A new type of chitosan hydrogel sorbent generated by anionic surfactant gelation

Sudipta Chatterjee, Tania Chatterjee, Seung H. Woo

*
Department of Chemical Engineering, Hanbat National University, San 16-1, Deokmyeong-Dong, Yuseong-Gu, Daejeon 305-719, Republic of Korea
a r t i c l e i n f o
Article history:
Received 24 October 2009
Received in revised form 19 December 2009
Accepted 21 December 2009
Available online 2 February 2010
Keywords:
Adsorption
Chitosan
Hydrogel beads
Sodium dodecyl sulfate
Surfactant
a b s t r a c t
A new type of chitosan hydrogel beads (CSB) with a coreshell membrane structure was generated by
sodium dodecyl sulfate (SDS) gelation process. CSB exhibited higher mechanical strength and acid stabil-
ity than chitosan hydrogel beads (CB) formed by alkali gelation. The effect of SDS concentration variation
during gelation on the adsorption capacity of CSB for congo red (CR) as a model anionic dye showed that
CSB formed by 4 g l
1
SDS gelation had the highest adsorption capacity. The maximum adsorption capac-
ity of CSB (208.3 mg g
1
) obtained from the Sips model was found slightly higher than that of CB
(200.0 mg g
1
). Membrane materials of CSB obtained after squeezing core water from the beads showed
approximately 25 times higher volumetric adsorption capacity than CB.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
The efuents discharged from textile industry contain a large
variety of dyes and it is estimated that around 1015% of the dyes
are lost in the efuent during the dyeing processes (Crini, 2006;
dos Santos et al., 2007). The discharge of dye containing efuents
to the receiving water bodies retards photosynthesis by aquatic
plants and phytoplanktons due to abnormal colouration of water
(Robinson et al., 2001). Furthermore, some dyes in the efuents
are toxic, carcinogenic or mutagenic to human beings (Crini,
2006). Azo dyes represent about 50% of all dyes and more than
53% of these commonly azo dyes are known to be highly resistant
to biological degradation process (Manu and Chaudhari, 2002).
Congo red (CR) is one of important azo dyes and it mainly occurs
in the efuents discharged from textile, paper, printing, leather
industries, etc. CR is metabolized to benzidine, a known human
carcinogen.
Various techniques such as coagulation/occulation (Hasani
et al., 2009), activated carbon adsorption (Kadirvelu et al., 2003),
oxidation (Malik and Saha, 2003), ozonation (Selcuk, 2005), elec-
trochemical oxidation (Radha et al., 2009), membrane separation
(Chiu et al., 2009), biological degradation (Gopinath et al., 2009),
etc., have been applied for the treatment of dye containing efu-
ents and most of the techniques are reported as expensive and
not environment friendly (Crini, 2006). Activated carbon is the
most widely used adsorbent for dye removal, but it is too expen-
sive and there is difculty in the regeneration process (Kadirvelu
et al., 2003). Various low-cost adsorbents such as coir pith acti-
vated carbon (Namasivayam and Kavitha, 2002), fungal and algal
biomasses (Khalaf, 2008), bacterial biomass (Vijayaraghavan
et al., 2008), neem leaf powder (Bhattacharrya and Sharma,
2004), activated desert plant (Bestani et al., 2008), palm kernel
seed coat (Oladoja and Akinlabi, 2009), etc., have been used for
the removal of dye from wastewater. However, low-adsorption
capacities of some of these adsorbents for dyes initiate further
search for new adsorbents.
Chitosan (CS) is a natural heteropolymer of glucosamine and
N-acetyl glucosamine residues, and obtained by alkaline deacety-
lation of chitin (a polymer made up of N-acetyl glucosamine
