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ELSEVIER Desalination 197 (2006) 262-272
www.elsevier.com/locate/desal

Removal of linear alkylbenzene sulfonate from a model solution

by continuous electrochemical oxidation

A. Sava~ Koparal*, Ebru 0nder, lJlker Bakir 0~itveren

Anadolu University, Applied Research Centerfor Environmental Problems 26470 Eski4ehir, Turkey
Tel. +90 (222) 3213550 ext. 6406; Fax +90 (222) 3239501; email: askopara@anadolu.edu.tr

Received 7 October 2005; accepted 8 December 2005

Abstract
The aim of this work is to investigate the feasibility of the removal of surfactants from water continuously by
means of direct electrochemical oxidation. Two different surfactant concentrations of 10 mgL-1 and 50 mgL-1 have
been studied for electrochemical oxidation and the effects of applied current density and solution flow rates on
energy consumption and removal efficiency have been investigated. The effects of the concentration of Na2SO 4
used as a supporting electrolyte and pH on the performance of the process have also been examined. As a conclusion,
it has been found that linear alkylbenzene sulfonate can be removed from water efficientlyby using electrochemical
oxidation requiring no chemicals and causing no sludge problem.
Keywords: Detergent; Electrochemical oxidation; Linear alkylbenzene sulfonate; Surfactant

1. Introduction alkylbenzene sulfonate (LAS) is an anionic sur-

face active material contained in high amounts in
Municipal wastewater is one of the important
municipal and industrial wastewaters discharged
pollution sources affecting the water quality
from textile, leather, food, paint, polymer, cosme-
adversely in many developed countries. Especially
tics, mining, oil recovery and paper industries [2].
wastewaters containing detergents are among the
Most of the surfactants cannot be biologically
basic constituents of organic pollution and they
degraded and accumulate in water bodies [3]. This
cause great environmental damage by entering the
affects the natural balance of waters, threatens the
soil, sea, lakes and rivers [1].
health of aquatic organisms and humans who eat
As a result of economic development and
them.
population growth, environmental problems caused
Besides the toxic effects of surfactants, their
by detergents are increasing day by day. Linear
existence in waters even under the toxic level
causes many adverse effects on biological life.
*Corresponding author.

0011-9164/06/$- See front matter © 2006 Published by Elsevier B.V.

doi: 10.1016/j.desa1.2005.12.024
 A.S. Koparal et al. / Desalination 197 (2006) 262-272
They cause pathological, physiological, bioche-
mical and other effects on aquatic animals. In
aquatic plants species, they have effects such as
break-up of the chlorophyll-protein complex,
death of the cell by damaging the membrane, delay
in metabolism and growth [4].
A large number of surfactants, including the
anionic types are not easily biodegradable. On the
other hand due to economic reasons, it is not
possible to use easily biodegradable surfactants
in all household and industrial applications. Thus
pretreatment methods such as ozonation and other
advanced chemical oxidation of surfactant
wastewater need to be developed which allow safe
use of refractory types of surfactants [4].
Although effective in improving the biode-
gradability 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]. Advanced
treatment technologies need to be applied to treat
the surfactants to be discharged to receiving en-
vironments, and electrochemical techniques have
an important role among these.
Electrochemical methods have the advantages
such as no chemicals requirement before and after
the treatment, producing no sludge, requiring
small area and low investment cost [6]. These
methods are environmentally friendly, and they
do not form new toxic wastes. They have been
successfully utilized in the purification of olive
wastewaters [7,8], domestic sewage [9], landfill
leachate [ 10,11], tannery wastes [ 12], textile wastes
[13]. However, there is a limited research report
on electrochemical oxidation ofsurfactants in lite-
rature [2,5,14,15]. In electrochemical oxidation
ofsurfactants, surfactant molecules are supposed
to decompose into smaller molecules or final pro-
ducts at the anode directly by a quite complex
mechanism applying sufficient current density
[14]. On the other hand, Lissens et al. [15] have
proposed a mechanism for non-ionic and cationic
detergents via hydroxyl radicals in the potential
region of water decomposition at alkaline pH.
263
In this study, the feasibility of direct electro-
chemical oxidation of LAS on the anode surface
has been investigated. Parameters that can affect
the performance of the process, such as current
density, initial concentration of surfactant, flow
rate and pH of the solution, and the concentration
of supporting electrolyte have been examined.
2. Experimental
Direct electrochemical oxidation of LAS has
been carried out using a bipolar packed bed reactor
due to its effectiveness in the case of solutions
with low conductivity, requiring minimum amount
of supporting electrolyte such as Na2SO 4. The
reactor consists of two concentric glass tubes with
diameters of 4 cm and 2.5 cm. Ruthenium oxide
raschig rings used as packing material having
8.2 mm outer diameter, 6.5 mm inner diameter
and 7 mm height, were placed in the inner tube as
bipolar electrodes consisting of 28 layers. Ruthe-
nium oxide was used as electrodes due to its capa-
bility to destroy refractory organics [ 16]. Two gra-
phite rods used as feeder electrodes were con-
nected to a DC power supply. When a potential
difference is applied between the electrodes, each
raschig ring becomes a small cell with one end
(-) and the other (+) (Fig. 1).
It has been reported by Leu et al. [5] that in
most of the seriously polluted streams, concentra-
tion of any kind of surfactant does not exceed
10 mgL 1. Therefore, a model LAS solution of
10 mgL 1was used, and a model solution of
50 mgL -1 was also studied to obtain the effect of
the initial concentration in the experiments. Acidic
(pH = 3) and basic (pH = 9) pHs besides the
original pH (pH = 5.5) of the solution were exa-
mined for both concentrations and measured by a
pH meter. To increase the conductivity of the solu-
tion of 60 gs/cm which is very low for an electro-
chemical process, sodium sulfate (Na2SO4) at dif-
ferent concentrations was added. The effects of
the parameters such as the initial LAS concentra-
tion, solution flow rate, pH and supporting electro-
lyte concentration on the removal efficiency,
264 A.S. Koparal et aL / Desalination 197 (2006) 262-272

