 200 mL/L of sludge was obtained after
the electrocoagulation process.

Fig. 7. Effect of different electrode pairs on the COD removal efficiency (pH = 7,
applied voltage = 10 V, spacing = 1 cm, effective area = 45 cm2).

than 4 it gives a red brownish colour gelatinous precipitate of

hydrous oxide [42]. Pollutants from wastewater were removed Fig. 8. Soluble COD removal efficiency with respect to time (at pH = 7, current
by either complexation or electrostatic attraction, followed by density = 0.65 A/cm2, spacing = 1 cm, effective area = 45 cm2).
 P. Aswathy et al. / Separation and Purification Technology 159 (2016) 108115
4. Conclusions
Electrocoagulation process was an effective technology for the
treatment of oily bilge water. The CODS removal efficiency of 85%
was obtained at the optimal operating conditions with a maximum
removal rate constant of 3
106 L/mg-min. The sludge character-
ization was carried out and XRD and FTIR results represent the for-
mation of aluminium hydroxide and the presence of hydrocarbons
and heavy metals which confirms the removal efficiency by elec-
trocoagulation process. Experimental measurement of COD gave
an acceptable fit for both Langmuir isotherm model and Freundlich
isotherm model with an acceptable analogous and a linear regres-
sion coefficient R2 of 0.998 and 0.997 respectively. A maximum
mass transfer coefficient of 7.5
105 m/s was obtained at an ini-
tial pollutant concentration of 9600 mg/L. Mass transfer coefficient
decreased from 2.1
103 m/s to 5.9
105 m/s when the elec-
trolysis time increased from 15 min to 120 min. Chemical coagula-
tion was found to be less effective than electrocoagulation for the
treatment of bilge water which showed a maximum CODS removal
of 59.3%. Among different combinations of Fe and Al electrodes,
AlAAl electrode combination had maximum CODS removal effi-
ciency of 85%. The minimum CODS removal efficiency of 67% was
obtained for FeAFe electrode combination. In real bilge water the
maximum CODS removal of 89.84% was achieved with AlAAl con-
figuration after an electrolysis time of 75 min at optimum
conditions.
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