residues), the next most abundant natural polysaccharide after
cellulose (Chung and Chen, 2008; Crini and Badot, 2008).
Recently, CS hydrogel beads have generated great interest for
removal of environmentally hazardous chemicals due to their bio-
degradability, low-cost, and multiple functional groups (Crini and
Badot, 2008; Chatterjee et al., 2009a,b). CS hydrogel beads are
more extensively used than ake and powder forms of this poly-
mer because of their high surface area and porosity (Varma et al.,
2004). CS hydrogel beads have shown surprisingly high adsorp-
tion capacities for numerous dyes and heavy metals, as compared
to various adsorbents surveyed in recent review papers (Crini,
2006; Guibal, 2004; Gupta and Suhas, 2009). Nevertheless, CS
hydrogel beads formed by conventional physical or alkali gelation
face serious impediments to commercial application, such as low-
mechanical strength, low-acid stability, and a large material vol-
ume. Different methods like chemical cross-linking (Chiou et al.,
2004), carboxy alkyl substitution (Cestari et al., 2004), carbon
nanotubes impregnation (Chatterjee et al., 2009c), etc., can
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.12.089
* Corresponding author. Tel.: +82 42 821 1537; fax: +82 42 821 1593.
E-mail address: shwoo@hanbat.ac.kr (S.H. Woo).
Bioresource Technology 101 (2010) 38533858
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improve mechanical stability of CS hydrogel beads, but still do
not yield enough strength for use in actual situations. Moreover,
sometimes these methods cause a signicant decrease in adsorp-
tion capacity (Crini and Badot, 2008).
Recently, the study on interactions between polymeric materi-
als and anionic surfactants has been a subject of fundamental re-
search (Thongngam and McClements, 2005; Trabelsi et al., 2006).
According to literature survey, fabrication of CS hydrogel beads
by anionic surfactant gelation and its application in the adsorption
research eld have not been reported to date. In this study, a new
type of CS hydrogel beads (CSB) was generated by anionic surfac-
tant gelation process using sodium dodecyl sulfate (SDS). A de-
tailed study of the mechanical properties of these materials
together with its adsorption performance for CR as a model anionic
dye was investigated.
2. Methods
2.1. Materials
CS (>85% deacetylation), SDS, and CR were purchased from Sig-
ma Chemical Co., USA. All other analytical grade chemicals were
purchased from Sigma Chemical Co., USA.
2.2. Surfactant and alkali gelation
Formation of chitosan hydrogel beads by SDS gelation (CSB) in-
volved dropwise (drop volume 20 ll) addition of CS solution
(1 wt.% CS in 2 vol.% acetic acid) into SDS solution of various con-
centrations between 1 and 50 g l
1
through a T-1000-B pipet tip,
Axygen scientic, USA. The subsequent beads formation in the
same SDS solution depletes the amount of SDS. In order to attain
the same amount of SDS in the beads with subsequent bead forma-
tion in the solution, maximumtwenty hydrogel beads were formed
in 10 ml SDS solution of desired concentration and beads were ta-
ken from the same SDS solution after 3 h. CS hydrogel beads
formed by alkali gelation (CB) involved dropwise addition of CS
(1 wt.%) in acetic acid solution (2 vol.%) to alkali mixture
(H
2
O:MeOH:NaOH = 4:5:1, w/w). As-prepared beads were exten-
sively washed with deionized water and preserved in aqueous
environment for future use.
2.3. Structure analysis
Optical micrographs of CB, and CSB by 4, 10, 20 and 50 g l
1
SDS
gelation were taken using Nikon Microscope Eclipse 80i, Japan. Ele-
