ORI GI NAL ARTI CLE

Highly Efcient Adsorption of Anionic Dyes from Aqueous

Solutions Using Sawdust Modied by Cationic Surfactant
of Cetyltrimethylammonium Bromide
Reza Ansari

Babak Seyghali

Ali Mohammad-khah

M. Ali Zanjanchi
Received: 15 July 2011 / Accepted: 17 February 2012 / Published online: 8 March 2012
AOCS 2012
Abstract In the present study, the adsorption behavior of
Congo Red (CR) dye from aqueous systems onto saw-
dust modied by cetyltrimethylammonium bromide,
CH
3
(CH
2
)
15
N(CH
3
)
3
Br (CTAB) was attempted. Adsorp-
tion experiments were carried out using both batch and
column modes under various operating conditions. The
effects of some important parameters such as solution pH,
adsorbent dosage, initial dye concentration and contact
time were investigated. Treatment of the equilibrium data
obtained in batch experiments was carried out using
Langmuir and Freundlich isotherm equations. Based on the
isotherm analysis, it was found that the adsorption of CR
dye onto SD ts well to the Langmuir model and the
adsorption pattern on CTAB modied sawdust (CTAB/SD)
followed the Freundlich isotherm which is indicative of
heterogeneity of the adsorption sites on the surfactant-
modied sawdust. The maximum adsorption capacity of
SD and CTAB/SD were found to be 5.2 and 9.1 mg g
-1
,
respectively, according to the Langmuir model. However,
much higher differences in sorption capacities were
observed for CTAB/SD and SD in the column system
(66.73 mg g
-1
). In order to nd out the possibility of the
exhausted column for frequent use, a regeneration study
was also carried out. It was found that the dye uploaded
column can be easily regenerated with a high performance
using ethanol as the washing solution.
Keywords Adsorption Congo Red Dye removal
Isotherm Sawdust Surfactant modication
Introduction
Extensive use of synthetic dyes in many industrial appli-
cations has produced large volumes of dye wastewater.
Many of them are considered hazardous and require careful
removal before discharge into the environment. Dye
wastewater is commonly characterized as high in salt and
organic content and low in biodegradation potential [1].
Direct discharge of dye efuents can cause serious prob-
lems to the environment due to contribution of high organic
loading, toxicity and aesthetic pollution related to color.
Contaminated dye can absorb and reect sunlight entering
the water stream causing interference with the growth of
bacteria to levels such that the biological degradation of
impurities is impeded and an ecological imbalance results.
The synthetic dyes usually contain azo-aromatic groups
which are of extreme environmental concern due to their
carcinogenic, mutagenic, and inert properties. The complex
aromatic structures of the dyes result in physicochemical,
thermal and optical stability and resistance to conventional
wastewater treatment [2]. Adsorption processes are being
employed widely for large-scale biochemical, chemical,
environmental recovery and purication applications [3].
Adsorption application follows a simple design, ease of
operation and guarantee of relatively high efciency.
Adsorption processes using activated carbons have been
widely proposed and used for the removal of both organic
Electronic supplementary material The online version of this
article (doi:10.1007/s11743-012-1334-3) contains supplementary
material, which is available to authorized users.
R. Ansari (&) B. Seyghali A. Mohammad-khah
M. A. Zanjanchi
Chemistry Department, Faculty of Science,
University of Guilan, POB 41635-1914, Rasht, Iran
e-mail: ransari@guilan.ac.ir
1 3
J Surfact Deterg (2012) 15:557565
DOI 10.1007/s11743-012-1334-3
and inorganic pollutants from aqueous efuents. However,
commercially available activated carbons are expensive
and, in recent years, a great deal of effort has been put into
the proposal and usage of low-cost adsorbents prepared
from naturally occurring materials and wastes for the
removal of dyes from wastewaters. Agricultural wastes are
the chief raw materials being studied for this purpose, for
they are renewable, usually available in large amounts and
potentially less expensive [36].
Anionic dyes are the most problematic because of their
bright color, as well as their water soluble reactive and
acidic properties [7]. Removal of anionic dyes using other
biosorbents has also been reported by some researchers
recently [2, 716]. Surfactant impregnation has been
applied for modication of various adsorbents such as
zeolite [17], biomass [18], bentonite [19], and coconut
coir pith [20] with good results. The variety of surfactants
and the synergism offered by mixed-surfactant systems
also explains the ever-growing interesting fundamental
studies and practical applications [21]. Continuous
adsorption in a xed-bed column is often desired from an
industrial point of view. It is simple to operate and can be
scaled-up from a laboratory process [22]. A continuous
packed bed adsorber does not run under equilibrium
