Separation and Purification Technology 67 (2009) 218–225

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Separation and Purification Technology

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An investigation on the adsorption of acid dyes on bentonite

based composite adsorbent
Shizhang Qiao a , Qiuhong Hu a , Fouad Haghseresht a , Xijun Hu b,∗ , Gao Qing (Max) Lu a
a
ARC Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, University of Queensland, Brisbane QLD 4072, Australia
b
Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong

a r t i c l e i n f o a b s t r a c t

Keywords: We report the adsorption study of two commercial dyes, Acid Red 18 (AR18) and Acid Yellow 23 (AY23),
Clay onto bentonite based composite adsorbent from aqueous solution. The modified bentonite adsorbent
Adsorption was developed with the expectation to better adsorb anionic dyes. Single dye adsorption equilibrium
Dye
was measured and the experimental data was analysed by the Langmuir, Freundlich and Redlich-Peterson
Remediation
isotherms. The results indicate that the Redlich-Peterson model provides the best correlation of the exper-
imental data. The adsorption capacities estimated from the Langmuir model for AR18 and AY23 were at
69.8 and 75.4 mg/g, respectively. Binary dye adsorption was also investigated. The results reveal that the
multicomponent nature of the dye wastewater introduces additional complications to the adsorption
process. Many new factors need to be taken into account, including the interactions between the adsor-
bate molecules, the variation in adsorption affinity, and the fraction of adsorption sites being shared by
each adsorbate.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction ation, and easy recovery or reuse of adsorbent [9,10]. It is a powerful

The disposal of coloured contaminated wastewaters into aquatic
systems from the textile, paper, carpet, and printing industries may
cause significant negative impact on the environment [1–3]. Such
wastewaters are aesthetically and environmentally damaging due
to the high concentration of persistent colour and the toxic or even
carcinogenic nature to aquatic life and human beings [4]. Hao et
al. [5] reported that cationic dyes were more toxic than anionic
dyes, and anthraquinone-based dyes are more resistant to degra-
dation due to their fused aromatic structures. Chromium-based
dyes can release carcinogenic chromium ions into the water and
disperse dyes have a tendency to bio-accumulate [6]. As dyes are
designed to resist breakdown with time and exposure to sunlight,
water, soap, and oxidizing agent due to their complex structure and
synthetic origins, they cannot be easily removed by conventional
physical, chemical or biological wastewater treatment processes,
such as flocculation–coagulation, ozonation, aerobic or anaerobic
digestion [7,8]. The removal of dyes from aqueous system has been
a technological challenge for many decades.
Comparing with other wastewater treatment, adsorption as
purification and separation technique has been shown to be one
of the effective and relatively cheap methods for removing dyes
and offering some advantages, such as high efficiency, simple oper-
∗ Corresponding author. Tel.: +852 23587134; fax: +852 23580054.
E-mail address: kexhu@ust.hk (X. Hu).
physiochemical wastewater treatment process which involves pas-
sive separation of adsorbate from an aqueous phase onto a solid
phase [3,11]. Adsorption process is often carried out in a batch
mode by adding adsorbent into a vessel which contains contam-
inated water, stirring the mixture for a sufficient time, then letting
the adsorbent settle, and drawing off the cleaned water [12]. After
adsorption, the dissolved dye molecules are attached onto the
adsorbent surface and the exhausted adsorbent might be regener-
ated for reuse purpose. The colour removal efficiency is affected by
many physical–chemical factors, such as the type and the structure
of dye, the chemical nature and surface properties of the adsorbent,
and most importantly the interaction between dye and adsorbent.
It is also influenced by the operating conditions such as dye con-
centration, adsorbent dosage, contact time, solution temperature,
pH, and the ionic strength [3].
The primary requirement for an economic adsorption process is
the selection and preparation of an adsorbent in which high adsorp-
tion capacity and sufficient selectivity are needed [13]. There have
been considerable amount of adsorbents applied in dye removal
study, ranging from activated carbons to agriculture waste mate-
rials, industrial by-products, biosorbents and clays [3]. Activated
carbons have been the most commonly used adsorbents because of
their enormous surface area and high adsorption capacity despite
the high cost to run the adsorption process [13,14]. Layered materi-
als with interlamellar reactivity, such as clays, have been tested as
alternative low-cost adsorbents due to their abundance in nature
and unique ion exchange and intercalation properties [15,16].