mental analyses of CB, and CSB formed with various SDS concen-
trations (5, 10, 20 and 50 g l
1
) were performed using Elemental
analyzer (EA1108, Fisons). Infrared (IR) spectra of CB and CSB
formed with various SDS concentrations (5, 10, 20 and 50 g l
1
)
were characterized using a FTIR Spectrophotometer (Nicolet
6700, Thermal) with KBr pellet.
2.4. Mechanical stability
The response of the CB and CSB to ultrasonication gives an in-
sight into the mechanical stability of the beads and it was deter-
mined by measuring weight loss after ultrasonication of 1 g wet
beads in 100 ml deionized water using 750 W ultrasonic processor
(VC 750, Sonics) with a high power sonic tip operated at 20 kHz
frequency and under various power amplitudes (a) 21%, (b) 25%,
(c) 30%, and (d) 35% for 10 min. The beads obtained after ultrason-
ication were collected using 1 mmsieve and percentage dry weight
loss of beads was measured from the weight difference of the
beads before and after ultrasonication.
2.5. Acid stability
Acid stability of gel particles was characterized by determining
the mass loss due to gel dissolution in acidic solution. The swelling
experiment of beads in acid solution was performed by adding 1 g
wet beads of CB and CSB in 50 ml deionized water of various pH
levels (pH 27) and the beads were allowed to swell for 6 h at
30 C in shaking condition. The percentage dry weight loss of the
beads was determined from the difference of wet weight of the
hydrogel beads before and after swelling.
2.6. Adsorption study
The adsorption capacity of CSB formed by 4 g l
1
SDS gelation
was compared with CB for adsorption of CR from 100 mg l
1
aque-
ous solution. Here CR was selected as a model anionic dye. Mem-
brane materials of the CSB (CSM) were obtained after squeezing
core water from the beads and the adsorption performance of
CSM was also evaluated in this study. The batch adsorption exper-
iments were performed in glass vials (20 ml) containing 10 ml CR
solution of desired concentration and 0.2 g wet adsorbent materi-
als at pH 5 and 30 C under shaking condition (150 rpm) for 24 h.
The performance of CSB formed in various SDS solutions from 2
to 50 g l
1
was studied for adsorption of 100 mg l
1
CR solution.
Equilibrium isotherm studies were carried out at a xed tempera-
ture (30 C) using CB and CSB formed by 4 g l
1
SDS gelation as
adsorbent materials, and different initial concentrations of CR
(101000 mg l
1
) were prepared from a stock solution
(1000 mg l
1
). The kinetics experiments were performed to deter-
mine equilibrium time for adsorption of CR (100 mg l
1
) onto CB
and CSB, and different time intervals up to 960 min were used
for this study. The amount of CR in solution before and after
adsorption was analyzed at its absorption maximum (k
max
,
497 nm) using a DR5000 spectrophotometer (HACH, USA). All the
experiments were conducted in triplicate. The amounts of CR ad-
sorbed by the adsorbent materials were calculated using the fol-
lowing equation:
q
C
0
C
eq
V
W
1
where q (mg g
1
) is the amount of CR adsorbed by the adsorbent
materials, C
0
and C
eq
(mg l
1
) are the initial and equilibrium li-
quid-phase concentration of CR, respectively, V (l) is the initial vol-
ume of dye solution, and W (g) is the dry weight of adsorbent
materials.
2.7. Adsorption isotherm models
The non-linear forms of the Langmuir, Freundlich and Sips iso-
therm models were used to analyze the equilibrium isotherm data
and these models were evaluated by the non-linear coefcients of
determination (R
2
) and a non-linear Chi-square test (v
2
). The
expression of the Langmuir model is given as:
q
e

