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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
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A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171
Value
pH
Turbidity (NTU)
Total dissolved solids (mg/l)
Anionic surfactant (mg/l)
9.1
45
2154
8068
A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171
167
168
A. Adak et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 165171
dCt
= K1 Ct
dt
(1)
dCt
= K1 dt
Ct
(2)
(3)
(4)
(5)
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)
(8)
(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
(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.
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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.
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
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.
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