Chemical Engineering Journal 191 (2012) 162–170

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Single and multicomponent acid dye adsorption equilibrium studies on tyre

demineralised activated carbon
O.S. Chan a , W.H. Cheung a,b , G. McKay a,∗
a
Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
b
School of Chemical and Biomolecular Engineering, The University of Sydney, NSW, 2006, Australia

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

Article history: This study investigated the adsorption properties of demineralised activated carbon adsorbents produced
Received 4 January 2012 from waste tyre char. The produced carbon was tested for its dye adsorption capacities in the textile
Received in revised form 28 February 2012 industry effluent treatment. Two acid dyes with different molecular sizes were used, namely Acid Blue
Accepted 28 February 2012
25 (AB25) and Acid Yellow 117 (AY117) to simulate the textile effluent. In a single component system,
it was found that the larger size dye, AY117, showed little adsorption and for both dyes the maximum
Keywords:
capacity is higher than the commercial activated carbon F400 for both dyes. Furthermore, the results of
Waste tyre
the single component system were fitted to equilibrium isotherm models using Langmuir, Freundlich,
Activated carbon
Dye removal
Redlich–Peterson and Langmuir–Freundlich or Sips for the single component system. The adsorption
Adsorbents of AB25 followed the Langmuir isotherm, while the adsorption of AY117 can be better described with
Binary system Langmuir–Freundlich model. A binary AB25–AY117 mixture was used to test the possibility of the molec-
ular sieve effect. For the binary component system, it is found that none of the predictive models work
well, hence the system is non-ideal. Overall, the correlative extended Freundlich isotherm models were
the best to fit the experimental data.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Wastewater treatment is one of the major problems that must
be dealt with in everyday life. In order to reduce the severe prob-
lems caused by water pollution, many countries and environmental
protection authorities are continually restricting the use of chem-
icals as well as tightening on the discharge limits. Consequently,
wastewaters containing toxic materials such as dyestuffs, organic
pollutants and metal ions must be carefully treated before dis-
charged. Adsorption is one of the most cost effective and efficient
technologies used in wastewater treatment while activated carbon
has been one of the most widely used adsorbents for adsorption
processes in wastewater treatment. During the past few years,
the decreasing availability and rising production costs have led
to sharp price rises for activated carbon and the prices of coal-
based grade has risen by 80% between the beginning of 2007 and
mid-2008 [1]. The unbalance of demand and supply also exerted
pressure on prices of other grades of activated carbon. As a result,
many researchers have been focusing on the production of acti-
vated carbon-like material by using low cost precursors, such as
∗ Corresponding author. Fax: +852 23580054.
E-mail address: kemckayg@ust.hk (G. McKay).
sawdust [2,3], cherry stones [4], peanut shell [5], bagasse [6] and
bamboo [7].
It is estimated that the total number of waste tyres in China
has already reached more than 112 million pieces in 2004 and
the amount projected to 2010 will be over 200 million [8]. The
most common disposal method for used tyre is to stockpile
in landfill. Landfilling the waste tyres is an uneconomical and
non-environmental friendly disposal method. Those chemically
cross-linked rubber molecules cannot be easily biodegraded and
neither melt nor dissolve. Stockpiling of tyres poses a fire haz-
ard and they can become a breeding ground for mosquitoes and
rodents. Therefore, reuse or recycling of waste tyres has become an
important social concern worldwide.
A better approach is reprocessing the tyres by pyrolysis into
more valuable products such as liquid fuel, gaseous fuel and tyre
char. However, the process is very energy intensive, even though
the tyre derived fuel from the pyrolysis produces the same amount
of energy as oil and 25% more than coal [9]. There will be 30–40 wt%
solid char produced during pyrolysis; hence, the process econ-
omy depends strongly on its application and market value. Studies
showed the activation of the tyre char could actually result in a
product with desirable properties such as high surface area and
porosity as commercially available activated carbon [10–16]. As a
result, this will be a sound solution to solve both the wastewater
treatment problem and the waste tyre problem.

1385-8947/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.02.089
 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170 163

