Colloids and Surfaces A: Physicochem. Eng.

Aspects 254 (2005) 165171

Removal of anionic surfactant from wastewater by alumina:

a case study
Asok Adak, Manas Bandyopadhyay, Anjali Pal
Civil Engineering Department, Indian Institute of Technology, Kharagpur 721302, India
Received 6 August 2004; accepted 4 December 2004
Available online 9 January 2005

Abstract
The adsorption characteristics of sodium dodecyl sulfate (SDS) on neutral alumina were studied in detail. Alumina was found to be an
efficient adsorbent for SDS and could be used for the removal of anionic surfactant (AS) from wastewater when it is present in high concentration
(several thousand ppm). In the present work the actual laundry wastewater was treated by both batch and continuous mode. The initial AS
concentration in wastewater was 8068 ppm. The optimum adsorbent dose and equilibrium time found were 120 g/l and 1 h, respectively.
Under optimised conditions the removal efficiency was found to be 94%. The removal of SDS by alumina follows the pseudo-second order
reaction kinetics. In column study the flow rate was maintained at 1.63 m3 /m2 /h. The breakthrough and exhaust time were found to be 48
and 86 min, respectively, using 10 cm column depth. Height of adsorption zone was found to be 5.5 cm and the rate at which the adsorption
zone was moving through the bed was 9.42 cm/h. The percentage of the total column saturated at breakthrough was found 75.5%. The value
of adsorption rate coefficient (K) and adsorption capacity coefficient (N) were obtained as 0.000824 l/(mg h) and 143460 mg/l, respectively.
After exhaustion, aqueous NaOH could efficiently regenerate alumina.
2004 Elsevier B.V. All rights reserved.
Keywords: Alumina; Anionic surfactant; Equilibrium time; Adsorption rate coefficient; Adsorption capacity coefficient

1. Introduction
In 1950 the detergents came in the market. The detergent
consists of both sequester (to keep dissolved minerals for
summing things up) and surfactants (to remove dirt). Surfactants are surface-active substance that lowers the surface tension of a solvent (usually water). They contain both strong hydrophobic and hydrophilic moieties. The hydrophobic group
is generally a hydrocarbon radical of 1020 carbon atoms.
The hydrophilic portion may or may not ionise depending on
the type of surfactant [1]. At low concentration, surfactant
molecules exist in the monomer state in aqueous solution,
but as the concentration increases they reach critical micelle
concentration (CMC) and then they begin to self-associate to
form a new pseudo-phase called micelle [2]. The synthetic

Corresponding author. Tel.: +91 3222 281920; fax: +91 3222 255303.
E-mail address: anjalipal@civil.iitkgp.ernet.in (A. Pal).

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.12.004

surfactants are of three major types: anionic, nonionic, and

cationic. Anionic and cationic surfactants together are called
ionic surfactant. Ionic surfactants constitute approximately
two-third of these surfactants. Cationic surfactants constitute
less than 10% of the ionic surfactants and rest is anionic surfactant. Thus anionic surfactants (AS) are the major class of
surfactants used in detergent formulations. The predominant
class of anionic surfactant is branched alkylbenzene sulfonate
(ABS), linear alkylbenzene sulfonate (LAS) and linear alkyl
sulfate. An example of linear alkyl sulfate is sodium dodecyl
sulfate (SDS), which is a representative of AS. Surfactants are
in widespread use throughout the world. The use of surfactant is gradually increasing day by day. It has been reported
[35] that the world surfactant production was 1.7, 1.8 and
9.3 million tons in the years 1984, 1987 and 1995, respectively. In domestic wastewater produced by the households,
surfactants invariably exist in significant amount due to the
enormous use of detergents for washing purpose. Reported

