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An alternative method for the removal of

surfactants from water: Electrochemical
coagulation
ARTICLE in SEPARATION AND PURIFICATION TECHNOLOGY JANUARY 2007
Impact Factor: 3.07 DOI: 10.1016/j.seppur.2006.06.006

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Separation and Purification Technology 52 (2007) 527532

An alternative method for the removal of surfactants from water:

Electrochemical coagulation

gu tveren

Ebru Onder,
Ali Savas Koparal , Ulker
Bakr O
Anadolu University, Iki Eylul Campus, Applied Research Center for Environmental Problems, 26480 Eskisehir, Turkey
Received 24 March 2006; received in revised form 9 June 2006; accepted 11 June 2006

Abstract
Feasibility of the removal of surfactants from model solution and the polluted water sample by electrochemical coagulation utilizing Fe2+ ions
from a soluble anode as an alternative method was investigated in this study. As a result of the studies the removal of surfactant having a concentration
of 10 mg L1 has been achieved with an efficiency of 100%. Experiments were conducted to examine the effects of applied current density, initial
concentration, supporting electrolyte concentration, coagulant dosage and pH on the removal efficiency. Energy consumption was calculated for
each experiment and optimum conditions have been determined. Addition of ferrous sulphate and hydrogen peroxide was seen to enhance the
efficiency of the process. The polarity of the reactor played an important role in the treatment of surfactants. Electrochemical coagulation of the
water sample from a local stream has also been conducted in high efficiencies. The results suggest that electrochemical coagulation is a promising
method for the treatment of water polluted by detergents.
2006 Elsevier B.V. All rights reserved.
Keywords: Electrochemical coagulation; Surfactant; Detergent

1. Introduction
Water is one of the abundantly available resources in nature
and is essential for animal and plant life. Pollution of water
bodies is increasing steadily due to industrial application and
urbanization. Nowadays, the worldwide production and use of
chemical compounds such as surfactant have increased tremendously which find their way into the environment. Many of these
compounds are biologically non-degradable and threat for environmental conservation [1].
Detergents are used to aid in cleaning equipment and surfaces
by restaurants, dairy farms, and food processing plants and are
among the basic constituents of organic pollutants in domestic
as well as industrial wastewaters causing great environmental
damages [2]. Due to their high volume use, detergent chemicals
have the potential for broadscale release into aquatic and terrestrial environment. It is quite frequent, especially in rural areas
with no sewerage system, municipal and industrial wastewater

Corresponding author. Tel.: +90 222 3213550x6406; fax: +90 222 3239501.

E-mail addresses: eonder@anadolu.edu.tr (E. Onder),

askopara@anadolu.edu.tr (A.S. Koparal), uogutver@anadolu.edu.tr
gu tveren).

(U.B.
O
1383-5866/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.06.006

containing detergent infiltrates into soil and ground waters from

septic tanks. Surfactants can reach humans, animals and plants
from the ground waters used as drinking water supplies [3].
Besides the toxic effects of surfactants their existence in
waters even under the toxic level causes many adverse effects on
biological life. They cause pathological, physiological and biochemical effects on aquatic animals. In aquatic plants species,
they have effects such as break-up of the chlorophyllprotein
complex, death of the cell by damaging the membrane, delay in
metabolism and growth [4].
A large number of surfactants are not easily biodegradable.
On the other hand it is not possible to use easily biodegradable surfactants in all household and industrial applications due
to the economic reasons. Thus, pretreatment methods such as
ozonation and other advanced chemical oxidation of surfactant
in the water need to be developed which allow safe use of refractory types of surfactants [4]. Although effective on improving
the biodegradability of refractory surfactants, ozonation or photocatalytic oxidation is a relatively costly method. Biological
treatment techniques require long time and increase the cost,
therefore they are considered not to be effective [5].
Electrochemical techniques have an important role among the
advanced treatment technologies and offer a good opportunity
to prevent and remedy pollution problems [6]. Electrochemical