1383-5866/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2009.03.012
 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225 219

Bentonite, predominantly montmorillonite, is the most common Table 1

mineral within the smectite group of 2:1 clay minerals. Because of
the isomorphous substitution, bentonite has net negative charges
on its layer lattice. This kind of charge is normally balanced by the
so-called exchangeable cations which can be replaced by others
[17–19]. The application of bentonite as an adsorbent is largely
based on its cation exchange property. However, it is this prop-
erty which makes bentonite unlikely to adsorb anionic species from
effluent. Research effort is therefore needed to improve its adsorp-
tion property. Currently, bentonite modification has been focused
on thermal treatment, ion exchange with cationic surfactants, acid
activation, and pillaring [10,20–23] which are found unsuitable for
this project. In our research, LDH-modified bentonite, a compos-
ite adsorbent, has been developed by introducing an exchangeable
anion into its structure with the expectation to remove anionic
dyes. The investigation on the selection of the modifying material,
and the optimisation of the modification process has been reported
elsewhere [24].
To investigate the adsorption process, single solute adsorption is
normally involved. The equilibrium isotherm technique has always
been used to describe the process because it is very important
to understand the adsorption process. The isotherm is normally
obtained at constant temperature when the adsorption equilibrium
has been attained. However, in many practical systems, a num-
ber of components from different categories are usually involved
in a single dyeing process. This kind of adsorption process will
become more complicated because of the competition between
adsorbates and the final distribution of components in both solid
and liquid phase [25]. In the study of multicomponent acid dye
adsorption onto activated carbon, Choy et al. [26] pointed out that
the adsorption mechanism may involve dye molecular size and
the specific chemical group participation in the adsorption pro-
cess.
This paper reports the adsorption equilibrium study of the ben-
tonite composite adsorbent for the removal of two commercial dyes
from aqueous solution. The adsorption experimental data of single
component capacities were estimated by fitting the experimental
data to widely accepted adsorption equilibrium isotherm models.
To better understand the adsorption process, the equilibrium study
on binary component system was also performed.
2. Materials and methods
2.1. Bentonite
Bentonite, a natural clay, with cation exchange capacity (CEC) of
75 mequiv./100 g for the product ActiveGel, was received from the
Unimin Australia Limited. It was used without any further purifica-
The composition of bentonite (in wt.%).
SiO2 Al2 O3 MgO Fe2 O3 Na2 O CaO K2 O TiO2 Others
65 16.28 3.98 3.75 1.75 0.75 0.29 0.27 0.09
tion. The composition of bentonite as oxide form provided by the
manufacturer is listed in Table 1.
2.2. Modification of bentonite
The composite adsorbent used in this project was LDH modi-
fied bentonite. LDH, a layered double hydroxide, as the modifying
anionic clay, with a designed formula of Mg2 Al(OH)6 Cl·2H2 O, was
synthesised in our laboratory according to the procedure reported
earlier [27]. In the modification process, highly dispersed bentonite
suspension was reacted with LDH colloid with weight ratio of 1:1
at room temperature for sufficient time. The resulting material
was separated, purified, and dried before being calcined at 673 K
in a muffle furnace for 4 h. This modified bentonite is denoted as
1.0L1BC. The details of the modification and optimisation processes
were reported elsewhere [24].
2.3. Adsorbate
Two commercial dyes, namely Acid Red 18 (AR18) and Acid Yel-
low 23 (AY23), were selected as adsorbate in this study because they
are widely used in dyeing wool, silk and other protein fibres, and
synthetic fiber nylon in industry. These dyes were purchased from
Sigma–Aldrich Australia. Their structure and properties are illus-
trated in Table 2, including colour index number, formula weight,
and maximum wavelength [28].
2.4. Determination of dye concentration
Aqueous dye solution was obtained by dissolving the dye into
distilled water at a certain concentration. To determine the dye
concentration, a calibration curve was first obtained from a series
of dye solutions with predetermined concentration. The maximum
absorbance of the dye was confirmed by scanning the dye aqueous
solution over the spectral range of 350–650 nm by using UV–vis
spectrophotometer (SHIMADZU UV-1206). The absorbance of those
standard samples was then measured at the corresponding maxi-
mum wavelength. A linear relationship between the absorbance
and the dye concentration was obtained to which it is called cali-
bration curve. In adsorption experiments, dye concentration can be
determined by following the equation and the constant acquired
from the calibration curve.