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influent concentration of LAS in domestic wastewater range

from 3 to 21 mg/l [3]. Surfactants have also been widely used
in textiles, fibers, food, paints, polymers, cosmetics, pharmaceuticals, mining, oil recovery, pulp-paper industries, etc. The
textile industries alone roughly consume 10% of the world
surfactant production, and the wastewater of these industries
(e.g. from cotton desizing and other textile finishing process)
contains high concentration of surfactant [68].
Surfactants are harmful to human beings, fishes and vegetation. They are responsible for causing foams in rivers and
effluent treatment plants and to reduce the quality of water.
Surfactants cause short term as well as long-term changes
in ecosystem. Due to all these reasons, many environmental
and public health regulatory authorities have fixed stringent
limits for anionic detergent as standard 0.5 mg/l for drinking water and relaxable up to 1.0 mg/l for other purposes
[9].
The conventional methods for surfactant removal from
the water environment involve processes such as chemical
and electrochemical oxidation [7,10], membrane technology
[11], chemical precipitation [12], photocatalytic degradation
[13], adsorption [3,1418], various biological methods [19],
etc. In most of the studies the surfactant concentrations were
in the range as found in public wastewater treatment plants.
There is a report, however, where anionic surfactant-rich
wastewater was treated by anaerobic digestion [6]. Actually,
treatment of surfactant wastewater containing >1000 ppm of
surfactant coming from different industries like textile, tannery, oil refinery, etc. is a very difficult task. Surfactant has
also been found to occur at high concentration levels in pond
water of villages because washing of clothes is directly being
done in the pond water [20]. Thus, the present research work
aims towards the study of the removal of AS from wastewater (where it is present in a very high concentration) by
adsorption on to neutral alumina. The alumina was found to
be very efficient adsorbent for the removal of AS. Adsorption of AS on positively charged alumina surface occurs due
to electrical attraction between positive surface and anionic
head groups of AS and also due to the interaction between
the long hydrocarbon chains of surfactant molecules to form
bilayer structure [21].

2. Materials and methods

2.1. Reagents
Acridine orange (ACO), SDS, glacial acetic acid, toluene
were from BDH (AR grade) and were used as received. All
other chemicals used in this study were of high purity and
used without further purification.
2.2. Adsorbents
Alumina was supplied by SRL, India and was used as
such without further grinding and sieving. The granulation of

neutral alumina is 70290 mesh ASTM, molecular weight is

101.96 and zero point charge (Zpc ) is 9.15. The surface area of
the alumina was found to be 900 cm2 /g. The X-ray defraction
analysis showed that the alumina had cubic structure.
2.3. Instrumentation
A high precision electrical balance (Sartorious GMBH)
was used for weighing. Digital pH meter (DHP-500, SICO,
India) was used for pH measurements. A spectrophotometer (Thermo Spectronic UV1, UK) was used for absorbance
measurement.
2.4. Analytical methods
A rapid and reliable solvent extraction spectrophotometric method has been developed for the determination
of AS. Acridine orange (ACO) chemically known as 3,6bis(dimethylamino) acridine (max = 467 nm) has the potential for being used as an ion-pairing agent with AS. The ionpair formed between AS and ACO is extractable in toluene.
Sample solution (10 ml) containing SDS in the range of
0.16.0 ppm was transferred into a 25 ml separating funnel.
ACO (5 103 M) and glacial acetic acid 100 l each was
added. Then 5 ml of toluene was added to it and shaken for
1 min. The aqueous layer was then discarded and the toluene
layer was used for absorbance measurement at 467 nm. The
method showed good results for other AS such as sodium decyl sulfate and sodium dodecyl benzene sulfonate when they
were present either alone or in a mixture, and the results were
comparable to the results obtained for SDS. The method was
applicable to AS bearing real wastewater and results obtained
were compared with those obtained using standard method
(i.e., methylene blue active substance method) [22] and the
spectrofluorimetric method [20].
2.5. Experimental studies
Actual AS bearing wastewater was collected from a smallscale laundry industry located at Dhobi Ghat near Kharagpur
Railway Station, India. The wastewater was analysed for its
composition, and the characteristics are shown in Table 1.
Since the pH of the wastewater was 9.1, it was brought down
to 5.5 by adding 2 ml of concentrated HCl in 5 l of wastewater.
Otherwise it was very difficult to remove AS from wastewater
by alumina since its Zpc is 9.15.
The batch experiments were carried out at 25 2 C in a
mechanical shaker at an agitation speed of 150 rpm. ExperTable 1
Characteristics of wastewater collected from a small-scale laundry industry
Parameters

Value

pH
Turbidity (NTU)
Total dissolved solids (mg/l)
Anionic surfactant (mg/l)

9.1
45
2154
8068

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167

Fig. 2. Effect of adsorbent dose on AS removal by alumina.

