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Enhanced electrochemical
oxidation of anionic
surfactants
a b b
Homg G. Leu , Sheng H. Lin & Tze M. Lin
a
Environmental Protection Bureau, Taoyuan
County, Taoyuan, 330, Taiwan, ROC
b
Department of Chemical Engineering, Yuan
Ze University, Neili, Taoyuan, 320, Taiwan,
ROC
Published online: 15 Dec 2008.
To cite this article: Homg G. Leu , Sheng H. Lin & Tze M. Lin (1998): Enhanced
electrochemical oxidation of anionic surfactants, Journal of Environmental
Science and Health, Part A: Toxic/Hazardous Substances and Environmental
Engineering, 33:4, 681-699
This article may be used for research, teaching, and private study
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J. ENVIRON. SCI. HEALTH, A33(4), 681-699 (1998)
ABSTRACT
peroxide hydrogen was investigated. The two anionic surfactants studied here were
alkylbenzene sulfonate (ABS) and linear alkylbenzene sulfonate (LAS), both of them
being widely used in the household and industrial detergents. Experiments were cond-
oxidation, power input and amount of hydrogen peroxide (H2O2) on the surfactant remo-
val and other water quality parameters. Optimum operating conditions were experimen-
tally determined. The enhanced version of electrochemical oxidation (i.e. with addition of
hydrogen peroxide) was found to be significantly more efficient than that without.
681
INTRODUCTION
receiving water body in many developing countries around the world. In the domestic
exist in significant amount due to detergents used for all kinds of washings (Ainsworth,
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1994). In fact, surfactants have also been widely used in textiles, fibers, food, paints,
polymers, plant protection, cosmetics, Pharmaceuticals, mining, oil recovery and pulp
As noted by Swisher (1987), a large number of surfactants, including the anionic types
employed in the present study, are not easily biodegradable. Due primarily to econo-mic
reasons, it is not possible to use easily biodegradable surfactants in all household and
developed which allow safe uses of refractory types of surfactant (Swisher, 1987). In the
past decades, ozonation and other advanced chemical oxidation has been suggested and
1978; Nakis, 1980; Medley and Stover, 1983; Nakis et al., 1985, 1987; Pelizzetti et al.,
1989; Brambilla et al., 1993; Adams et al., 1994, 1996). Those investi-gators had found
atment methods which are as efficient and yet less expensive to implement would be
highly desirable. A method with a potential of meeting these requirements and deserving
attention is the electrochemical method. This method employs electric energy to oxidize
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 683
pollutants in the aqueous solution. During the electrochemical oxidation process, bypo-
chorite is generated which, being a strong oxidant, accounts mainly for oxidation of
pollutant by the process. Hence it would be of much practical and academic interest to
electrochemical oxidation process has also been employed successfully to treat various
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Belectsen, 1985; Camninellis and Pulgarin, 1993; Leffrang et al., 1995; Lin and Peng,
1995, 1996; Lin and Wu, 1996; Polcaro and Palmas, 1997). The purpose of this study is
treating the wastewater containing anionic surfactants. Experimental tests were carried
out to examine the effects of operating variables on the oxidation efficiencies of the
electrolytic cell was a 1.5 liter pyrex beaker equipped with a magnetic stirrer. Two pairs
of anodic and cathodic electrodes (cast iron plates) situated approximately 1.5 cm apart to
each other and dipped in the surfactant wastewater. The total effective surface area of
electrodes was 22.6 cm2. The current input was controlled by an ammeter and the total
power consumption was integrated and registered by a power integrator. In each run,
approximately 1 liter of sample surfactant wastewater was placed in the electrolytic cell.
In the enhanced oxidation test runs, a desired amount of hydrogen peroxide (H2O2) was
added to the electrolytic cell before the electrical current was turned on. Addition of H2O2
was found to be highly beneficial for the electrochemical process in improving the waste-
684 LEU, LIN, AND LIN
1. D. C. Power Supply
ECS b o < ¿I».