q
m
K
L
C
e
1 K
L
C
e
2
where C
e
is the equilibriumconcentration of CR (mg l
1
) in the solu-
tion, q
e
is the equilibrium CR concentration (mg g
1
) on the adsor-
bent, and q
m
(mg g
1
) and K
L
(l mg
1
) are Langmuir constants
related to the adsorption capacity and energy of adsorption,
respectively.
The expression of the Freundlich model is:
q
e
K
F
C
1
n
e
3
3854 S. Chatterjee et al. / Bioresource Technology 101 (2010) 38533858
K
F
is the Freundlich constant related to the sorbent capacity of sor-
bent and n is an empirical parameter representing the heterogene-
ity of site energies.
Sips model is a combination of Langmuir and Freundlich models
and it is expressed as:
q
e

q
max
K
eq
C
n
e
1 K
eq
C
n
e
4
K
eq
(l mg
1
) represents the equilibrium constant of Sips equa-
tion and q
max
(mg g
1
) is the maximum adsorption capacity. Sips
isotherm model is characterized by the heterogeneity factor, n.
2.8. Desorption studies
Desorption studies were carried out with CR loaded beads ob-
tained from an adsorption system with 10 ml of CR solution
(100 mg l
1
), and 0.2 g wet weight of beads (CB and CSB). After
adsorption for 24 h at pH 5, the beads were separated by ltration
and CR concentration in the ltrate was measured spectrophoto-
metrically. The beads were washed gently with deionized water
to remove unadsorbed CR molecules. After washing, beads were
transferred into 10 ml of deionized water adjusted to pH 1013
and CR desorbed from the beads to the solution was measured
after 24 h.
3. Results and discussion
3.1. Formation of CS hydrogel beads by alkali and SDS gelation
Formation of CB involves neutralisation of each droplet of CS
solution in alkali solution and this process generates a physical
hydrogel bead that contains only water and CS in the free amine
form. The neutralisation of NH