Fig. 1. Schematic diagram of fixed bed column experimental set up.

iments were carried out to find the optimum adsorbent dose

for this particular wastewater containing 8068 mg/l of AS.
Wastewater (10 ml) with varying adsorbent doses (0180 g/l)
was shaken for 2 h. The optimum adsorbent dose was found
to be 120 g/l. The sorption equilibrium time was studied using optimum adsorbent dose of 120 g/l and the shaking time
was varied from 0 to 6 h. In all cases, after shaking, the samples were allowed to settle for 5 min and then filtered through
ordinary filter paper and used for analysis.
Fixed bed column study was conducted using a column of
20 mm diameter and 550 mm length. The column was packed
with alumina and the depth was 100 mm (Fig. 1). The column
was charged with AS bearing wastewater in the up flow mode
with a volumetric flow rate of 8.5 ml/min (1.63 m3 /m2 /h).
The samples were collected at certain time intervals and were
analysed for remaining AS concentration.
After exhaustion of the alumina by AS it is necessary to
regenerate it for further use. Experiments for the regeneration of exhausted alumina were carried out by using aqueous
NaOH.

3. Results and discussions

3.1. Batch adsorption experiments
3.1.1. Effect of adsorbent dose
In the batch study it is very necessary to find optimum
adsorbent dose of the adsorbent and also the contact time
for maximum possible removal of the adsorbate. A series of
10 ml samples of AS bearing wastewater were shaken for
2 h with adsorbents at varying doses (0180 g/l). The initial
concentration for AS was 8068 ppm. It was found that the
removal of AS increases with the increase of alumina dose
and the removal remained almost constant (Fig. 2) beyond
the adsorbent dose of 120 g/l. The removal of AS at a dose of
120 g/l of alumina was found to be 94%. Hence 120 g/l was
selected as the optimum adsorbent dose. In this context it
is worth mentioning that when experiments were conducted
with SDS-spiked distilled water the removal efficiency was

found to be 55% for initial concentration of 8000 ppm with

adsorbent dose of 120 g/l. The removal efficiency for wastewater was more in comparison to that of SDS-spiked distilled
water, and that is due to total dissolved solids (TDS) present
at high concentration levels in wastewater. Thus TDS had a
positive effect on the removal of AS. The presence of TDS
decreases the lateral repulsive force between the head groups
of the ionic surfactant causing more surfactant adsorption
[23].
3.1.2. Sorption kinetics
In batch experiments, kinetic study is very important to
find out the contact time of the adsorbent with adsorbate and
for evaluating reaction coefficients. The kinetic study was
conducted on the AS bearing wastewater with optimum adsorbent dose of 120 g/l and the shaking time was varied from
0 to 6 h. Fig. 3 shows the removal of AS with respect to time.
The rate of adsorption was very rapid initially. It was noticed
that 87% removal of AS took place within half an hour and
then gradually increased upto 94% and 96% in 1 and 6 h,
respectively. Because of such a quick sorption rate it can be
inferred that in this case the process is predominantly film
diffusion controlled, and this is triggered by the high concentration difference between the bulk solution and solid phase
[24].
In order to investigate the mechanism of solute adsorption
onto the adsorbent, four kinetic models viz., first order reaction model [25] based on the solution concentration, pseudofirst order equation of Lagergren et al. [26] based on the solid
capacity, second order reaction model based on the solution
concentration and pseudo-second order reaction model of Ho
and Mckay based on the solid phase sorption [27] were analysed and a comparison of the best fit sorption mechanism
were made.

Fig. 3. Removal of AS by alumina with respect to time.