E. Onder
et al. / Separation and Purication Technology 52 (2007) 527532

528

Fig. 1. Experimental set-up.

coagulation, which is one of these techniques is the electrochemical production of destabilization agents that brings about
charge neutralization for pollutant removal and it has been used
for water or wastewater treatment. In this technique, ferrous ions
generated at the anode is oxidized to the ferric state with dissolved oxygen in the water which reacts with hydroxide ions
formed at the cathode causing a coprecipitation of the impurities with the insoluble ferric hydroxide. The reactions at the
anode, cathode and in the bulk solution are as follows:
At the cathode:
2H2 O + 2e H2 + 2OH

(1)

At the anode:
Fe Fe2+ + 2OH
O2

Fe2+ Fe3+

(in the solution)

(2)
(3)

Ferric state of iron in the solution may form monomeric

ions, ferric hydroxo complexes and polymeric species with
hydroxide ions such as FeOH2+ , Fe(OH)2 + , Fe2 (OH)2 4+ and
Fe(OH)4 depending on the pH range, which transform finally
into Fe(OH)3 which is a dense, rapid settling floc in the solution
(Eq. (4)):
Fe3+ + 3OH Fe(OH)3

(4)

Usually, aluminum or iron plates are used as electrodes in the

electrocoagulation process. Electrochemically generated metallic ions from these electrodes can undergo hydrolysis near the
anode to produce a series of activated intermediates that are
able to destabilize the finely dispersed particles present in the
waterwastewater to be treated. The destabilized particles then
aggregate to form flocs [7].
The advantages of electrocoagulation include high particulate removal efficiency, compact treatment facility, relatively
low cost and possibility of complete automation [8,9]. This
method is characterized by reduced sludge production, minimum requirement of chemicals and ease of operation [9,10].
Although, there are numerous reports related with electrochemical coagulation as a means of removal of many pollutants from
water and wastewater [1114], any study about surfactants has
not been reported yet in the literature. Therefore, the purpose

of this study was to employ electrochemical coagulation in

the treatment of water containing linear alkylbenzene sulfonate
(LAS) and sodium lauryl ether sulfate (SLES).
2. Experimental
Electrochemical coagulation of surfactants has been carried
out using a reactor of 1 L and a magnetic stirrer made from cast
ironas the electrodes and applying different currents in a reactor within specified time periods (01 h). The reactor used in this
study was a cylindrical electrochemical reactor and the performance of the reactor has been evaluated in batch experiments.
The experimental set-up is shown in Fig. 1. The volume of the
reactor, which has diameter of 11 cm and height of 13 cm, is 1 L.
Approximately, 1 L of solution has been treated in the reactor.
After the treated solution was filtered by filter paper, the filtrate
has been analysed to determine the remaining concentration of
the surfactant in the solution. Water sample containing detergents taken from Porsuk river, which is a local stream, have been
treated by applying same method without adding any chemicals.
All chemicals used in experiments were of analytical grade.
Surfactants have been supplied from SODAS Company in
Turkey. Linear alkylbenzene sulfonate (LAS) and sodium lauryl
ether sulfate (SLES) have been used in model solutions prepared
by distilled water to have initial concentrations of 10, 50 and
300 mg L1 . Molecular weight and purity of LAS is 320 g mol1
and 96.5%, respectively. Molecular weight and purity of SLES
is 288.38 g mol1 and 99.5%, respectively. The chemical structures of LAS and SLES are in Fig. 2.

Fig. 2. Chemical structures of LAS and SLES.