3
sites into NH
2
leads to the disap-
pearance of ionic repulsions between polymer chains, and the
physical hydrogel bead is formed by physical cross-linking of poly-
mer chains involving hydrogen bonds and hydrophobic interac-
tions (Ladet et al., 2008). Physical hydrogel formation of CS
simply involves the process of hydrophobic/hydrophilic balance
(Montembault et al., 2005).
Formation of CSB begins when drops of CS solution are added to
SDS solution (250 g l
1
). The mixing between the two solutions is
not instantaneous because CS solution droplets are viscous. The
oppositely charged surfactant (SDS) and polyelectrolyte (CS) come
into contact with one another by means of counter-diffusion across
the surfactant/polyelectrolyte solution interface. Unlike the deep
penetration of small OH

ion during alkali gelation into the CS

droplet, complex formation occurs only at the interface due to
the large size of the surfactant molecule, and a gel capsule is
formed around the drop. This effect results in shrinkage of the
polyelectrolyte drop, and hydrogel beads are thus formed by asso-
ciative phase separation (Lapitsky and Kaler, 2004). Such a network
is stabilised by a combination of electrostatic, iondipole, and
hydrophobic interactions (Thongngam and McClements, 2004).
After the rst soft membrane layer is rapidly formed, surfactant
molecules are still able to penetrate through the layer, and a sec-
ond membrane layer is formed by contact with chitosan molecules
that are diffused to the inner surface. Ultimately, a shell membrane
composed of thin layers is formed.
3.2. Structure of hydrogel beads
Optical microscope images of hydrogel beads (gure not
shown) illustrate that CB consist purely of CS molecules, whereas
CSB formed by 4 g l
1
SDS gelation consist of a sparsely gelled core
encapsulated by a dense shell, indicating a coreshell structure.
The images of CSB at different stages of gelation (gure not shown)
clearly indicate that SDS complexation continues in SDS solution
even after bead formation, and structural organisation of the beads
changes with time after formation in the same solution. Cross-sec-
tions of CSB exhibit a multi-membrane structure. As SDS concen-
tration is increased in the gelling solution, stronger and denser
hydrogel beads are formed. Additionally, shrinkage is observed
from osmotic action of the shell membrane, by which more water
molecules in the shell are released at high concentrations of SDS in
the gelling solution.
The results of elemental analysis of CSB formed by various SDS
concentrations are listed in Table 1. The sulfur (S) content of CSB is
close to the stoichiometric molar ratio, but this value slightly in-
creases with an increase in SDS concentration in the gelling solu-
tion. The determination of SDS content of CSB is purely based on
S (%) obtained by elemental analysis because the amount of S in
CSB is solely contributed by SDS molecules. Thereby, the increase
in SDS concentration during gelation increases SDS content in
CSB (Table 2).
FTIR spectra of CB (gure not shown) show characteristic peaks
assignment of CB: 3442 cm
1
(wide peak of OH stretching over-
lapped with NH stretching), 2878 cm
1
(CH stretching),
1651 cm
1
(amide II band, NH bending and C@O stretching of
acetyl groups), 1382 cm
1
(OH bending and CN stretching) and
1071 cm
1
(bridge COC stretching and CO stretching). Charac-
teristic peaks obtained for CSB (gure not shown) with various
SDS concentrations during gelation (5, 10, 20, 50 g l
1
) are:
3441 cm
1
(wide peak of OH stretching overlapped with NH
stretching), 2923 and 2853 cm
1
(CH stretching), 1635 cm
1
(amide II band, NH bending and C@O stretching of acetyl groups),
1467 cm
1
(asymmetric CH bending of CH
2
group), 1379 cm
1
(OH bending and CN stretching) and 1061 cm
1
(bridge COC
stretching and CO stretching). The appearance of new spectral
Table 1
Elemental analysis of CSBs with various concentrations of SDS.
Element (%) SDS concentration (g l
1
)
5 10 20 50
N 3.36 0.03 3.40 0.02 3.41 0.03 3.37 0.01
C 47.52 0.31 47.50 0.34 47.42 0.08 48.14 1.98
H 8.46 0.07 8.46 0.11 8.38 0.05 8.49 0.30
S 6.14 0.32 6.52 0.16 6.71 0.04 6.77 0.01
Data represents average of three replicates with standard deviations.
SDS (g l
-1
)
0 5 10 15 20 25
D
r
y