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A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171

3.1.2.1. First order reaction model. First order rate equation

based on the solution concentration can be represented as

dCt
= K1 Ct
dt

(1)

Rearranging Eq. (1)

dCt
= K1 dt
Ct

(2)

Integration Eq. (2) for the boundary conditions t = 0 to t = t

and Ct = C0 to Ct = Ct gives the form
ln Ct = ln C0 K1 t

(3)

So Eq. (2) dictates that a plot of ln Ct versus t indicates the

linear plot of first order equation. Fig. 4(a) shows the plot of
ln Ct versus t. A best-fit line was drawn and correlation coefficient (R2 ) was found to be very poor 0.5465, which indicated
that the adsorption did not follow first order reaction.
3.1.2.2. Pseudo-rst order model. The pseudo-first order kinetic model based on the solid capacity for sorption analysis
is of the form
dqt
= KS1 (q1 qt )
dt

(4)

Integrating Eq. (4) for the boundary conditions t = 0 to t = t

and qt = 0 to qt = qt gives the linearized form as shown by Eq.
(5):
ln(q1 qt ) = ln(q1 ) KS1 t

coefficient, R2 = 0.8016) indicates that the pseudo-first order

reaction model is better followed than the first order reaction
model.

(5)

Therefore from Eq. (5) it can be inferred that a linear plot of

ln(q1 qt ) versus t indicates the reaction to be of pseudo-first
order. A plot of ln(q1 qt ) versus t for the current media under
consideration is shown in Fig. 4(b). The linear fit (correlation

3.1.2.3. Second order model. Second order rate equation is

widely used for metal ion sorption, which can be represented
as

dCt
= K2 Ct2
dt

(6)

Rearranging Eq. (6) and integrating for the boundary conditions t = 0 to t = t and Ct = C0 to Ct = Ct we get
1
1

= K2 t
Ct
C0

(7)

So Eq. (7) dictates that a linear plot of 1/Ct versus t indicates

that the reaction rate is of second order. A plot of 1/Ct versus t for the current media under consideration is shown in
Fig. 4(c). The linear fit (correlation coefficient, R2 = 0.8713)
indicates that the second order reaction model is better followed than pseudo-first order reaction model.
3.1.2.4. Pseudo-second order model. A pseudo-second order rate expression based on the sorption equilibrium capacity
may be represented as
dqt
= k[qe qt ]2
dt

(8)

Rearranging Eq. (8) and integrating the obtained equation for

the boundary conditions t = 0 to t = t and qt = 0 to qt = qt we
get
1
1
=
+ kt
(qe qt )
qe

(9)

Fig. 4. (a) Linearized first order reaction kinetics, (b) linearized pseudo-first order reaction kinetics, (c) linearized second order reaction kinetics, and (d)
linearized pseudo-second order reaction kinetics.

A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171

169

which is the integrated rate law for a pseudo-second order

reaction.
Rearranging Eq. (9)
t
1
1
= + t
qt
h qe

(10)

where h = kqe2 .
Eq. (10) indicates that a linear plot of t/qt versus t confirms that the reaction rate follows pseudo-second order kinetics. A plot of t/qt versus t for the current media under
consideration is shown in Fig. 4(d). The linear fit (correlation coefficient, R2 = 1.0) indicates that the reaction follows
the pseudo-second order reaction model. Hence the reaction
rate constant was calculated based on the pseudo-second order model and it was 0.012353 g/(mg min). Fig. 5 shows the
plot of qt versus t for experimental data and theoretical data
based on the pseudo-second order model. The deviations between the experimental and theoretical values were found to
be very negligible.
3.2. Adsorption mechanism
The adsorption of AS on positively charged alumina surface is largely dependent on the concentration of AS. At low
concentration AS is adsorbed as monomers and the adsorption is due to the electrostatic attraction between the negative head groups of AS and positively charged alumina surface (Fig. 6). At higher concentration, AS begins to form
bilayer on the alumina surface. The adsorption is due to
the electrostatic attraction between the ions and the charged
solid surface and interaction between the hydrocarbon chains.
Micelle-like aggregates are formed on the solid surface. The
monolayered structure is called hemimicelle and the bilayered structure is called admicelle. At concentration above
CMC, the adsorption is almost constant. In the present study,
the AS concentration was above CMC of AS and the adsorption of AS on alumina was due to the electrostatic attraction
between the ions and the charged solid surface and interaction between the hydrocarbon chains. Thus, admicelles were
expected to form in the present study.