conditions and the effect of ow condition (hydrody-
namics) at any cross-section in the column affects the
ow behavior downstream. The ow behavior and mass
transfer aspects become peculiar beyond a particular
length to diameter ratio of the column [23]. In order to
design and operate xed-bed adsorption process success-
fully, the breakthrough curves under specied operating
conditions must be predictable. The shape of this curve is
inuenced by the individual transport process in the col-
umn and in the adsorbent [24]. Successful design of a
column adsorption process requires prediction of the
concentrationtime prole or breakthrough curve for the
efuent. Many mathematical models have been developed
to describe dye adsorption by different adsorbents. The
design of the adsorption process is based on the accurate
generation of breakthrough curves [25].
In this paper, we have reported the performance of
sawdust modied by CTAB as an efcient sorbent for
adsorption of Congo Red, a typical anionic dye (CR) from
aqueous solutions. The adsorption capacities of SD and
CTAB/SD for CR dye removal were compared in both
batch and column systems. Batch experiments were per-
formed for nding the optimized dye removal conditions
and obtaining adsorption isotherms. Fixed bed column tests
were conducted to ascertain their practical applicability.
The inuence of various operating parameters such as the
effect of pH inuent dye concentration, ow rate and bed
height were studied to optimize the conditions for maxi-
mum dye removal.
Materials and Methods
Materials and Equipments
All chemicals used were of analytical reagent grades and
used without further purication. All experiments were
carried out in aqueous solutions prepared with distilled
water. Sawdust samples (SD) were obtained from a local
carpentry workshop (North of Iran). Congo Red (CR) and
cetyltrimethylammonium bromide (CTAB) or hexadecyl-
trimethyl-ammonium bromide (IUPAC name, MW =
364.45 g/mol) were purchased from the Merck Chemical
Company. A solution of 200 mg L
-1
Congo Red (MW =
696.66 g mol
-1
) was prepared in distilled water. Congo
Red (CR) or 1-naphthalenesulfonic acid, 3,3
0
-(4,4
0
-bipheny-
lenebism(azo)) bis (4-amino-) disodium salt is a benzidine-
based anionic diazo dye (Fig. 1).
All of the working solutions were prepared by diluting
the stock solution with distilled water to the needed con-
centration. The pH adjustments were carried out using
dilute NaOH and HCl solutions. A Metrohm pH meter
(model 827) with a combined double junction glass elec-
trode was used for pH measurements. Surface morphology
analysis of the adsorbents was carried out using the scan-
ning electron microscopy (SEM) technique employing an
XL30 apparatus (Philips Co., Netherlands) operated at an
accelerating potential of 17 kV. A single beam Perkin-
Elmer UVVis spectrophotometer with a 1 cm cell was
used for measuring all the absorption data. Analysis of CR
in the solutions was carried out spectrophotometrically via
the calibration curve obtained using Beers law (A = ebc).
CR dye shows an intense absorption peak in the visible
region at 485 nm. This wavelength corresponds to the
maximum absorption peak of the CR monomer. Dye con-
centrations in the ltrate solutions were estimated by
measuring the absorbance at maximum wavelengths of the
dye and computed from the calibration curves.
Preparation of Sawdust Modied by Cationic
Surfactant
Sawdust samples obtained from a local carpenter working
with Narra wood (Pterocarpus indicus) was rst washed
Fig. 1 Molecular structure of Congo Red (CR) dye
558 J Surfact Deterg (2012) 15:557565
1 3
copiously with distilled water in order to remove any dust or
impurities and nallydriedat a temperature of about 60 Cfor
2 h in an air circulating oven. In order to have uniform mod-
ication and reproducible results, the substrate sawdust was
sieved (3550 mesh) before modication. Sawdust (35 g)
was shaken for 5 h with 500 mL of CTAB solution having a
concentration of 4.0 g L
-1
. The particulates were then l-
tered, washed with copious distilled water, dried at about
50 C (in an oven). The dried particles (CTAB/SD) were
sieved again (3550 mesh size was selected) in order to
increase the repeatability and reproducibility of the results.
Batch Adsorption Studies
Batch mode studies were conducted with xed amounts
(0.21.0 g) of adsorbents which were shaken separately at
150 rpm in an aqueous solution of the CR dye (50 mL) of
varying concentration (50200 mg L
-1
) at room tempera-
ture for denite time periods. At the end of the pre-deter-
mined time intervals, the adsorbent was removed by simple
ltration. The ltrates were analyzed for residual (unad-
sorbed) concentration of CR. All experiments were carried
out for at least three times with respect to each condition,
the average values are presented. The amount of CR
adsorbed by the adsorbent (q
t
) at each time interval t, was
calculated using the following equation (Eq. 1):
q
t