2. Digital Ammeter
?®ñ
±t 3. Power Integrator
4. Parallel Cast Iron Anodes
5. Parallel Cast Iron Cathodes
6. Magnetic Bar Stirrer
7. Sampling Port
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8. Electrolytic Cell
9. Digital Magnetic Stirring Controller
FIGURE 1
Experimental Setup.
water quality. During the electrochemical treatment (with or without) of surfactant waste-
water, a small amount of iron was continuously dissolved into the wastewater from the
cast iron electrodes. The dissolved iron when combined with OH" would form many
small floes during the electrochemical process. The floes were difficult to settle out of
waste-water because of their small sizes. This phenomenon was observed frequently in
the present study. Presence of small floes in wastewater would interfere with COD, NTU,
color absorbance and metal ion measurements. To overcome the floe settling problem,
centrifugation of all samples for 5 min would suffice. On the other hand, chemical
coagulation of the wastewater after the electrochemical treatment using a low dosage of
equally effective. Test runs using both methods for all samples after electrochemical
oxidation yielded practically the same results. Hence centrifugation was adopted for
convenience for small samples (i.e. less than 10 ml). In case of large samples, like the
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 685
wastewater sample which needed further ensuing treatment, chemical coagulation was
using a GBC 932 atomic absorption spectrophometer (GBC Scientific Equipment, Ltd.,
Victoria, Australia).
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Two surfactants considered here were of anionic type. They were alkylbenzene
sulfonate (GR grade ABS), obtained from Ferak Laborat GmbH, Germany, and linear
alkylbenzene sulfonate (GR grade LAS), obtained from E. Merck GmbH, Germany. Both
ABS and LAS are sulfonated alkyl sodium salt, but the former has many side chains on
the alkyl group while the latter has a linear alkyl group only. This may account for the
greater biodegradability of LAS than ABS. Regardless of its lower biodegradability, ABS
is still widely used in various household and industrial detergents due to its lower cost.
However, LAS has been gaining wider acceptable lately. In the present studies, the ABS
and LAS concentrations were limited to a maximum around 10 mg/1 due to the fact that
beyond that concentration level, foaming in the aqueous solution would be a severe
problem. Furthermore, past experiences of the present authors in monitoring the water
quality of seriously polluted streams revealed no more than 10 mg/1 of any kind of surf-
complex process (Pletcher and Walsh, 1990). It is generally believed that there are two
tively, at the anode and cathode (Pletcher and Walsh, 1990). With sufficient power
supply, the surfactant molecules are decomposed into small molecule or end products at
the anode. Electro-flotation occurs at the cathode due to evolution of chlorine and/or
hydrogen. Generation of the gases can be easily detected by the gas bubbles observed in
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The sample surfactant solution for the present electrochemical oxidation was pre-
pared by mixing an appropriate amount of anionic surfactant with deionized water. The
conductivity of the sample surfactant solution was observed to be lower than 300 jimho/
To remedy this deficiency, addition of appropriate amount of table salt was found to be
highly efficient for this purpose. Figure 2 demonstrates the increase in conductivity of the
linear with a slope of 1.4, implying that for an increase of 1 mg/1 in salt concentration,
Krstajic and Nakic (1987), the added chloride ion in the aqueous solution will be first
2 Or— >Cl 2 + 2e
The hypochloric acid (HCIO) is a strong oxidant. This may account for the strong effect
of salt concentration on the ABS and LAS removal as displayed in Figures 3(a) and 3(b),
respectively. Note that 0.01 M of NaCl is equal to 584.5 mg/1 which is in turn equivalent
to 818 lunho/cm according to Figure 2. Figure 3(a) indicates that for a salt concentration
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 687
5000
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FIGURE 2
exceeding 0.05M (equivalent to about 4,100 |imho/cm conductivity), its effect on the