Table 2
Structure and properties of selected dyes.

Name Chemical structure Colour index number F.W. max (nm)

Acid Red 18 (AR18) 16255 604.48 506

Acid Yellow 23 (AY23) 19140 534.37 425

220 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225
Table 3
Initial single and binary dye solutions for adsorption equilibrium isotherm study.
Dye solution Concentration ratio Dye initial concentration range
(mg/L)
AR18 60–420
AR18 and AY23 1:1 AR18: 30–210; AY23: 30–210
1:0.25 AR18: 60–420; AY23: 15–105
0.25:1 AR18: 15–105; AY23: 60–420
AY23 60–420
In the binary dye adsorption system, the calculation of dye
concentration for one dye should consider the interference from
another one because of the likely overlap of their absorbance.
In a binary system with components A and B, the measurement
would be conducted at wavelength 1 and 2 , respectively, giv-
ing absorbance of A1 and A2 . Dye concentration of the particular
component can be determined by the following equations [26]
kB2 A1 − kB1 A2
CA =
kA1 kB2 − kA2 kB1
kA1 A2 − kA2 A1
CB =
kA1 kB2 − kA2 kB1
where kA1 , kB1 , kA2 , and kB2 are the calibration constants for com-
ponents A and B at wavelength 1 and 2 , respectively.
2.5. Adsorption isotherm study for single and binary dye systems
2.5.1. Preparation and method for adsorption equilibrium study
Batch adsorption experiments were performed for the adsorp-
tion equilibrium isotherm study. A series of dye solutions with
consecutively increasing initial concentrations, as shown in Table 3,
were prepared by diluting a stock dye solution and placed in a
number of 250 ml conical flasks. A sufficient amount of adsorbent,
3 g/L, was brought into contact with these known volumes of dye
solutions. These testing bottles were sealed and agitated in a ther-
mostatic shaker at 30 ◦ C for 24 h, which was found to be sufficient to
attain equilibrium. After equilibrium, each sample withdrawn was
filtrated through a 0.45 ␮m membrane filter in order to remove
the particles from the system. The residual dye concentration was
then determined by the UV–vis. The mass balance at equilibrium is
defined as
(C0 − Ce )V = (qe − q0 )m
where q0 and qe are amount of dye adsorbed at initial and equilib-
rium, V is the sample volume and m is the mass of adsorbent.
A study on binary dye adsorption was performed in which the
concentration ratio of the two dyes was varied (Table 3), making up
three types of binary dye systems, i.e. CA = CB , CA mixed with 0.25CB ,
and 0.25CA mixed with CB , C refers to dye concentration, and A or B
denotes dye.
2.5.2. Single component adsorption equilibrium isotherms
Several adsorption equilibrium models have been widely
accepted for the study of liquid/solid phase adsorption behaviour,
such as the Langmuir, Freundlich, Redlich-Peterson. By applying
these models along with other techniques, some very useful infor-
mation about the adsorption system can be predicted, including
adsorption capacity, adsorption mechanism, and the interaction
between adsorbate and adsorbent [29,30].
2.5.2.1. Langmuir isotherm equation. The Langmuir equation was
developed to analyse the adsorption of gas molecules. It has been
successfully applied to many other real sorption systems, such as
adsorption from liquid phase. It is so far the simplest and the most
widely used expression. The application of the Langmuir equation
assumes that the adsorption site is homogeneous in which each
site accommodates one molecule or one atom; the adsorption is
monolayer coverage, and there is no interaction between adsorbed
molecules. The Langmuir isotherm is represented by the following
equation [31]
Q0 bCe
qe = (4)
1 + bCe
where qe is the amount of dye adsorbed per unit mass of adsor-
bent (mg g−1 ); Ce is the equilibrium dye concentration (mg L−1 );
Q0 and b are the Langmuir constants representing the monolayer
adsorption capacity (mg g−1 ) and the energy of adsorption (L mg−1 ),
respectively.
2.5.2.2. Freundlich isotherm equation. The Freundlich equation is
one of the earliest empirical equations explored for heterogeneous
systems and is not restricted to the formation of a monolayer. It is
very popular to be used for the adsorption of solute from aqueous
solution. The well-known expression of the Freundlich model is as
(1)
[30]
1/n
(2) qe = Kf Ce (5)
where Kf and n are temperature dependent Freundlich constants,
they reveal the adsorption capacity (mg g−1 ) and the intensity of
adsorption. The parameter n is usually greater than unity.
2.5.2.3. Redlich-Peterson isotherm equation. As a combination of
both Langmuir and Freundlich systems, this equation gives a com-
promise method to analyse the experimental data. It can be written
as [32]
K1 Ce
qe = p (6)
1 + K2 Ce
where K1 and K2 are Redlich-Peterson constants and p is the expo-
nent which lies between 1 and 0.
2.5.3. Binary component adsorption equilibrium study
In the study of binary dye adsorption process, two different
approaches have been adopted by researchers when preparing the
liquid phase system, one is the equal mass concentration, C0,A = C0,B
[26,33], and another one is to fix one component concentration at
different constant numbers [34,35]. In this work, the principle of
(3) the first method was adopted but the ratio of the two component
concentration was varied. The details of the initial concentration of
the two components in the binary system are introduced in Table 3.
The experimental results were analysed by the extended Langmuir