Fig. 5. Plot of qt vs. t for experimental data and theoretical data based on
the pseudo-second order model.

Fig. 6. Formation of bilayer of AS on alumina surface.

3.3. Fixed bed column for AS removal from wastewater

Fixed bed column study was conducted using a column of
20 mm diameter and 550 mm length. The column was packed
with alumina and the depth was 100 mm. The column was
charged with AS bearing wastewater in the up flow mode
with a volumetric flow rate of 8.5 ml/min (1.63 m3 /m2 /h).
The breakthrough curve for AS using alumina was shown in
Fig. 7. The breakthrough time (corresponding to C/C0 = 0.1)
and exhaust (corresponding to C/C0 = 0.9) time were found to
be 48 and 86 min, respectively. The corresponding volumes
of wastewater treated were 0.408 and 0.731 l, respectively.
Height of adsorption zone was found to be 5.5 cm and the
rate at which the adsorption zone was moving through the bed
was 9.42 cm/h. The percentage of the total column saturated
at breakthrough was found to be 75.5%.
The fixed bed column was designed by logit method. The
logit equation can be written as



C/C0
KNX
ln
=
(11)
+ KC0 t
1 C/C0
V
where C is the solute concentration at any time t, C0 the initial solute concentration (8068 ppm), V the approach velocity
(163 cm/h), X the bed depth (10 cm), K the adsorption rate
constant (l/(mg h)) and, N the adsorption capacity coefficient
(mg/l).
Rearranging Eq. (11)



C
KNX
ln
(12)
=
+ KC0 t
C0 C
V

Fig. 7. Breakthrough curve for AS using alumina.

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A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171

removal of AS by alumina followed pseudo-second order reaction kinetics. In the column study the breakthrough time
was found to be very less due to the high AS concentration
in the wastewater. Column in series could be used for better
performance. In both batch and column study the turbidity
was removed up to 90%. After exhaustion of alumina it could
be used for the removal of different organic pollutants like
dye, phenol, benzene, toluene, aniline, etc. from water environment, or it could efficiently be regenerated by treating
with NaOH solution for its further use for AS removal with
a fresh lot of wastewater.
Fig. 8. Linearized form of logit model.

Plot of ln C/(C0 C) versus t gives a straight line with

slope KC0 and intercept KNX/V from which K and N
could be calculated. Plot of ln C/(C0 C) versus t was
shown in Fig. 8. The value of adsorption rate coefficient (K) and adsorption capacity coefficient (N) were obtained as 0.000824 l (mg h) and 143460 mg/l, respectively.
The values could be used for the design of adsorption
columns.

Acknowledgements
The authors are thankful to Professor Kunio Esumi, Department of Applied Chemistry, Faculty of Science, Tokyo
University of Science, for invaluable discussions.

References
3.4. Regeneration study
After AS removal the alumina becomes useless unless it is
regenerated or is used for some other purposes. The exhausted
alumina can be used for the removal of different organic pollutants like dye, phenol, benzene, toluene, aniline, etc. from
water environment. This removal phenomenon is called adsolubilization [28]. The regenerated alumina can also be used
for removing AS from fresh AS bearing wastewater. The zero
point charge of the alumina used for the experiments was
9.15, which indicated that the removal of AS by alumina
was not possible at pH > 9.15. This was corroborated from
the fact that when experiments were carried out with SDS
spiked distilled water at pH > 9.15 the removal was negligible. Hence, aqueous NaOH could be used for the regeneration of exhausted alumina after AS removal. While regenerating the exhausted alumina, 500 g/l of exhausted alumina
was shaken for 1 h at 150 rpm with 0.25 M NaOH solution.
It was noticed that 90% of AS was desorbed from the surface of alumina. After regeneration the alumina was again
used for the removal of AS and the efficiency was 92% of the
original.