w
e
i
g
h
t

l
o
s
s

(
%
)
0
20
40
60
80
100
120
CB (21%)
CB (25%)
CB (30%)
CB (35%)
CSB (21%)
CSB (25%)
CSB (30%)
CSB (35%)
Fig. 1. Mechanical stability test of CB and CSB formed at various SDS concentrations
(5, 10 and 20 g l
1
). The value in the parenthesis of the legend represents power
amplitude during ultrasonic operation.
S. Chatterjee et al. / Bioresource Technology 101 (2010) 38533858 3855
peaks especially in the region of 16501550 cm
1
, and at
2923 cm
1
indicates binding of dodecyl sulfate with the amine
group of CS molecules during SDS gelation. Thereby, FTIR results
clearly suggest that the interactions between CS and oppositely
charged SDS molecules lead to complex formation, in which gluco-
samine units of CS form salt bonds with SDS. The nal bead struc-
ture forms via hydrophobic interactions between non-polar
segments of SDS in aqueous solution.
3.3. Mechanical stability of hydrogel beads
Mechanical stability testing of the beads is given as mass loss
under ultrasonication. Fig. 1 shows that CSB showed much less
mass loss than CB after ultrasonication, indicating that beads
formed by SDS gelation are mechanically more stable than physical
hydrogel beads of CS. The percentage dry weight loss of CSB after
ultrasonication decreased with an increase in SDS concentration
during gelation. It has been reported in earlier publication (Chat-
terjee et al., 2009c) that mechanical stability of CB was greatly en-
hanced by carbon nanotube (CNT) impregnation. The weight loss of
CNT impregnated CB was 2.02% after ultrasonication under 25%
power amplitude for 10 min, whereas, that for CB and CB cross-
linked with epichlorohydrin (ECH) was 51.61% and 40.21%, respec-
tively. In this study, CSB formed by 5, 10 and 20 g l
1
SDS gelation
exhibited 1.14%, 0.42% and 0% weight loss, respectively, after ultra-
sonication under 25% power amplitude for 10 min. The less mass
loss of CSB than CNT impregnated CB or cross-linked CB indicates
the effectiveness of SDS gelation method for enhancing mechanical
stability of CB.
3.4. Acid stability of hydrogel beads
Acid stability test of hydrogel beads indicated that the mass loss
of CB was found to increase with a decrease in pH of the solution
(gure not shown). Complete solubilisation of CB at pH 2 indicates
poor acid stability because free positive charges develop in beads
due to protonation of the amine groups of CS and the resulting mu-
tual repulsion causes swelling. CSB formed by 5 g l
1
SDS gelation
did not show any mass loss or pH-sensitive swelling under acidic
conditions, even in a pH 2 solution. In the previous study (Chatter-
jee et al., 2009c), CB after CNT impregnation did not show any
additional acid stability. The acid stability of CB was only enhanced
after ECH cross-linking, and interestingly, the weight loss of CSB
(0.4%) was obtained much less than CB cross-linked with ECH
(24.8%) in a pH 2 solution. Therefore, SDS gelation could provide
a good acid stability of CS hydrogel beads without additional
cross-linking treatment.
3.5. Effect of SDS concentration on CR adsorption
SDS concentration variation (250 g l
1
) during gelation exhib-
ited effects on the adsorption capacity of CSB (mg g
1
) for CR
(100 mg l
1
). The maximum adsorption capacity of CSB was ob-
served with 4 g l
1
SDS gelation and at concentrations of SDS great-
er than 4 g l
1
, CSB showed a decrease in adsorption capacities. The
increase of adsorption capacity up to 4 g l
1
SDS gelation is attrib-
uted to hydrophobic interactions between CR and SDS molecules
dominating over the charge repulsions by the same molecules dur-
ing adsorption. The increase in SDS concentration during gelation
increases the SDS content in CSB (Table 2) and makes the beads
denser; this may cause increased charge repulsion between CR
and negatively charged groups of free SDS molecules and obstruct
mass transfer of CR into the interior adsorption site during
adsorption.
3.6. Volumetric adsorption capacity
Table 3 shows that CSB formed by 4 g l
1
SDS gelation exhibited
better adsorption capacity (115.8 mg CR g
1
dry weight of beads)
than CB (83.1 mg CR g
1
dry weight of beads) for adsorption from
a 100 mg l
1
CR solution, and that was most likely due to increased
hydrophobic interactions between SDS and CR. The volumetric
adsorption capacity of beads (mg CR ml
1
material volume) was
obtained by multiplying q
e
(mg g
1
) of adsorbent materials with
the g dry weight ml
1
of materials, which was increased from