equation [30]
Q0,i bi Ce,i
qe,i =  (7)
1+ bi Ce,i
For two species A and B, for example, Eq. (7) can be expressed as
Q0,A bA Ce,A
qe,A = (8)
1 + bA Ce,A + bB Ce,B
Q0,B bB Ce,B
qe,B = (9)
1 + bA Ce,A + bB Ce,B
2.6. Characterisation methods
X-ray diffraction (XRD) pattern was obtained from random pow-
dered sample by using Rigaku Miniflex instrument with cobalt K␣
radiation at 30 kV and 15 mA to identify the specific crystal struc-
tures. The data was collected at a scanning speed of 2◦ /min over 2
range of 2–30◦ .
Scanning electron microscopy (SEM) analysis was performed by
using JEOL 6400 microscope with Pt coating. Transmission electron
 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225
Fig. 1. Adsorption equilibrium isotherm data of AR18 on 1.0L1BC fitting to various
isotherm equations.
microscopy (TEM) image was obtained with JEOL 2010 microscope
on dispersed sample deposited onto copper micro-grid.
Nitrogen adsorption/desorption isotherms were measured at
77 K with Quadrasorb SI (QuadraWin 2.0) apparatus. The samples
were degassed overnight at 473 K prior to the experiments. The spe-
cific surface area was calculated by the Brunauer, Emmett and Teller
(BET) equation using the adsorption data in the relative pressure of
0.05–0.3.
3. Results and discussion
3.1. Adsorption isotherm study for single solute
The adsorption equilibrium experimental data for dye AR18 and
AY23 onto the LDH-modified bentonite adsorbent, 1.0L1BC, are
presented in Figs. 1 and 2, respectively. The fitting results show
that the Freundlich and Redlich-Peterson isotherms correlate the
adsorption behaviour reasonably well compared with the Lang-
muir equation, indicating some heterogeneity of the adsorbent
surface. According to Giles classification for solution adsorption,
the isotherms for AR18 and AY23 are H type curves, featuring high
affinity adsorption. As we can see from each isotherm, it is verti-
Fig. 2. Adsorption equilibrium isotherm data of AY23 on 1.0L1BC fitting to various
isotherm equations.
221
Table 4
Adsorption parameters derived from nonlinear Langmuir, Freundlich and Redlich-
Peterson equations.
Isotherm equations Parameters AR18 AY23
Q0 (mg/g) 69.8 75.4
Langmuir b (L/mg) 14.71 56.07
r2 0.8923 0.795
kf 43.81 53.51
Freundlich 1/n 0.1267 0.0978
r2 0.9477 0.8285
k1 (L/g) 3159.68 8207.75
Redlich- k2 (L/mg) 61.5 133.07
Peterson p 0.9131 0.9378
r2 0.9711 0.8491
cal for the initial slope in which dye has been removed completely
in such dilute solutions, suggesting very high adsorption affinity
of dyes towards adsorbent. Following this sharp initial rise, the
isotherm reaches a plateau where the adsorption equilibrium has
been reached. All the available adsorption sites are full of dyes at
this stage and monolayer coverage has fulfilled. It would be difficult
for adsorbate to find more accessible site in this case due to the long
plateau [36].
The adsorption parameters derived from the three isotherms
are listed in Table 4. The Redlich-Peterson model exhibits the
best fitting results, evidenced by the higher correlation coeffi-
cients although both Langmuir and Freundlich models can provide
reasonable good fittings. This suggests the homogeneous and het-
erogeneous nature of the adsorbent surface to which the adsorption
process is complex. The adsorption capacities for AR18 and AY23
estimated from the Langmuir expression are at 69.8 and 75.4 mg/g,
respectively.
3.2. Dye adsorption mechanism study
It is estimated that many factors could play important roles on
the dye removal process, such as dye structure, adsorbent surface
chemical properties, and most importantly the specific interactions
between adsorbent and adsorbate.
AR18 and AY23 are water soluble acid dyes with substituted
sulfonic acid functional groups in their structure. There are three
sulfonic groups on AR18 structure in which two of them share one
benzene ring, while two such functional groups occupy two sep-
arate benzene rings for AY23 (Table 2). The adjacent location of
the two sulfonic groups and the unsymmetric ionic distribution of
AR18 might disturb its adsorption behaviour towards the adsor-
bent. On the other hand, more spatial area is needed for AR18 to be
accommodated on the adsorbent surface because AR18 needs three
active sites while AY23 only occupies two if they are adsorbed on
flat orientation. Considering the effect of molecular size for the two
dyes in which AR18 is higher than AY23, the diffusion of AR18 is
slower than that of AY23 both in aqueous solution and on the adsor-
bent surface, the adsorption capacity could suffer the consequence
[29].
The difference in adsorption capacity should be related to the
surface chemistry of the adsorbent. After the modification process,
the LDH-modified bentonite seems to compromise both bentonite
and LDH structures, evidenced by the peak at about 7◦ for ben-
tonite and the diffractions at 13◦ and 27◦ derived from LDH, as
shown in XRD patterns in Fig. 3. The obvious peaks suggest that
the modified materials exhibit well ordered crystal structure. The
SEM image of bentonite exhibits regular layered structure with a
very high aspect ratio (Fig. 4). After LDH modification, the small
flakes of LDH nanoparticles seem to be bound onto the bentonite
surface, evidenced by the small patches attaching on a big ben-
tonite sheet. This may be indicative of ordered nanocomposite in
222 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225