ABS removal becomes relatively small, achieving a 92% ABS removal after 30 min of
electrochemical oxidation which is excellent. The effect of salt concentration on the LAS
removal is shown in Figure 3(b). This figure shows a different removal characteristics of
LAS from that of ABS. After 30 min of electrochemical oxidation, the LAS removal was
increased by 25.5% from 43% to 68.5% as the salt concentration was increased from
0.0 IM to 0.03M. However, as the salt concentration was increased by ten times from
0.03M to 0.3M, the LAS removal was only improved by 22.5%, being elevated from
68.5% to 91%. The smaller increase of LAS removal as a function of the salt concentra-
tion indicates that a NaCl concentration greater than 0.03M will be necessary for
>
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O
u
Oí
oo
CD
0.1 MNaCI
O 0.07 MNaCI
• 0.05 MNaCI
(a) A 0.03 MNaCI
A 0.01 MNaCI
I
12 IS 24 30
Time, min
ü 0.30 MNaCI
• 0.15 MNaCI
0.09 MNaCI
0.05 MNaCI
12 18 24 30
Time, min
FIGURE 3
Figures 4(a) and 4(b) demonstrate the changes in surfactant concentration, turbidity
(NTU) and power consumption during the electrochemical oxidation process for ABS
and LAS, respectively. The power supply seems to increase nearly linearly with treatment
time due to constant power input. It is of interest to note in both figures that a fast
was caused by the increasingly large number of floes generated during the
electrochemical oxidation period. Those small floes remained suspended due to mixing
The pH effects on the surfactant removal, power consumption and the final pH of
aqueous solution are shown in Figures 5(a) and 5(b) for ABS and LAS, respectively, after
15 min of electrochemical oxidation. Figure 5(a) reveals that there is relatively little
initial pH effect on the ABS removal. The LAS removal is seen in Figure 5(b) to increase
steadily with initial pH below pH 5 and after that the initial pH effect becomes rather
small. The initial pH effect on the final pH of the aqueous solution is relatively small,
being varied between 8 and 11. The two figures however show a rather strong initial pH
effect on the power consumption. The decrease in power consumption was caused by a
decrease of voltage in the power supply with increasing initial pH as observed in the test
runs. From the above observations, it could be concluded that an initial pH about 7 or
generation of a strong oxidant (hypochloric acid) in the aqueous solution. During the
into the aqueous solution from the iron plate electrodes (Pletcher and Walsh, 1990). The
690 LEU, LIN, AND UN
10
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FIGUKE4
The Surfactant Concentration, Power Consumption and NTU as a Function of Time with
0.07M NaCl for ABS and 0.09M for LAS Oxidation.
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 691
100
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FIGURE 5
Effect of pH on the Surfactant Removal, Final Solution pH and Power Consumption with
2.5 A Current and after 15 min of Oxidation.
692 LEU, LIN, AND LIN
Fe ion can be beneficially utilized if hydrogen peroxide (H2O2) is externally supplied. The
rationale is mat simultaneous presence of Fe ion and H2O2 in the aqueous solution will
produce Fenton-like reaction which is itself a strong oxidation process for pollution
abatement (Lin and Peng, 1995). Hence addition of a small amount of H2O2 will enhance
the electrochemical oxidation process. Figures 6(a) and 6(b) demonstrate the effect of
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H2O2 on the efficiencies of ABS and LAS removal, respectively, by the electrochemical
oxidation. The two figures clearly shows the advantage of 100 mg/1 HiO2 addition. With
decrease much more rapidly than that without H2O2 addition. Furthermore, addition of
100 mg/1 H2O2 delays the time for rapid NTU increase from the starting time to
approximately 8 min, at that time the surfactant concentration was already rather low.
dation, the amount of H2O2 was varied between 50 and 200 mg/1 in Figures 7(a) and 7(b)
for ABS and LAS treatments, respectively. Figure 7(a) shows that a large improvement in
the ABS removal was realized as the H2O2 concentration was elevated from 50 mg/1 to
100 mg/1. But beyond that the improvement with increasing H2O2 dwindled considerably.