4. Conclusions
Alumina can be used for the removal of AS from wastewater when it is present in high concentration. In the wastewater under consideration the AS concentration was 8068 ppm
and the pH was 9.1. The pH of the wastewater was lowered
by adding acid to get more removal by alumina. In batch
study the optimum adsorbent dose and equilibrium time were
found to be 120 g/l and 1 h, respectively. Under optimised
conditions 94% AS could be removed from wastewater. The

[1] L.L. Schramm, Surfactants: Fundamentals and Applications in the

Petroleum Industry, Cambridge University Press, 2000, p. 3.
[2] K. Shinoda, E. Hutchinson, J. Phys. Chem. 66 (1962) 577.
[3] S. Gupta, A. Pal, P.K. Gosh, M. Bandyopadhyay, J. Environ. Sci.
Health, Part A 38 (2003) 381.
[4] D. Myers, Surfactant Science and Technology, VCH Publishers,
1988, p. 1.
[5] A. Dhouib, N. Hamad, I. Hassayri, S. Sayadi, Process Biochem. 38
(2003) 1245.
[6] H. Feithenhauer, U. Meyer, Bioresour. Technol. 82 (2002) 115.
[7] S.H. Lin, C.M. Lin, H.G. Leu, Water Res. 33 (1999) 1735.
[8] M.K. Patel, A. Theib, E. Worrell, Resour. Conserv. Recy. 25 (1999)
61.
[9] C.S. Rao, Environmental Pollution Control Engineering, Wiley Eastern Ltd., 1995, p. 301.
[10] G. Lissens, J. Pieters, M. Verhaege, L. Pinoy, W. Verstraete, Electrochim. Acta 48 (2003) 1655.
[11] I. Kowalska, M. Kabsch-Korbutowicz, K. Majewska-Nowak, T. Winnicki, Desalination 162 (2004) 33.
[12] B. Shiau, J.H. Harwell, J.F. Scamehorn, J. Colloid Interf. Sci. 167
(1994) 332.
[13] T. Zhang, T. Oyama, S. Horikoshi, J. Zhao, N. Serpone, H. Hikada,
Appl. Catal. B: Environ. 42 (2003) 13.
[14] S.G. Dick, D.W. Fuerstenau, T.W. Healy, J. Colloid Interf. Sci. 37
(1971) 595.
[15] P.D. Purakayastha, A. Pal, M. Bandyopadhyay, J. Environ. Sci.
Health, Part A 37 (2002) 925.
[16] P.D. Purakayastha, A. Pal, M. Bandyopadhyay, Int. J. Environ. Poll.
9 (2003) 421.
[17] A.C. Savitsky, B.H. Wiers, R.H. Wendt, Environ. Sci. Technol. 15
(1981) 1191.
[18] B.P. Sing, Ind. J. Environ. Protect. 14 (1994) 748.
[19] H. Terabkova, B. Kralova, J. Nahlik, Int. Biodeter. Biodegr. 44 (1999)
233.
[20] A. Pal, M. Bandyopadhyay, Int. J. Chem. Technol. 7 (2000)
105.
[21] P. Somasundaran, D.W. Fuerstenau, J. Phys. Chem. 70 (1966) 90.
[22] APHA-AWWA-WPCF, Standard Methods for the Examination
of Water and Wastewater, APHA-AWWA-WPCF, 1989, pp. 5
55.

A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171
[23] L. Luciani, R. Denoyel, J. Rouquerol, Colloids Surf. A: Physicochem. Eng. Aspects 178 (2001) 297.
[24] M.S. Onyango, H. Matsuda, T. Ogada, J. Chem. Eng. Jpn. 36 (2003)
477.
[25] L.D. Benefield, C.W. Randall, Biological Process Designs for
Wastewater Treatment, Prentice-Hall Inc., 1980, p. 1.

171

[26] S. Lagergren, B.K. Svenska Ventenskapsakad, Handl. 24 (1898), as

cited by Wasay et al., Water Res. 30 (1996) 1143.
[27] Y.S. Ho, G. Mckay, Process Biochem. 34 (1999) 451.
[28] K. Esumi, S. Yamamoto, Colloids Surf. A: Physicochem. Eng. Aspects 137 (1998) 385.