Fig. 3. XRD patterns for bentonite, its derivative and LDH.

Fig. 5. TEM image of LDH-modified bentonite (1.0L1B).

which LDH particles fill in the bentonite external and internal space
and intercalated into the bentonite surface. The TEM image in Fig. 5
provides insight into the structure and agglomeration within the
LDH-modified bentonite adsorbent. It is obvious that there are a
large number of overlapped hexagonal LDH molecules on the ben-
tonite surface. The LDH molecules in the composite adsorbent could
change bentonite surface chemical property and make considerable
contributions to the adsorption of the anionic dyes.
After the adsorption equilibrium experiment, all the dye loaded
adsorbents were collected and dried for the further nitrogen
adsorption characterisation. The results of the adsorbent 1.0L1BC,
dye AR18 and AY23 loaded samples are compared in Fig. 6. The
shape and the obvious hysteresis loop on these isotherms indi-
cate a predominant mesoporous structure with slit-shaped pores
or plate-like particles for these samples [37]. The surface area of

Fig. 6. Nitrogen adsorption isotherms of adsorbent 1.0L1BC, AR18-loaded, and

AY23-loaded samples. Solid symbols represent adsorption and open symbols for
Fig. 4. SEM image of bentonite (left) and LDH-modified bentonite (1.0L1B) (right). desorption.
 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225 223

Table 5
Structure parameters of adsorbent 1.0L1BC, AR18-loaded, and AY23-loaded samples.