Figure 7(b) demonstrates the effect of H A on the LAS removal. It is clear in this figure
that the optimum amount of H2O2 occurs at 150 mg/1 for LAS. This is higher the 100 mg/1
Pertaining to Figures 7(a) and 7(b), the changes in the surfactant and residual H2O2
concentrations and NTU are displayed in Figure 8(a) and 8(b) for ABS and LAS, respec-
tively. It is noted in Figure 8(a) that after 8 min of electrochemical oxidation, the ABS
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 693
10 30
I
^ \
(a)
v
\
\ \
M~^_ - — • ' *
•
1 NTU-> - 20
" \ /
I 6 1
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\\ /
- \^ /
- 10
/ A • Electrochemical _
) /
f A 0 Electrochemical/H202
2 -
/ ^ t 4 - ABS Cone.
i 1 , 1 , 1 ,
o 12 18 24 30
Time, min
100
ABS Removal
0»)
2
¿
A • Electrochemical
A O Electrochemical/HjOj
6 12 18 24 30
Time, min
FIGURE 6
Surfactant Removal for Electrochemical Oxidation versus that of Enhanced Version with
150 mg/1 H A and 2.5 A Current.
694 LEU, UN, AND LIN
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>
o
i
00
ffl
<
6 8 10 12 14 16
Time, min
FIGURE 7
30 -i 100
•s,
1
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Î
20
o -Jo
6 8 10 12 14 16
Time, min
30 - , 160
l&-
120.
20
80
¿
o
O "3
CO
40Î Î
0 2 4 6 8 10 12 14 16
Time, min
FIGURE 8
The Surfactant Concentration, NTU and Residual Amount of H2O2 in the Solution as a
Function of Time with 100 mg/1 H2O2.
696 LEU, UN, AND LIN
and residual H2O2 concentrations level off while NTU starts a rapid rise. Hence this can
accepted as the reaction time for ABS wastewater treatment. The same optimum
oxidation time is reflected in Figure 8(b) for LAS wastewater treatment. It should be
noted that the opti-mum oxidation time does not seem to be affected by addition of H2O2.
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density which is defined as the current input divided by the surface areas of electrodes.
Since the surface area of electrodes for the present study was fixed at 148.5 cm2, the 2.5
A current input employed in the previous figures was equivalent to 16.8 mA/cm2. Figure
9 displays the effect of current density on the surfactant removal, reaction time and power
consumption. The current density shown in this figure is equivalent to the current input
between 1.5 and 3 A. It is observed here that the big changes of these parameters occur
between 10 and 16.8 mA/cm2. After that, the improvements become much smaller and
hence 16.8 mA/cm2 (or 2.5 A current input) can be considered as the optimum power
input.
CONCLUSIONS
The electrochemical oxidation process could only proceed when the conductivity of
wastewater, addition of table salt (or other electrolytes) was found necessary. A salt
(NaCl) concentration greater than 0.05M amply met this requirement and would con-
rapidly and reached a maximum surfactant removal in about 8 min. Addition of a small
ELECTROCHEMICAL OXIDATION OF ANIONIC SURFACTANTS 697
100 30
Surfactant . 4.0
Removal
1
20
O.
E
Power —> 3.0
c
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2.0
<s
12 14 16 18 20 22 24
2
Current Density, mA/cm
FIGURE 9
Effect of Current Density on the Surfactant Removal, Reaction Time and Power
Consumption with 100 mg/1 H2O2.
amount of hydrogen peroxide (larger than 100 mg/1 NaCl) was found to significantly
peroxide did not seem to affect the optimum operating condition stated below. For
operating conditions include: 0.05M NaCl, 16.8 mA/cm2 current density (or 2.5 A
ACKNOWLEDGMENTS
The authors are grateful to Environmental Protection Bureau of Taoyuan County, Taiwan
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