E. Onder
et al. / Separation and Purication Technology 52 (2007) 527532

Na2 SO4 , Fe2 SO4 and H2 O2 have been added to increase

the conductivity, to aid the coagulation of the solution and
to increase the removal efficiency due to formation of Fentons reagent, respectively. Different pH values such as 3,
9 and 11 representing acidic and basic conditions have also
been examined besides the original pH (pH 4.5) of the
solution.
A power supply (Elsim, 220 V) for applying potential difference to the electrodes, a digital multimeter (DT 3800B) to
control the current input, a magnetic stirrer (Electro-Mag) to stir
the solution and to be used as an electrode have been employed
in the experiments. Surfactant concentrations have been determined by means of an ionmeter (Orion 710A Benchtop pH/ISE)
and an ion-selective electrode (Cole Parmer).
During the electrochemical treatment of model solution, a
small amount of iron was continuously dissolved into the solution from the cast iron electrode, and combined with OH to
form flocs that coprecipitate with the pollutants in the water. A
stirring rate of about (200 rpm) was applied to allow the flocs to
grow large enough for precipitation.
BOD, COD, turbidity and conductivity have been used as
analytical methods for evaluation of treatment of the surfactant.
Method number of the BOD is 5210B (5-day BOD test), method
number of the COD is 5220B (open reflux method), method
number of the turbidity is 2130B (nephelometric metho) and
method number of the conductivity is 2510B (laboratory conductivity) in standard methods [15].
In preliminary experiments, the effects of operational parameters were studied in an attempt to achieve a more efficient
treatment of surfactant. The optimised parameters were then
applied for the treatment of the model solution and the water
sample to evaluate the treatment performance.
3. Results and discussion
The most widely used electrode materials in electrochemical
coagulation are aluminium and iron [16]. Iron was used in this
study because of ease of availability and cheapness.
3.1. Performance characteristics of electrochemical
coagulation
3.1.1. Applied current density
Applied current in electrocoagulation determines the coagulant dosage produced as expected. To obtain the effect of applied
current density on the removal efficiency and energy consumption different current densities have been applied and the results
have shown in Fig. 3(a and b). The energy consumption value
has been determined as follows:
energy consumption =

IVt
(C0 C)Q

where I is the applied current (A), V the potential value (V), t the
time (h), C0 the initial concentration of the surfactant (mg L1 ),
C the concentration of the surfactant at any time (mg L1 ) and
Q is the flow rate of the model solution.

529

Fig. 3. Variation of removal efficiency and energy consumption for different

applied current density (initial concentration: 10 mg L1 ).

An increase in applied current density have resulted in an

increase in removal efficiency. This increase is due to much
more formation of iron ions, which play an important role in the
precipitation, at higher current densities. For the solution with a
concentration of 50 mg L1 , the removal efficiency of 86% has
been achieved with an energy consumption of 0.1209 kWh g1
at a current density of 0.368 mA cm2 in 30 min. When current
density was 0.460 mA cm2 , a removal efficiency of 90% has
been achieved with an energy consumption of 0.3111 kWh g1
in the same duration with the same concentration. This expected
behaviour is explained by the fact that the treatment efficiency
was mainly affected by charge loading which equals It, where I
is the applied current, t is the time.
Energy consumption values for different current densities can
be seen in Fig. 3(b). There is no significant increase in energy
consumption values within 10 min of electrolysis time. Beyond
this point increase in removal efficiency due to increase in current density has been observed along with increase in energy
consumption with higher rates in higher current densities. There
was no difference in energy consumption values at the current
densities of 0.368 and 0.460 mA cm2 , while the lowest current density corresponds the lowest energy consumption value
as expected. Rapid increase after 10 min may be due to the losses
by Joules effect because of an increase in temperature especially
in higher current densities. However, the cost of the process is
determined by the consumption of the soluble electrode besides
the energy consumption. Therefore, the amount of iron oxidized
to achieve high removal efficiency of >90% was calculated at


E. Onder
et al. / Separation and Purication Technology 52 (2007) 527532

530

Fig. 4. Variation of removal efficiency and energy consumption for two different
initial concentration of LAS (applied current density: 0.460 mA cm2 ).