Samples SBET (m2 /g) Vtotal (cm3 /g)

1.0L1BC 64.7 0.239

1.0L1BC-AR18 13.4 0.078
1.0L1BC-AY23 18.5 0.077

the adsorbent decreases dramatically after the adsorption of dyes,

as shown in Table 5, from 64.7 m2 /g for adsorbent to 13.4 m2 /g for
AR18 loaded sample, and to 18.5 m2 /g for AY23. This is indicative
that dye adsorption occurred inside the adsorbent gallery where
the organic dye molecules filled into the adsorbent porous system.
On the same reason, the considerable drop of the pore volume after
the loading with dyes could be explained. The large reduction hap-
pens to dye AR18 which is likely due to the pore blockage caused
by its big geometrical molecular size [38].
It is expected that the inherent anion exchange capacity derived
from LDH in adsorbent 1.0L1BC plays an important role for the
adsorption of anionic dyes. In aqueous solution, anionic dye, such
as dye with sulfonic functional group, dissociates negative anion
(Eq. (10)). Dye removal happens when the adsorbent is brought
into contact with the dye functional group. The adsorption pro-
cess is likely to be ion exchange, a unique property for clays, as the
removal of one anionic group is accompanied by the release of one
exchangeable anion (Eq. (11)) [39]. Because the adsorbent has been
calcined before the dye adsorption process, dye removal is quite
possible enhanced by the regeneration of LDH structure from its
mixed oxides (Eqs. (12) and (13)), causing the intercalation of the
anionic dye into the LDH structure [40]
Dye–SO3 Na  Dye–SO3 − + Na+
Mg2 Al(OH)6 Cl·2H2 O + Dye–SO3 −  Mg 2 Al(OH)6 O3 S–Dye
+ 2H 2 O + Cl−
400 ◦ C
2Mg2 Al(OH)6 Cl · 2H2 O −→ (Mg2 Al)2 O7 + 8H2 O + 2Cl− + others
(Mg2 Al)2 O7 + 2Dye–SO3 −  2Mg2 Al(OH)6 O3 S–Dye
To apply ion exchange model for the dye adsorption system, ion
exchange between A and B follows mass action law that can be
described as [41]
Fig. 7. Adsorption isotherms of AR18 on adsorbent 1.0L1BC in single, and
AR18 + AY23 binary system.
3.3. Binary dye adsorption
The adsorption behaviour of AR18 and AY23 in their binary sys-
tem has been studied and the results are presented in Figs. 7 and 8,
respectively. For comparison, the single dye equilibrium isotherm
is displayed together with the binary solute adsorption results. The
interaction between these two dyes can be observed when con-
sidering the two figures together. With the decrease of the AR18
fraction in the binary system, the adsorption of AR18 decreases
in Fig. 7 and meanwhile the adsorption of AR23 have increased
(10)
as illustrated in Fig. 8, evidenced by the plateau levels of these
isotherms. In each individual graph, as expected, the adsorption
capacity for AR18 or AY23 achieves the highest value in their
single component system. The available adsorption site is being
(11) shared by these two dyes. With the ratio change between these
two dyes, the adsorption capacity also alters. The trend of the
amount of dye adsorbed in these two figures is very similar but
the degree is different. When their fraction decreases from 1 to
0.25, the reduction of the amount of dye adsorbed for AY23 is
(12) more remarkable than that for AR18, from around 54 to 12 mg/g
for AY23, and from 52 to 15 mg/g for AR18. The adsorbent sur-
face has different affinity towards different dyes. Although the real
(13)
initial concentration in binary system of CA mixed with 0.25CB
is exactly the same with the single dye system, the amount of

A + B̄  Ā + B (14)

where overbar indicates the ionic species in the ion exchange phase.
The separation factor ˛A–B is defined as
qA CB
˛A–B = (15)
qb CA

The relationship between the separation factor ˛A–B in ion exchange

model and the Langmuir equilibrium parameter b has the following
form [42]

˛A–B = 1 + bC0 (16)