C
0
C
t
V
w
1
And the amount of CR removed (%) was calculated using
Eq. 2:
%Removal
C
0
C
t
C
0
100 2
where q
t
is the amount of CR adsorbed per unit weight of
adsorbent at any time t (mg g
-1
); C
0
and C
t
are the initial
and liquid-phase concentrations of the CR solution at any
time t (mg L
-1
), respectively; V is the volume of the CR
dye test solution (L); and w is the amount of the sorbent
used (g). When t is equal to the equilibrium agitation time
(i.e., C
t
= C
e
, q
t
= q
e
), then the amount of dye adsorbed at
equilibrium, q
e
, (mg g
-1
) is calculated using Eq. 1.
Fixed Bed Column Studies
Continuous ow sorption experiments were conducted in a
glass column (1.0 cm internal diameter and 50 cm height).
1.0 g of the selected adsorbent (CTAB/SD) was packed into
glass columns with the same dimensions separately. Solutions
of CR dye with constant concentration of 50 mg L
-1
and optimal pH values (pH = 6.0) was passed through the
columns at a constant ow rate of 3.0 mL min
-1
. Outlet
solutions were collected for analysis of remaining dye
concentration at the same regular time intervals. For investi-
gation of the effect of initial dye concentration, the experi-
ments were carried out using CRsolution with concentrations
of 20, 50 and 100 mg L
-1
. The experiments of four different
bed depths, 2.5 cm (0.50 g), 5 cm (1.0 g), 7.0 cm (1.4 g),
10.5 cm (2.0 g), were operated at the same inuent CR con-
centration (50 mg L
-1
) and ow rate (3.0 mL min
-1
),
respectively. The column sorption capacity was estimated as
follows (Eq. 3):
q
c

R C
0
C
i
V
eff
m
3
where C
0
and C
i
are the initial and efuent concentration of
dye in the liquid phase (mg L
-1
), V
eff
is the volume of the
efuent solution (L) and m is the mass of sorbent (g).
Subsequently, desorption percentage was calculated using
the following equations (Eqs. 4, 5):
%Desorption
m

m
o
100 4
m

C
e
V
0
and m
o
C
o
C
e
V 5
where, m
o
(mg) is the mass of dye previously sorbed onto the
adsorbent, m