different current densities according to the Faradays law:

m=

ItM
nF

(5)

where M is the molecular weight of iron, n the number of electrons transferred in the reactor and F is the Faradays constant
(96,500 C mol1 ). From this point of view, electrode consumption per liter of treated water increased significantly with
increase in current density being equal 0.298 and 0.373 g L1
for 0.368 and 0.460 mA cm2 , respectively.
3.1.2. Initial concentration
The variation of removal efficiency and energy consumption
for two initial concentrations of 10 and 50 mg L1 have shown in
Fig. 4. As it can be seen from this figure that an increase in initial
concentration has resulted in a decrease in removal efficiency.
This is likely due to lack of coagulant for adsorbing excess surfactant in high concentration since total amount of coagulant
(i.e. Fe(OH)3 ) is constant for all surfactant concentrations at the
same conditions. Specific energy consumption with 50 mg L1
was lower than that of 10 mg L1 because the amount of surfactant removed per unit time for the same removal efficiency was
larger.
To observe the effect of type of surfactant on the removal efficiency of the process, sodium lauryl ether sulfate (SLES) has also
been used in a model solution. LAS concentration was obtained
to be 1 mg L1 whereas SLES concentration was 2.5 mg L1
at the same time period of 10 min. This result has shown that
the removal of surfactant can be achieved effectively by electrochemical coagulation with both type of surfactant.
3.1.3. Supporting electrolyte
One of the important factors for the electrochemical processes, which consist of heterogeneous electron transfer reactions at the electrode surface is the conductivity of the solution
to be treated [17]. On the other hand, essential mechanism in

Fig. 5. Effect of supporting electrolyte on removal efficiency and energy

consumption (initial concentration: 10 mg L1 ; applied current density:
0.275 mA cm2 ).

electrochemical coagulation is aggregation by van der Waals

forces since flocculation of pollutants with iron is caused by their
adsorption of iron hydroxide aggregates. Yet, sodium sulfate
(Na2 SO4 ) has been used as a supporting electrolyte to observe
the effects of it in this study. Although it has a negligible effect
on the removal efficiency, energy consumption has lowered dramatically as shown in Fig. 5. This must be due to the presence
of an electrolyte (i.e. iron hydroxide aggregates) having opposite charge already, effectively reducing the repulsive potential
between the colloids making it possible leading to aggregation.
Energy consumption was much higher in the case of absence of
Na2 SO4 because of high resistance in the solution due to poor
conductivity. On the other hand ferrous sulfate (Fe2 SO4 ) has
been added to increase the coagulant concentration and therefore the efficiency of electrochemical coagulation and hydrogen
peroxide (H2 O2 ) has been added to form Fentons reagent and
to increase the removal efficiency of the iron reactor. Energy
consumption has also decreased when FeSO4 and H2 O2 were
added as expected. For example; for the solution of 300 mg L1 ,
the removal efficiency of 98% has been achieved with an energy
consumption of 6.1 105 kWh g1 in 4 min at the current density of 0.460 mA cm2 by adding 0.01 M Fe2 SO4 and 0.05 M
H2 O2 whereas the removal efficiency and the energy consumption were 39% and 3.0 104 kWh g1 , respectively without
Fe2 SO4 and H2 O2 as can be seen in Fig. 6. Thus, removal
efficiency increased 2.5-fold and energy consumption lessened
5-fold by adding FeSO4 and H2 O2 into the solution.
3.1.4. pH
pH is an important parameter in chemical and electrochemical coagulation. The effect of pH on the surfactant removal
efficiency and energy consumption can be seen in Fig. 7(a and
b). This method bases on the formation of Fe(OH)3 due to the
reaction of Fe3+ generated at the anode and OH ions generated
at the cathode. Insoluble hydrous ferric oxide is produced over


E. Onder
et al. / Separation and Purication Technology 52 (2007) 527532

Fig. 6. Effect of 0.01 M FeSO4 and 0.05 M H2 O2 on the removal efficiency and
energy consumption (initial concentration: 300 mg L1 ; applied current density:
0.460 mA cm2 ).