Solutioninlet where V is the potential (V), I is the current (A)

and Q is the flow rate (Lh-1).
Since the current density is an important factor
affecting the efficiency and energy consumption
of an electrochemical system, three different cur-
~,,,, ~ Cooling
Electrode ~" ~ t e r outlet rent densities of 7.7, 11.5 and 15.4 mAcm -2 were
Connection also examined.
>- Raschigrings A power supply (Elsim, 220V), a digital multi-
:h Isolation
meter (DT 3800B), a magnetic stirrer (Electro-
Mag) and a pH meter (Orion, 420A) were used in
the experiments. The solution flow rate was mea-
sured using a rotameter (Rota 870909-3601).
Determination of the surfactant concentrations
before and after oxidation was carried out by an
ionmeter (Orion 710 A Benchtop pH/ISE) and an
Cooling ion-selective electrode (Cole Parmer).
'~ , inlet
W'eter

Cathode ~ 3. Results and discussion

Fig. 1. Bipolar packed bed electrochemical reactor used
in direct electrochemical oxidation of LAS.
energy consumption and mass transfer coefficient
have been investigated.
The removal efficiency and energy consump-
tion of the electrochemical oxidation were calcu-
lated using the following equations:
where Cois the initial concentration ofLAS solu-
tion (mgL-a), C is the concentration of LAS solu-
tion (mgL 1) at time t.
Energy consumption (kWh g-a)
m VxI
(Co-c)x
3.1. Effect o f current density
The efficiency of an electrolytic system depends
largely on the energy consumption per unit amount
of organics removed. Energy consumption is di-
rectly affected by the current density applied to
the system. The effect of applied current density
on the removal efficiency and energy consumption
for this study is illustrated in Fig. 2. An increase
in the applied current density resulted in an in-
crease in the transport of the surfactant to the anode
surface therefore in removal efficiency. Energy
consumption also increased due to the increase in
the current as expected according to Eq. (2). For
the solution with a concentration of 50 mgL -a, the
removal efficiency of 90% was achieved with an
(1) energy consumption of 7.62 kWhg -t at a flow rate
of 0.336 Lh-1 and a current density of 11.5 mAcm 2.
When a current density of 15.4 mAcm 2was applied,
a removal efficiency of 94% was achieved with an
energy consumption value of 11.32 kWhg -a for
the same concentration at the same flow rate.
(2) 3.2. Effect o f initial LAS concentration
The variation of removal efficiency and energy
 A.S. Koparal et al./ Desalination 197 (2006) 262-272 265

100

@ Removal Efficiency, %
Energy Consumption, kWhg-1

>2
95
f i
lO

I
90

, 5

8 10 12 14 16
Current Density, mAcm-2

Fig. 2. Variation of the removal efficiency and energy consumption with applied current density (initial concentration: 50
mgL-l; flow rate: 0.336 Lh-~).