mg is the mass of the released dye in the

regenerated solution; V
0
is the volume of regenerant solution
(L). V is the inlet dye solution (L), C
o
and C
e
are the initial
(inlet) and equilibrium (outlet) concentrations (mg L
-1
) of
dye, respectively.
Result and Discussion
Scanning Electron Micrographs (SEM)
The surface morphology of an adsorbent plays important
role on the adsorption capacity. The scanning electron
microscopic (SEM) micrographs of SD and CTAB/SD are
shown in Fig. 2a, b. The SEM of SD (Fig. 2a) indicates a
heterogeneous, porous morphology. Modication of the
surface of SD due to sediment of the CTAB is evident from
the formation of a white layer of uniform thickness and
coverage (Fig. 2b). Based on the BET analysis carried out
for SD, the specic surface area of SD was found to be very
low (78 m
2
/g). So, it might be concluded that dye uptake
by SD is not governed by its surface area; instead the
surface chemistry of the SD due to the presence of various
functional groups determines its sorption properties.
Batch Experiments
Effect of pH
The pH is one of the most important factors affecting many
adsorption processes. In order to investigate the inuence
J Surfact Deterg (2012) 15:557565 559
1 3
of initial pH on the CR removal by SD and CTAB/SD,
experiments were carried out over a pH range of 2.010.0
while the other conditions were kept constant (initial con-
centration of 100 mg L
-1
, sorbent dosage of 0.8 g and
contact time of 60 min). The results obtained from this
investigation are shown in Fig. 3.
As the results show, more than 90% CR dye removal is
observed in the pH range 4.010.0 and the sorption
capacity of CTAB/SD does not change signicantly in this
pH range. Maximum dye removal observed at optimum pH
values for CTAB and SD are [99 and 60% respectively.
Therefore, modication of sawdust surface by cationic
surfactant (CTAB) can enhance the number of positive
sites and increase the adsorption of CR anions consider-
ably. This can be due to the high electrostatic attraction
between the positively charged surface of the adsorbent
(CTAB/SD) and CR dye molecules which are negatively
charged species. Sawdust is a heterogeneous bioadsorbent
which consisting mainly of cellulose, hemicellulose and
lignin ingredients and thus possess various functional
groups, such as carboxyl and hydroxyl, etc. which are
mostly negatively charged. The poor sorption capacity of
SD for CR dye removal can be due to the repulsive elec-
trostatic interactions between the dye molecules and the
negative sites on the surface of the SD particles. However,
sawdust much the same as most biomaterials is more
suitable adsorbent for taking up of positively charged
species such as heavy metal ions. This can be due to the
presence of chelating properties of the functional groups
present in its complex structure.
The decrease in the removal percentage of CR by
CTAB/SD at low pH values is probably due to the poor
chemical stability of the cationic surfactant in strong
inorganic acids. Lower adsorption of CR dye onto CTAB/
SD at pH[9 can be due to the presence of excess OH
-
ions which compete with the dye anions for the adsorption
sites. A similar trend was observed for the adsorption of
Congo Red by calcium-rich y ash and Jute stick powder
[11, 26]. However, for pH values ranging from 4.0 to 8.0,
the sorption could be explained taking into account other
sorption mechanisms, such as hydrogen bonds or pp
stacking interactions [12]. Based on the data shown in
Fig. 3, the most suitable pH values for CTAB/SD and SD
were 6.0 and 2.0 respectively.
Effects of Adsorbent Dosage
The effect of adsorbent dosage was studied at initial dye
concentration of 100 mg L
-1
and optimal pH value of
adsorbents. When the dried adsorbents dosage was
increased from 0.2 to 1.0 g, the dye removal (%) of SD and
CTAB/SD changed from 21.0 to 65.0% and 70.0 to 99.9%,
respectively (Fig. 4).
It was observed that the percentage of dye removal
increases with increases in adsorbents dosage. This is a
result of increased surface area and availability of more
adsorption sites. However, no increase in the amount of
dye adsorption was observed with increasing the adsorbent
dosage above 0.4 g for CTAB/SD. As the data show
(Fig. 4), CTAB/SD is a more efcient adsorbent for the
removal of CR from aquatic solutions than the untreated
SD. Of the two adsorbents used in this study, CTAB/SD
Fig. 2 SEM images of a SD (91000) and b CTAB/SD (9500)
Fig. 3 Effect of pH on the removal of CR by SD and CTAB/SD
(initial dye concentration = 100 mg L
-1
, adsorbent dosage = 0.80 g
and contact time = 60 min)
560 J Surfact Deterg (2012) 15:557565
1 3
allowed a greater removal at all levels of the adsorbent
dosage.
Effect of Initial Dye Concentration
Five different concentrations, i.e., 50, 80, 120, 150 and
200 mg L
-1
, respectively, were selected to investigate the
effect of initial dye concentration (C
0
) onthe adsorptionof CR
onto a xed amount (0.80 g) of the adsorbents SDand CTAB/
SD at optimal pH values for each adsorbent. As shown in
Fig. 5, the adsorption capacity for SD increased rapidly with
the initial dye concentration from 50 to 120 mg L
-1
, and
tended to remain stable when C
0
was above 120 mg L
-1
.
However, a linear increase in the adsorption capacity for CR
was observed for CTAB/SD from 50 to 200 mg L
-1
.
As the data clearly indicate, with increasing initial dye
concentration from 50 to 200 mg L
-1
, the amount of dye
adsorbed increased from 2.2 to 4.2 and 3.1 to 12.2 mg g
-1
,
using SD and CTAB/SD respectively. The adsorption
capacity of surfactant-modied (CTAB/SD) is consider-
ably higher than untreated sawdust especially at higher
initial concentrations of the dye. It can be concluded that
the adsorption capacity is highly dependent on the initial
concentration of dye in solution. This is due to an
increasing driving force to overcome all mass transfer
resistances of the dye molecules between the aqueous and
solid phase at a high initial dye concentration.
Effect of Contact Time
The effect of contact time on the percentage of dye removal
was examined using 0.80 g adsorbents with the initial CRdye
concentration of 100 mg L
-1
and optimal pH value of
adsorbents. The mixture was agitated in a mechanical shaker
for different periods of contact time (560 min).
As the results indicate (Fig. 6), CTAB/SD adsorbent
shows a fast rate of adsorption during the rst 5 min of
exposure time. About 95% of CR dye is removed in less
than 10 min. CTAB/SD afforded a rapid uptake and greater
removal at all periods of contact compared to SD which is
consistent well with the previously presented data in this
paper. The high removal rate at the start of the contact time
can be due to the large amount of surface area available for
adsorption of the dye at the initial stage of adsorption.
Adsorption Isotherms
Analysis of equilibrium data is important for developing an
equation that can be used to compare different materials under
different operational conditions and to design and optimize an
operating procedure [27]. The Langmuir and Freundlich iso-
therm models are commonly used for wastewater treatment
applications. Langmuir [28] developed a theoretical equilib-
riumisothermrelatingthe amount of gas adsorbedona surface
to the pressure of the gas. The Langmuir isotherm takes an
assumption that the adsorption occurs at specic homoge-
neous sites within the adsorbent. The equation is given as:
q
e

q
m
K
L
C
e
1 K
L
C
e
6
The equation can be linearized to the following equation:
1
q
e