0.023 g ml
1
for CB to 0.45 g ml
1
for CSM. The volumetric adsorp-
tion capacity (47.0 mg ml
1
) for CSM was signicantly enhanced
compared to that for CB (1.9 mg ml
1
), which represents a 25 in-
crease. Therefore, signicant enhancement of the volumetric
adsorption capacity of CSM could enhance applicability in real
wastewater treatment.
3.7. Adsorption isotherm
Fig. 2 exhibits the tting of equilibrium adsorption isotherm
data for CB and CSB by 4 g l
1
SDS gelation to the non-linear form
of Langmuir, Freundlich and Sips isotherm models. The results of
non-linear R
2
and v
2
for three adsorption isotherms are shown in
Table 4. The Sips isotherm model appeared to be the best tting
model for CR adsorption onto CB because of highest R
2
(0.993)
and lowest Chi-square, v
2
(2.69) values. The results of non-linear
R
2
(0.997) and v
2
(1.60) of Langmuir model, and R
2
(0.997) and
v
2
(1.70) of Sips model for adsorption of CR onto CSB indicated that
adsorption isotherm data for CSB exhibited good t with both
models. The value of n for CR adsorption onto CSB was close to
Table 2
CS and SDS contents of CSBs with various SDS concentrations.
Adsorption SDS concentration (g l
1
)
5 10 20 50
Sulfur (S) content (g) g
1
dry weight of beads
a
0.061 0.003 0.065 0.002 0.067 0.000 0.068 0.000
SDS content (g) g
1
dry weight of beads 0.553 0.028 0.587 0.014 0.605 0.003 0.610 0.001
CS content (g) g
1
dry weight of beads 0.447 0.028 0.413 0.014 0.395 0.003 0.390 0.000
mol NH
2
of CS g
1
dry weight of beads 0.0024 0.0002 0.0022 0.0001 0.0021 0.0000 0.0021 0.0000
mol SDS mol
1
NH
2
of CS 0.818 0.094 0.936 0.054 1.005 0.008 1.030 0.002
Data represents average of three replicates with standard deviations.
a
S content of CSB obtained by elemental analysis.
Table 3
Adsorption capacities of different type adsorbent materials
a
.
Type q
e
(mg CR g
1
) q
e,v
(mg CR ml
1
)
CB 83.1 1.14 1.87 0.03
CSB
b
115.8 0.96 2.66 0.03
CSM
b
103.5 1.01 47.0 0.12
a
Initial CR concentration was 100 mg l
1
.
b
The materials were produced by the gelation with 4 g l
1
SDS solution
3856 S. Chatterjee et al. / Bioresource Technology 101 (2010) 38533858
unity (n = 1.02), indicating that adsorption onto CSB is homoge-
neous. The close similarity between maximum adsorption capacity
values obtained from Langmuir (208.1 mg g
1
) and Sips
(208.3 mg g
1
) isotherm models for CSB beads indicated homoge-
neous adsorption process. The maximum adsorption capacity of
CSB (208.3 mg g
1
) and CB (200.0 mg g
1
) obtained from the Sips
isotherm model was similar, whereas maximum adsorption capac-
ity of CSB (208.1 mg g
1
) obtained from the Langmuir isotherm
model was higher than that of CB (179.2 mg g
1
). Thereby,
mechanically improved CSB exhibited similar (Sips isotherm) or
higher (Langmuir isotherm) maximum adsorption capacity than
CB.
The comparison of maximum adsorption capacity of CSB
(208.3 mg g
1
) with that of other adsorbents used for adsorption
of CR such as 6.70 mg g
1
of activated carbon prepared from coir
pith (Namasivayam and Kavitha, 2002), 41.20 mg g
1
of neem leaf
powder (Bhattacharrya and Sharma, 2004), 66.23 mg g
1
of palm
kernel seed coat (Oladoja and Akinlabi, 2009), and 330.62 mg g
1
of N,O-carboxymethyl CS (Wang and Wang, 2008) indicated that
CSB could be used as an effective adsorbent for adsorption of CR
from aqueous solutions. Moreover, adsorption performance of this
sorbent could be further improved by surface modication or
impregnation with various chemicals and materials as CR adsorp-
tion capacity increased by cetyl trimethyl ammonium bromide
impregnation (Chatterjee et al., 2010) or carbon nanotubes impreg-
nation (Chatterjee et al., 2009d).
3.8. Kinetic study
Experimental kinetic data for adsorption of CR onto CB and CSB
from a 100 mg l
1
solution have been illustrated in Fig. 3 and equi-
librium adsorption time for both adsorption systems was 420 min.
Two simplied kinetic models including pseudo-rst-order and
pseudo-second-order equations, and intra-particle diffusion mod-
el, were used in this study.
The non-linear form of the pseudo-rst-order rate equation is
given as:
q
t
q
e
1 e
k
1
t
5
where q
e
and q
t
are the amounts of CR adsorbed (mg g
1
) at equilib-
rium and at a predetermined time (t), respectively, and k
1
(min
1
) is
the rate constant of this equation. The constants, k
1
and q
e
values
obtained from this rate model are given in Table 5.
The non-linear form of pseudo-second-order rate equation is
expressed as:
q
t