consumption for two initial concentrations of
10 mgL -~ and 50 mgL -~ is represented in Figs. 3a
and 3b. As can be seen from these figures, an in-
crease in the initial concentration has resulted in
a decrease in the removal efficiency due to an in-
crease in the oxidation load at the anode at high
surfactant concentration. However, the electrode
efficiency in terms of grams ofsurfactant removed
per residence time in hours per applied current as
ampere and per square meter of the anode was
been increased approximately 5 times at the same
current density when the concentration of sur-
factant was increased to 50 mgL -I as can be seen
from Fig. 3a. Thus, the absolute surfactant re-
moval for 50 mgL -~ was approximately five-fold
higher compared to 10 mgL i with the same cur-
rent density. At a higher initial concentration, since
the amount of the surfactant removed for the same
removal efficiency was larger, the specific energy
consumption was much smaller compared to that
with a lower concentration as seen from Fig. 3b.
3.3. Effect offlow rate
An increase in flow rate has resulted in a de-
crease in the removal efficiency as it can be seen
from Fig. 4a. A high detention time resulting from
a low flow rate has caused an increase in the re-
moval efficiency. Much lower energy consump-
tion has been obtained with a higher flow rate
because of lower applied potentials as shown in
Fig. 4b. On the other hand, the electrode efficiency
has been increased by 12 times with 10 mgL -1
(Fig. 4a) and 15 times with 50 mgL -1 (not shown)
at the same current density when the flow rate
was increased to 6 Lh -1.
Starting with 50 mgL 1the final concentration
of 2.5 mgL -1 has been achieved at 0.336 Lh -1
whereas the final concentration was 6 mgL -1 at
6 Lh -1 with the energy consumption values o f
10 kWhg -~ and 0.52 kWhg -1 respectively provided
that the other conditions were same. Thus, the
decision about economics of the process should
be made according to the demand and restriction
of the effluent quality.
3.4. Effect of pH
The effect o f p H on the removal efficiency and
energy consumption is shown in Figs. 5a,b. It can
266 A.S. Koparal et aI. / Desalination 197 (2006) 262-272

(a) 100

[] 10mgL"1 ~
[] 50 mgL"1 ~'~ J ~
;g 10mgL"1 i
o

O - 2
o

8O 0

6 8 10 12 14 16
Current Density, mAcm-2

(b) 60

-- (~ 10 m g L -1
f ,
--I~-- 50 ragE-1

./

"7
40
",..~

/
E

20
;sd

i i I i

8 10 12 14 16
Current Density, mAcm -2
Fig. 3. Variation of the removal efficiency, electrode efficiency and energy consumption with applied current density fo~
two different initial concentrations of LAS (supporting electrolyte concentration: 14.2 gL-~ NazSO4; flow rate: 0.336 Lh-1).
 A.S. Koparal et al. / Desalination 197 (2006) 262-272 267

(a) 100 - 5
- - ~ : ~ - - 10mgL"1
- - - - - l - - - 50 mgL"1
~.~\ - )-- lOmgL-1

95
E

e-

90

85

~Zf

80 i i o
6 10 12 14 16
Current Density, mAcm-2

(b) 60

~)-- 0.336 Lh"t

/
~--~--- 6Lh-I
J
J
J

b~ :J
~ 4o

t-
O
rJ

o ~ , ~ i i

6 8 l0 12 14 16
Current Density, rnAcm-2

Fig. 4. Variation of the removal efficiency, electrode efficiency and energy consumption with applied current density for
different flow rates (14.2 gL / Na2SO4' 10 mgL -1 LAS).
268 A.S. Koparal et al. / Desalination 197 (2006) 262-272