1
q
m

1
K
L
q
m
1
C
e
7
Fig. 4 Effect of adsorbent dosage on the removal of CR by SD and
CTAB/SD (initial dye concentration = 100 mg L
1
and contact
time = 60 min)
Fig. 5 Effect of initial dye concentration on the adsorption capacity
of SD and CTAB/SD (adsorbent dosage = 0.80 g and contact
time = 60 min)
Fig. 6 Effect of contact time on the removal of CR by SD and
CTAB/SD (initial dye concentration = 100 mg L
1
and adsorbent
dosage = 0.80 g)
J Surfact Deterg (2012) 15:557565 561
1 3
Where, q
m
is the maximum amount of adsorption which
complete monolayer coverage on the adsorbent surface
(mg g
-1
) and is related to the surface area of adsorbent, K
L
is the Langmuir constant (L mg
-1
) which implies
adsorption enthalpy and its value depends on the nature
of adsorbate and the adsorbent surface. The Langmuir
constants K
L
and q
m
can be determined from the linear plot
of 1/C
e
versus 1/q
e
or C
e
/q
e
versus C
e
. According to Hall
et al. [29] the favorable adsorption of the Langmuir
isotherm can be expressed in terms of a dimensionless
constant separation factor or equilibrium parameter R
L
.
R
L

1
1 K
L
C
i
8
where, C
i
is the maximum initial CR concentration
(mg L
-1
). The values of this parameter are basically
classied into four groups, indicating the shape of the
isotherm, in which R
L
[1 is unfavorable, R
L
= 1 is linear,
0 \R
L
\1 is favorable, and R
L
= 0 is irreversible.
Freundlich [30] presented the earliest known sorption
isotherm equation. This empirical model can be applied to
non-ideal sorption on heterogeneous surfaces as well as
multilayer sorption and is expressed by the following
equation,
q
e
K
F
C
1=n
e
9
Equation 9 can be subsequently linearized by taking
logarithms:
log q
e
log K
F