a pH range of 3.013.0. It can be seen from Fig. 7(a) that good

removal efficiencies have been obtained in all pHs. However,
original pH of the model solution (pH 4.5) can be preferred even
if a small deficiency because of requiring no chemical. Energy
consumption values for different pHs can be seen in Fig. 7(b).
There is no significant difference in energy consumption values

531

Fig. 8. Effect of the polarization of the reactor on the removal efficiency and
energy consumption (initial concentration: 10 mg L1 ; applied current density:
0.460 mA cm2 ).

within 10 min of electrolysis time. Beyond this point increase

in removal efficiency has been observed with increase in energy
consumption especially in original pH. After 10 min, the energy
losses due to the temperature increase has been important as
mentioned before. In the original pH of the surfactant solution,
pH was as high as 7 after 60 min, whereas the final pH was 5
starting with pH 3. This increase in pH can be expected especially when the initial pH is lower than 7 because of formation
of OH ions at the cathode. Therefore, pH adjustment will not
be required after treatment.
3.1.5. Polarization of the reactor
The effect of polarization of the reactor on the removal efficiency and energy consumption can be seen in Fig. 8. When the
reactor was used as positive electrode-anode (i.e. stirrer is negative electrode-cathode) the high concentration of iron hydroxide
in the vicinity of the anode enhanced the coagulation of pollutants. Thus, a higher removal efficiency has been obtained as
shown in Fig. 8. When the reactor was used as negative electrode the flocs have moved rapidly outwards, which did not
enhance the coagulation significantly. Energy consumption was
lower when the reactor was anode as expected as shown in Fig. 8.
However, producing water containing 1 mg L1 surfactant is significantly more costly (by a factor of 2) than producing water of
2 mg L1 even in this case. This fact should be considered for
the economic evaluation of the process.
4. Treatment of polluted water sample

Fig. 7. Effect of pH on removal efficiency and energy consumption (initial concentration: 50 mg L1 ; applied current density: 0.368 mA cm2 ).

Water sample taken from Porsuk river, which is a local stream

has also been treated using electrochemical coagulation without
adding any chemicals. The characteristics of the water sample
taken from Porsuk river can be seen in Table 1. As a result of the
studies, LAS concentration of 2 mg L1 has been achieved with
relatively low energy consumption of 0.012 kWh g1 as it can be

532

E. Onder
et al. / Separation and Purication Technology 52 (2007) 527532

Table 1
The characteristics of the water sample from the local river before and after
electrochemical coagulation (surfactant concentration: 12.66 mg L1 )

Chemical oxygen demand (mg L1 )

Biochemical oxygen demand (mg L1 )
Conductivity (S/cm)
Turbidity (NTU)
pH

Before treatment

After treatment

91
48
58
1.08
8.44

36
16
14
0.29
8.03

low energy consumption of 0.012 kWh g1 by applying electrochemical coagulation. Moreover, the final pH of the treated
water within the discharge limit and needs no pH adjustment.
Consequently, electrocoagulation can be considered as a suitable
method for removing surfactants from waters.
Acknowledgement
This study was supported by Anadolu University Research
Fund.
References

Fig. 9. Variation of removal efficiency and energy consumption with time for
the polluted water sample (initial concentration: 12.66 mg L1 ; applied current
density: 0.460 mA cm2 ).

seen in Fig. 9. Characteristics of the water after treatment have

also changed as shown in Table 1. According to these results,
removal efficiencies of COD, BOD and turbidity have been 60,
67 and 73%, respectively for polluted water sample. It can be
seen from Fig. 9 that pH has not been changed noticeably.
5. Conclusions
The removal of surfactants can be achieved efficiently by
using electrochemical coagulation not depending on the type
of surfactant. This method has advantages such as requiring no
chemicals and causing no sludge problem. Ferrous sulfate and
hydrogen peroxide with low concentrations have been added
to aid the coagulation of the solution and increase the removal
efficiency while decreasing energy costs. Removal efficiency of
nearly 100% has been achieved for the solution of 300 mg L1 in
a short time of 4 min. Studies with polluted water samples have
shown that surfactants can be removed under the limits with

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