(a) 100

- - ' 4 i ~ - ~ pH 3 / <
~ pH 5.5 /
--" pH9 / ~
/
/ / z
j/
~ 9O /
/ /

80

70 F i
8 10 12 14 16
Current Density, mAcro -2

(b) 80
J
+ pH3 ~.-/
pH 5.5 /
~-- pH9
/
7
6o / f

0
r..)
~ 40 -

~ J

20 4 - - ,
6 8 10 12 14 16
Current Density, mAcm -2
Fig. 5. Effect of pH on the removal efficiency and energy consumption (initial concentration: 10 mgL1; flow rate:
0.336 Lh-l).
 A.S. Koparal et al. / Desalination 197 (2006) 262-272
be seen from Fig. 5a that the removal efficiency
of the surfactant has decreased at both higher and
lower pH values. This is probably due to the com-
petitive reactions taking place at the electrodes.
For example an increase in OH- concentration will
lead the oxygen evaluation as a competitive reac-
tion at the anode. A higher removal efficiency
(Fig. 5a) and lower energy consumption values
(Fig. 5b) have been observed at a pH value of 5.5
which was the original pH of LAS solution of
10 mgL -~. Thus, adding any chemical is not neces-
sary to promote the process efficiency by adjust-
ing pH.
3.5. Effect o f supporting electrolyte
The model solution has a conductivity of about
60 gs/cm, which is insufficient for effective
electrochemical oxidation of organics. This is be-
cause low concentrations of species to be oxidized
in wastewater lead to low mass transfer rate of
the species onto the electrode surface and high
energy consumption resulting from low conduc-
tivity. This deficiency was corrected by addition
of an appropriate amount ofNa2SO 4 as a support-
ing electrolyte leading to a higher removal effi-
ciency and lower energy consumption due to
lower applied voltage as shown in Figs. 6a,b. This
result has also been confirmed by the mass transfer
coefficient value. However, a significant increase
in the removal efficiency was not observed when
the supporting electrolyte concentration increased
from 14.2 gL -~ to 21.3 gL -~. On the other hand,
21.3 gL -1NazSO4 can also be an appropriate alter-
native if the decrease in energy consumption ob-
served in the use of 21.3 gL -1Na2SO ~ is compar-
able with the cost of NazSO4. Therefore, 14.2 gL 1
or 21.3 gL -~ of supporting electrolyte concentra-
tion can be accepted to be adequate for the electro-
chemical removal of LAS.
3.6. The effects o f all parameters on mass trans-
fer coefficient
The mass transfer coefficient calculated for the
269
single pass plug flow reactor has increased with
an increase in the flow rate, as expected, and it is
well described by the equation:
C =exp(-Qk) (3)
Co
where k is the mass transfer coefficient (ms -~) and
A is the electrode surface (m2).
For example, the calculated mass transfer
coefficient was 4.04x10 -5 ms -1 at a flow rate of
0.336 Lh -~ whereas it was 40.0x 10-5 ms -~ at a flow
rate of 6 Lh -~ in the same conditions. At the same
flow rate, an increase in concentration has caused
a slight decrease in the mass transfer coefficient.
This result has been confirmed by the removal
efficiency decrease with higher concentration. For
example, mass transfer coefficient o f 4.04×
10-5 ms -1 has been obtained with the concentration
of 10 mgL -I whereas it has been 3.16×10 -s ms -~
with the concentration of 50 mgL 1. The support-
ing electrolyte concentration has a strong effect
on the mass transfer coefficient as expected caus-
ing it to be approximately 3 fold when the concen-
tration of the supporting electrolyte was increased
to 14.2 gL -1 from 9.94 gL -1.
The highest mass transfer coefficient value of
4.0x 10-5 ms -~ obtained at the original pH of LAS
solution of 10 mgL -~. This result has been in agree-
ment with the others. All results for mass transfer
coefficients are shown in Table 1.
4. Conclusions
It can be concluded fi'om these results that LAS
can be efficiently removed from water by applying
electrochemical oxidation. This method has
advantages such as requiring no chemicals and
causing no sludge problem.
The concentration of LAS decreased below the
suggested concentration of 2 mgL -1 set as a limit
in the Turkish regulations, with an energy con-
sumption of l kWhg -1 or about 8 kWhm -3 in the
case of the initial concentration of 10 mgL -1.
270 A.S. Koparal et al. / Desalination 197 (2006) 262-272

100

~ _ S f --4

9o/ i

80
6

;>
O 7O
J
J
i

6ot - 9.94 gL-1 Na2SO4

14.2 gL-1 Na2SO4
----!~ 21.3gL"1Na2SO4
5O
6 8 10 12 14 16
Current Density, mAcro -2

80

7O

, 60

.~ 50 J

r~ 40
J zj ~

f
~ 30

~ J~ j/J • - 9.94 gL-1Na2SO4

/-
20 ( ~ # -- 14.2gL-1Na2SO4
--~+ 21.3 gL-1Na2SO4
10
6 8 10 12 14 16
Current Density, macro -2

Fig. 6. Effect o f supporting electrolyte concentration o n the removal efficiency and energy c o n s u m p t i o n (initial c o n c e n
tration: 10 m g L ~; flow rate: 0.336 Lh-~).
 A.S. Koparal et al. / Desalination 197 (2006) 262-272 271

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