1
n
log C
e
10
where, q
e
is the amount of dye adsorbed per unit of
adsorbent (mg g
-1
), C
e
is the concentration of dye solution
at adsorption equilibrium (mg L
-1
), K
F
(mg
1-1/n
g
-1
L
1/n
)
and n (dimensionless parameter) are the empirical Fre-
undlich adsorption isotherm constants relating to the
adsorption capacity and adsorption intensity respectively. It
is generally assumed that systems obey this equation and
that adsorption results in a multilayer instead of a single
monolayer. The favorable adsorption of this model can be
characterized such that if a value for n is above unity,
adsorption is favorable and a physical process [2]. The
magnitude of the Freundlich constant n gives a measure of
favorability of adsorption. The values of n between 1 and
10 (i.e., 1/n \1) represents a favorable sorption. The
Freundlich isotherm is linear if 1/n = 1 and, as 1/
n decreases, the isotherm becomes more nonlinear [31].
The calculated constants for the above mentioned models
together with correlation coefcients have been summa-
rized in Table 1.
As the obtained isotherm parameters show (Table 1),
CTAB/SD has a high adsorption capacity for anionic CR
dye in the solution. This shows that modication of saw-
dust by CTAB greatly improves its sorption properties
toward CR dye. It can also be seen that for CTAB/CD, the
Freundlich model yields a much better t than the Lang-
muir model. This, however, is indicative of the heteroge-
neity of the adsorption sites on the CTAB/SD particles and
multilayer adsorption than monolayer predicted by the
Langmuir equation. But for SD, the experimental results
indicate that sorption of CR onto SD follows the Langmuir
model. A good t of the Langmuir isotherm to the exper-
imental data for SD conrms that the adsorption is
monolayer. The R
L
values for the adsorption of CR onto
adsorbents are 0 \R
L
\1 also shows that the adsorption
process for both SD and CTAB/SD is favorable.
Fixed Bed Column Experiments, Breakthrough
Curve Analysis
Effect of pH
The breakthrough curves are obtained from the plot of
C
t
/C
0
versus efuent volume (V
eff
) in continuous or ow
systems. The breakthrough curves for CTAB/SD obtained
at different pH values are shown in Fig. 7. As the results
show, maximum dye removal occurred at pH of 6.0 for
CTAB/SD adsorbent. As we have already shown, the same
optimal pH value was observed in batch system for CTAB/
SD. The breakpoint observed in the breakthrough curve
occurred after passing about 750 mL of the dye solution.
Instead, the breakpoint for unmodied SD happened very
quickly (V
b
* 20 mL). On the other hand, modication of
sawdust with cationic surfactant (CTAB) improved its
sorption capacity toward CR anionic dye more than
35 times. A great enhancement in sorption capacity of SD
is resulted upon its simple modication CTAB surfactant.
Electrostatic interaction between the positive charged
introduced by cationic surfactant (CTAB) on the surface of
modied sawdust and the negatively charged CR dye
Table 1 Isotherm constants for the adsorption of CR on SD and CTAB/SD
Adsorbent Langmuir constants Freundlich constants
q
m
(mg g
-1
) K
L
(L mg
-1
) R
L
R
2
K
F
n R
2
SD 5.18 0.052 0.0877 0.9867 1.03 3.18 0.9040
CTAB/SD 9.07 16.71 0.0003 0.9418 8.10 3.94 0.9876
562 J Surfact Deterg (2012) 15:557565
1 3
molecules, can be considered as the main reason for the
improved sorption capacity of the CTAB/SD adsorbent.
Due to the fast happening of breakpoint and negligible
sorption capacity of SD for CR dye sorption, the further
column studies was carried out only for CTAB/SD
adsorbent.
Effect of Inuent Dye Concentration
on the Breakthrough Curve of CTAB/SD
The effect of inuent CR concentration on the shape of the
breakthrough curves is shown in Fig. 8. As shown in
Fig. 8, the break point of the curve begins after the passage
of about 1,600, 700 and 180 mL of the CR solution for
CTAB/SD when inuent concentration was 20, 50 and
100 mg L
-1
, respectively. It is illustrated that the break
point of the curve decreased with increasing inuent CR
concentration. As inuent concentration increased, sharper
breakthrough curves were obtained. This can be explained
by the fact that a lower concentration gradient caused a
slower transport due to a decrease in the diffusion coef-
cient or mass transfer coefcient. With increasing of the
inuent concentration, the steeper is the slope of break-
through curve and the break point of the curve occurred
more quickly. These results demonstrate that the change of
concentration gradient affects the saturation rate and break
point of the curve, which implies that the diffusion process
is concentration dependent.
Effect of Flow Rate and Bed Depth
on the Breakthrough Curve of CTAB/SD
To investigate the effect of ow rate, the breakthrough
curves at different ow rates (3.012.0 mL min
-1
) were
plotted while the other conditions such as inuent dye
concentration, sorbent dosage and pH were held constant.
For investigation of the effect of bed height, the
breakthrough curves at different bed depths (2.510.5 cm)
were plotted at constant inuent concentration (C
0
= 50
mg L
-1
), and ow rate (v = 3.0 mL min
-1
). The data
obtained from the related breakthrough curves (Supple-