q
2
e
k
2
t
1 q
e
k
2
t
and h k
2
q
2
e
6
where h represents the initial adsorption rate (mg g
1
min
1
) and k
2
(g mg
1
min
1
) is the pseudo-second-order rate constant. The val-
ues of q
e
, k
2
and h obtained from rate model are presented in Table
5.
The correlation coefcient (R
2
) values of the pseudo-rst-order
equation were 0.998 and 0.994 for CB and CSB, respectively. For the
pseudo-second-order model, the correlation coefcient (R
2
) values
were 0.988 and 0.991 for CB and CSB, respectively. The R
2
values of
both rate models for each adsorption system indicated that CR
adsorption onto CB and CSB could be better explained by pseu-
do-rst-order rate model than pseudo-second-order rate model.
As shown in Table 5, the q
e
values of CB (83.34 mg g
1
) and CSB
(116.92 mg g
1
) obtained from pseudo-rst-order rate model were
in better agreement with q
e (exp)
value of CB (83.19 mg g
1
) and
CSB (115.90 mg g
1
), respectively, than q
e
values of CB
(96.59 mg g
1
) and CSB (140.15 mg g
1
) obtained from pseudo-
second-order rate model.
C
e
(mg l
-1
)
0 200 400 600 800 1000
q
e

(
m
g

g
-
1
)
-50
0
50
100
150
200
250
Experimental data (CB)
Langmuir non-linear (CB)
Freundlich non-linear (CB)
Sips non-linear (CB)
Experimental data (CSB)
Langmuir non-linear (CSB)
Freundlich non-linear fit (CSB)
Sips non-linear fit (CSB)
4 g l
-1
SDS gelation,
pH 5, 30
0
C
Fig. 2. Plot of q
e
vs. C
e
for adsorption of CR onto CB and CSB formed by 4 g l
1
SDS
gelation; pH 5 and 30 C.
Table 4
Constants for equilibrium isotherm models with error analysis values.
Langmuir isotherm model
Adsorbent K
L
(l mg
1
) q
m
(mg g
1
) Error analysis
R
2
v
2
CB 0.026 179.2 0.980 12.86
CSB 0.046 208.1 0.997 1.60
Freundlich isotherm model
Adsorbent K
F
(l g
1
) 1/n Error analysis
R
2
v
2
CB 26.91 0.291 0.938 23.00
CSB 39.17 0.262 0.893 51.09
Sips isotherm model
Adsorbent q
max
(mg g
1
) K
eq
(l mg
1
) n Error analysis
R
2
v
2
CB 200.0 0.054 0.72 0.993 2.69
CSB 208.3 0.044 1.02 0.997 1.70
t (min)
0 200 400 600 800 1000 1200
q
t

(
m
g

g
-
1
)
0
20
40
60
80
100
120
Experimental data (CB)
Pseudo-first-order (CB)
Pseudo-second-order (CB)
Intra particle diffusion (CB)
Experimental data (CSB)
Pseudo-first-order (CSB)
Pseudo-second-order (CSB)
Intra particle diffusion (CSB)
4 g l
-1
SDS gelation
C
0
= 100 mg l
-1
, pH 5
Fig. 3. Plot of q
t
vs. t for adsorption of CR onto CB and CSB formed by 4 g l
1
SDS
gelation; initial CR concentration, 100 mg l
1
; pH 5.
S. Chatterjee et al. / Bioresource Technology 101 (2010) 38533858 3857
The intra-particle diffusion equation is given as:
q
t
k
p
t
0:5
7
k
p
is the intra-particle diffusion rate constant (mg g
1
min
0.5
) and
the values of k
p
for CB and CSB were 4.96 and 5.76 mg g
1
min
0.5
,
respectively (Table 5). The correlation coefcients (R
2
) values for CB
(0.947) and CSB (0.953) indicated that intra-particle diffusion has a
signicant role in initial stage of adsorption in the study.
3.9. Desorption study
Desorption studies help to understand the mechanism of
adsorption and also help in the recovery of CB and CSB. The results
indicated that CSB exhibited less increase in desorption (from
16.18% 0.89 to 25.06% 1.72) than CB (from 25.92% 1.01 to
36.84% 2.060) with pH change from 10 to 13. CB showed very
low-desorption for CR with pH change because of strong bond for-
mation between CR and CS molecules and involvement of some
interactions other than electrostatic interactions. Moreover, the
less desorption for CSB than CB with pH change suggests strong
hydrophobic interactions between CSB and CR molecules.
4. Conclusions
CS hydrogel bead formed by SDS gelation (CSB) produced dense
coreshell membrane structure, and it showed higher mechanical
strength and acid stability than conventional CS hydrogel bead
formed by alkali gelation (CB). CSB formed by 4 g l
1
SDS gelation
exhibited slightly higher adsorption capacity than CB for congo red
(CR). Membrane materials of CSB (CSM) generated by removing
core water had approximately 25 times higher volumetric adsorp-
tion capacity than CB for CR. Thus, generation of CSM from CSB
could enhance the technical and commercial importance of con-
ventional CB in the eld of wastewater treatment by solving its
major limitations.
Acknowledgement
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education, Science and Technology (grant num-
ber 2009-0079636).
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Table 5
Constants of different rate models for CB and CSB
a
.
Adsorbent q
e (exp)
Pseudo-rst-order equation Pseudo-second-order equation Intra-particle diffusion
(mg g
1
) q
e (cal)
(mg g
1
) k
1
(min
1
) q
e (cal)
(mg g
1
) k
2
(g mg
1
min
1
) h (mg g
1
min
1
) k
p
(mg g
1
min
0.5
)
CB 83.19 83.34 0.010 96.59 1.24 10
4
1.16 4.96
CSB 115.90 116.92 0.007 140.15 5.61 10
5
1.10 5.76
a
Initial CR concentration was 100 mg l
1
.
3858 S. Chatterjee et al. / Bioresource Technology 101 (2010) 38533858