If ion A is preferred, the separation factor is larger than unity,

whereas if ion B is preferred, it is smaller than unity.
It is obvious that the separation factors are greater than unity
for the adsorption of the two dyes. Therefore, the LDH-modified
bentonite adsorbent is effective for the removal of AR18 and AY23 Fig. 8. Adsorption isotherms of AY23 on adsorbent 1.0L1BC in single, and
in aqueous solution. AY23 + AR18 binary system.
224 S. Qiao et al. / Separation and Purification Technology 67 (2009) 218–225
Fig. 9. Extended Langmuir equation (calculation) and experimental data for AR18 (left) and AY23 (right) adsorption in binary system AR18 + AY23 with CAR18 equal to CAY23 .
dye adsorbed is totally different between them. This suggests the
present of another dye do affect the adsorption behaviour of the cur-
rent dye. The competition between the two dyes for the available
adsorption sites changes the adsorption capacity. It is clear that the
multicomponent nature of the wastewater introduces additional
complications which requires many new factors to be taken into
account [43].
In binary system when the initial concentrations of these two
dyes are equal, their adsorption equilibrium experimental data are
presented in Fig. 9. The amount of dye adsorbed for AR18 is at about
35 mg/g which is higher than that of AY23 at 27 mg/g. The inter-
action between the two dyes in binary system is obvious because
in single dye system the adsorption capacity of them are in the
descending order of AY23 > AR18 (Table 4). However, in binary sys-
tems the dye with relative lower adsorption capacity in the single
component system is preferentially to be adsorbed. The existence of
AY23 enhances the affinity of AR18 towards adsorbent. AR18 is more
favourable to be removed by adsorbent 1.0L1BC than AY23 from
their binary system. Allen and co-workers had the similar results
regarding the adsorption of basic dye in binary component system
[33].
It has been reported that the extended Langmuir equation could
be used in multicomponent dye adsorption system, and in some
cases, good degree of prediction could be achieved [26]. Therefore,
in this work, the experimental data of binary dye adsorption at equal
initial concentration, for the pair of AR18 and AY23 were analysed
by this model and the results are also displayed in Fig. 9. The solid
lines in these plots are the prediction results using the extended
Langmuir equation. It can be seen that there is significant differ-
ence between the experimental data and the plots predicted by
the extended Langmuir equation in all systems. The amount of dye
removed predicted for AR18 is much lower than the experimen-
tal results, but much higher for AY23. It is not surprising to get
such poor prediction results because the application of extended
Langmuir equation is under the same assumption with the pure
component system, i.e. the adsorbent surface is homogeneous and
there is no interaction between the adsorbed molecules. In fact,
these requirements are hardly fulfilled in real systems because the
effect of surface heterogeneity and interaction between adsorbate
molecules in binary system are generally significant. Therefore, the
extended Langmuir model is not suitable to represent the result in
competition system.
4. Conclusions
This paper presented the equilibrium study on the adsorption
of two commercial dyes, namely Acid Red 18 (AR18) and Acid Yel-
low 23 (AY23), by using the LDH-modified bentonite adsorbent.
In the single component dye adsorption system, the equilibrium
experimental data can be analysed well with three different models,
Langmuir, Freundlich, and Redlich-Peterson. The Redlich-Peterson
model yields the best fitting results, indicating the complex feature
of the adsorbent surface. The adsorption capacity evaluated from
the Langmuir equation was utilized to interpret the experimental
results and found to be reasonable. The adsorbent is effective in
the removal of these two anionic dyes. Three binary dye adsorp-
tion systems were investigated. It was found that the adsorption in
multicomponent wastewater system is very complicated. The avail-
able adsorption site is being shared by the two components but the
fraction is variable. The present of AY23 enhances the adsorption
of AR18 due to the different affinity of adsorbent towards different
dyes in the dye mixture.
The experiment study reveals that the LDH-modified bentonite
adsorbent is a promising adsorbent for the application of anionic
dye removal. However, theoretical calculation indicates that the
extended Langmuir equation fails to represent the experimental
results well because of the significant competition and interaction
between the dyes.
Acknowledgements
This work was financially supported by the Australian Research
Council (ARC) and Phoslock Water Solutions Ltd Australia through
the Linkage Project Program, the ARC Centre of Excellence for Func-
tional Nanomaterials, and the Research Grants Council (RGC) of
Hong Kong (CERG, Project No. 613705).
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