mentary material 1) as well as initial inuent concentration
have been summarized in Table 2.
As the results show (Table 2), the breakpoint generally
occurred faster at higher ow rates. The breakpoint of the
curve reaching saturation also increased signicantly with
a decrease in the ow rate. When, at a low rate of inuent,
CR had more time to contact with CTAB/SD that resulted
in higher removal of CR ions in column. The reason is that
at a higher ow rate the rate of mass transfer increases, i.e.,
the amount of dye adsorbed onto a unit bed height (mass
transfer zone) increases with increasing ow rate leading to
Fig. 7 Breakthrough curves for adsorption of CR on CTAB/SD at
different pH values (C
0
= 50 mg L
-1
, v = 3 mL min
-1
, Z = 5.0 cm)
Fig. 8 Breakthrough curves for adsorption of CR on CTAB/SD at
different initial dye concentrations (pH = 6, v = 3 mL min
-1
and
Z = 5.0 cm)
Table 2 Values of breakthrough curve parameters obtained at dif-
ferent conditions
Operational parameters Adsorption parameters
V
b
(mL) q
b
(mg g
-1
) q
c
(mg g
-1
)
Initial concentration (mg L
-1
)
20 1,600 33.54 47.87
50 700 38.91 59.70
100 180 21.86 42.67
Flow rate (mL min
-1
)
3 700 38.91 59.70
6 450 22.92 42.71
12 300 19.96 33.60
Bed height (cm)
2.5 280 29.13 66.73
5 700 38.91 59.70
10.5 1,700 42.92 54.16
V
b
is the breakpoint volume, q
b
is the breakpoint adsorption capacity,
q
c
is the column adsorption capacity. Both q
b
and q
c
were calculated
using Eq. 3
J Surfact Deterg (2012) 15:557565 563
1 3
faster saturation at the higher ow rate [32]. Increasing the
bed height in the column was also led to a higher removal
efciency of CR dye. Higher uptake of dye at greater bed
heights can be due to an increase in adsorbent particles and
contact time of dye molecules with the adsorbent particles
which provides more binding sites and binding time for the
sorption.
Desorption Study
To make the adsorption process more economical, it is
necessary to regenerate the spent adsorbent. Moreover
desorption process of the dye can help the researcher in
elucidating the mechanism of an adsorption process. For
the desorption study, the dye uploaded columns were
treated with different chemicals. Maximum desorption was
observed when ethanol was employed as washing or re-
generant solution (% desorption [98). The fact that the
desorption process occurred using ethanol, an organic
agent, conrms that adsorption of CR onto CTAB/SD
mostly occurred via a chemisorption mechanism [32].
Conclusions
It was found that modication of sawdust by cationic
surfactant (CTAB) via simple treatment leads to a great
increase in sorption capacity of sawdust for uptake of
Congo Red dye from aqueous solutions. Electrostatic for-
ces between the positively charged active sites in CTAB
modied sawdust and the negatively charged adsorbate in
solution (CR) seems to be the main reason for the sorption
improvement. Maximum adsorption occurred at pH = 2.0
for SD and pH = 6.0 for CTAB/SD adsorbents. Adsorption
of CR on CTAB/SD followed the Freundlich model, while
adsorption of SD followed the Langmuir adsorption model.
The maximum adsorption capacities of SD and CTAB/SD
were found to be 5.2 and 9.1 mg g
-1
, respectively, based
on the monolayer Langmuir model which implies the
chemisorption mechanism. From adsorption experiments
performed in column or non-equilibrium conditions, it was
found CTAB/SD is much more efcient than SD when
compared in the batch system.
The results showed an increase in adsorption capacity
with an increase in initial dye concentration and bed height,
and sorption capacity decreased with increasing ow rate.
The highest bed capacity of 66.73 mg g
-1
was obtained
using 50 mg L
-1
inlet dye concentration, 2.50 cm bed
height and 3.0 mL min
-1
ow rate. Desorption studies
with the column system for CTAB/SD suggested that most
of the dye was held by CTAB/SD via strong electrostatic
forces, chemisorption as well as ion exchange processes.
CTAB/SD seems to be a cost effective, efcient, and very
promising adsorbent for the removal of anionic dyes from
dye polluted wastewaters such as textiles efuents.
Acknowledgments The authors would like to acknowledge nan-
cial support from the Postgraduate Studies of University of Guilan,
Rasht, Iran.
References
1. Alinsa A, Khemis M, Pons MN, Leclerc JP, Yaacoubi A,
Benhammou A, Nejmeddine A (2005) Electro-coagulation of
reactive textile dyes and textile wastewater. Chem Eng Process
44:461470
2. Vimonses V, Lei S, Jin B, Chow CWK, Saint C (2009)
Adsorption of Congo Red by three Australian kaolins. Appl Clay
Sci 43:465472
3. Dolphen R, Sakkayanwong N, Thiravetyan P, Nakbanpote W
(2007) Adsorption of Reactive Red 141 from wastewater onto
modied chitin. J Hazard Mater 145:250255
4. Visa M, Andronic L, Lucaci D, Duta A (2011) Concurrent dyes
adsorption and photo-degradation on y ash based substrates.
Adsorption 17:101108
5. Barzias FA, Sidiras DK (2007) Dye adsorption by prehydrolysed
beech sawdust in batch and xed-bed systems. Bioresour Technol
98:12082121
6. Lin JX, Zhan SL, Fang MH, Qian XQ, Yang H (2008) Adsorption
of basic dye from aqueous solution onto y ash. J Environ
Manage 87:193200
7. Smaranda C, Gavrilescu M, Bulgariu D (2011) Studies on sorp-
tion of Congo Red from aqueous solution onto soil. Int J Environ
Res 5:177188
8. Mall ID, Srivastava VC, Agarwal NK, Mishra IM (2005)
Removal of Congo Red from aqueous solution by bagasse y ash
and activated carbon: kinetic study and equilibrium isotherm
analyses. Chemosphere 61:492501
9. Purkait MK, Maiti A, Das Gupta S, De S (2007) Removal of
Congo Red using activated carbon and its regeneration. J Hazard
Mater 145:287295
10. Grabowska EL, Gryglewicz G (2007) Adsorption characteristics
of Congo Red on coal-based mesoporous activated carbon. Dyes
Pigm 74:3440
11. Acemioglu B (2004) Adsorption of Congo Red from aqueous
solution onto calcium-rich y ash. J Colloid Interface Sci
274:371379
12. Ozmen EY, Yilmaz M (2007) Use of b-cyclodextrin and starch
based polymers for sorption of Congo Red from aqueous solu-
tions. J Hazard Mater 148:303310
13. Pavan FA, Dias SLP, Lima EC, Benvenutti EV (2008) Removal
of Congo Red from aqueous solution by anilinepropylsilica
xerogel. Dyes Pigm 76:6469
14. Han R, Ding D, Xu Y, Zou W, Wang Y, Li Y, Zou L (2008) Use
of rice husk for the adsorption of Congo Red from aqueous
solution in column mode. Bioresour Technol 99:29382946
15. Ahmad AA, Hameed BH (2010) Fixed-bed adsorption of reactive
azo dye onto granular activated carbon prepared from waste.
J Hazard Mater 175:298303
16. Zambrano JB, Szygula A, Ruiz M, Sastre AM, Guibal E (2010)
Biosorption of reactive black 5 from aqueous solutions by
chitosan: column studies. J Environ Manage 91:26692675
17. Mendoza-Barron J, Jacobo-Azuara A, Leyva-Ramos R, Berber-
Mendoza MS, Guerrero-Coronado RM, Fuentes-Rubino L, Mar-
tinez-Rosakes JM (2011) Adsorption of arsenic (V) from a water
564 J Surfact Deterg (2012) 15:557565
1 3
solution onto a surfactant-modied zeolite. Adsorption 17(3):
489496
18. Bingol A, Ucun H, Bayhan YK, Karagunduz A, Cakici A,
Keskinler B (2004) Removal of chromate anions from aqueous
stream by cationic surfactant-modied yeast. Bioresour Technol
94:245249
19. Kheni A, Bouberka Z, Sekrane F, Kameche M, Derriche Z
(2007) Adsorption study of an industrial dye by an organic clay.
Adsorption 13:149158
20. Sureshkumar MV, Namasivayam C (2008) Adsorption behavior
of Direct Red 12B and Rhodamine B from water onto surfactant-
modied coconut coir pith. Colloids Surf A Physicochem Eng
Asp 317:277283
21. Ogino K, Kakihara T, Uchyama H, Abe M (1988) Solution
properties of mixed surfactant system sodium dodecyl sulfate and
alkyl polyoxyethylene ether system. J Am Oil Chem Soc
65:405411
22. Chern JM, Chien YW (2002) Adsorption of nitrophenol onto
activated carbon: isotherms and breakthrough curves. Water Res
36:647655
23. Singh S, Srivastava VC, Mall ID (2009) Fixed-bed study for
adsorptive removal of furfural by activated carbon. Colloids Surf
A Physicochem Eng Asp 332:5056
24. Vazquez G, Alonso R, Freire S, Gonzalez-Alvarez J, Antorrena G
(2006) Uptake of phenol from aqueous solutions by adsorption in
a Pinus pinaster bark packed bed. J Hazard Mater B133:6167
25. Kalavathy H, Karthik B, Miranda LR (2010) Removal and
recovery of Ni and Zn from aqueous solution using activated
carbon from Hevea brasiliensis: batch and column studies. Col-
loids Surf B Biointerface 78:291302
26. Pandal GC, Dasl SK, Guha AK (2009) Jute stick powder as a
potential biomass for the removal of Congo Red and Rhodamine
B from their aqueous solution. J Hazard Mater 164:374379
27. Parab H, Joshi S, Shenoy N, Lali A, Sarma US, Sudersanan M
(2006) Determination of kinetic and equilibrium of Co (II), Cr
(III), and Ni (II) onto coir pith. Process Biochem 41:609615
28. Langmuir I (1916) The constitution and fundamental properties
of solids and liquids. J Am Chem Soc 38:22212295
29. Hall KR, Eagleton LC, Acrivos A, Vermeulen T (1966) Pore- and
solid-diffusion kinetics in xed-bed adsorption under constant-
pattern conditions. Ind Eng Chem Fund 5:212223
30. Freundlich H (1906) Over the adsorption in solution. Z Phys
Chem 57A:385471
31. Ho YS, Porter JF, McKay G (2002) Equilibrium isotherm studies
for the sorption of divalent metal ions onto peat: copper, nickel
and lead single component systems. Water Air Soil Pollut
141:133
32. Namasivayam C, Muniasamy N, Gayatri K, Rani M, Rangana-
than K (1996) Removal of dyes from aqueous solutions by cel-
lulosic waste orange peel. Bioresour Technol 57:3743
Author Biographies
Reza Ansari (Ph.D.) is an associate professor in analytical chemistry.
His elds of interest: water and wastewater treatment, green
chemistry, electrochemistry and preparation electrochemical sensors
for environmental monitoring. Chemistry Department, University of
Guilan.
Babak Seyghali is a graduated M.Sc. student in the eld of
environmental analytical chemistry, Chemistry Department, Univer-
sity of Guilan.
Ali Mohammad-Khah (Ph.D.) is an assistant professor in analytical
chemistry. His elds of interest: environmental chemistry, pollution
control, and electrochemistry, University of Guilan.
M. Ali Zanjanchi (Ph.D.) is a full professor in analytical chemistry.
His elds of interest: spectroscopy, porous materials, and the
application of photocatalysis in pollution remediation. Chemistry
Department, University of Guilan.
J Surfact Deterg (2012) 15:557565 565
1 3