2. Materials and methods

Nomenclature
2.1. Adsorbents
aL Langmuir isotherm constant (L/mmol)
aF Freundlich isotherm constant (L/g) The starting material was the tyre char, TC, from a commercial
aLF Langmuir–Freundlich isotherm constant (L/mmol) waste tyre pyrolysis plant in China. The received tyre char under-
aR Redlich–Peterson isotherm constant (L/mmol) went a series of pre-treatments prior to the activation to ensure
aij dimensionless extended Freundlich isotherm con- all the tyre chars are consistent in terms of quality. First, the tyre
stant. char was crushed and sieved to a particle size smaller than 2 mm,
bF dimensionless Freundlich isotherm constant and then the residual steel was removed by a magnet. Finally, the
bR dimensionless Redlich–Peterson constant tyre char was pyrolysed once again at 550 ◦ C for 2 h to ensure the
Co initial liquid-phase concentration (mmol/L) volatile compounds in the char were removed.
Ce equilibrium liquid-phase concentration (mmol/L) After the pre-treatment, approximately 120 g of tyre char was
KiF dimensionless extended Freundlich isotherm con- demineralised with HCl at different conditions and then washed
stant until the pH was close to that of deionised water (∼5.6) and dried
KL Langmuir isotherm constant (L/g) in a vacuum oven. Approximately 30 g of demineralised tyre char
KL,i Langmuir isotherm constant in multicomponent was placed into the horizontal furnace for activation. Nitrogen gas
(L/g) (N2 ) was used as a purge gas for 1 h before heating up to ensure the
KLF Langmuir–Freundlich isotherm constant (L/g) removal of residual air. The tyre char was then heated at 15 ◦ C/min
KR Redlich–Peterson isotherm constant (L/g) until the desired temperature was achieved. The product was then
m weight of adsorbent (g) activated isothermally for different periods of time using steam
n dimensionless Langmuir–Freundlich isotherm con- from water feed as oxidising agent at a flowrate of 0.45 mL/min
stant and with 100 mL/min N2 as carrier gas. After the activation, the
nij dimensionless extended Freundlich isotherm con- furnace was cooled down with the N2 purging continuously until
stant the temperature reached below 200 ◦ C. The activated carbon was
P dimensionless P-factor washed with deionised water until the pH came close to that of
qe equilibrium solid-phase concentration (mmol/g) deionised water and then the activated char was dried in an oven
qmono monolayer capacity of Langmuir equation (mmol/g) at 100 ◦ C before further use. The methods of characterisation were
s mole fraction of sorbate in adsorbed phase described in detail elsewhere [17], and the physical properties of
SSE sum of the squares of the error nine activated carbons, C1–C9 were prepared under the conditions
t min contact time listed in Table 1.
T temperature (K)
V liquid-phase volume (L)
2.2. Sorbates

Greek letters
AB25 and AY117 were used in the study of single component and
 dimensionless interaction factor
equimolar binary systems. Properties of the acid dyes are shown in
spreading pressure
Table 2.
max maximum absorption wavelength

2.3. Aqueous adsorption test

Superscript
o single component
Subscripts
calc calculation
exp experiment
i ith component in a multisolute system
j jth component in a multisolute system
In this study, the activated carbon was produced from the
char resulting from pyrolysis of waste tyre. Adsorption capac-
ities of the produced carbon for acid dyes were investigated
and in order to simulate effluents treatment from the textile
industry, two acid dyes with different molecular sizes were
used, namely, Acid Yellow 117 (AY117) and Acid Blue 25
(AB25). The single adsorption data were then modelled using
the conventional isotherm equations including Langmuir, Fre-
undlich, Redlich–Peterson and Langmuir–Freundlich isotherms.
Similarly, the binary dye adsorption test was conducted and
was also modelled with conventional isotherm models including:
extended Langmuir, extended-Redlich–Peterson (RP), extended-
Langmuir–Freundlich (LF) and some empirical models including:
extended-Freundlich, P-factor and the interaction factor model and
finally, the ideal adsorbed solution theory (IAST)-Langmuir and
IAST-Langmuir–Freundlich isotherms.
A constant mass of adsorbent (0.05 g) was weighed into 60 mL
glass bottles and contacted with 50 mL of dye solutions of different
initial concentration from 0.025–2 mmol. The bottles were sealed
and placed in a shaker until equilibrium was reached. Samples were
then withdrawn by syringe, filtered through a 0.22 ␮m syringe fil-
ter, diluted to an appropriate level and analysed using a Varian Cary
1E UV/vis spectrophotometer to determine the residual equilib-
rium liquid-phase dye concentration. The equilibrium adsorption
capacity, qe (mmol/g), at different dye concentrations was deter-
mined by a mass balance on the dye:
V
qe = (Co − Ce ) (1)
m
where Co (mmol/L) is the initial concentration, Ce (mmol/L) is the
equilibrium concentration in the liquid phase, V is the volume of
liquid phase (L), and m is the mass of the absorbent (g).
For a binary system, the calibration for cross interference was
carried out as previously described [18]. Dye concentrations were
calculated as follows: for a bisolute system of components A and B
measured at 1 and 2 , respectively to give optical densities of d1
and d2 :
kB2 d1 − kB1 d2
CA = (2)
kA1 kB2 − kA2 kB1
kA1 d2 − kA2 d1
CB = (3)
kA1 kB2 − kA2 kB1
164 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170

Table 2

surface area (m2 /g)

Properties of the acid dyes.

t-Plot external
Acid Blue 25 Acid Yellow 117

Abbreviation AB25 AY117

MW(g/mol) 416.4 848

97.9
Charge −1 −2

120
347
931
203

96
157
119
374
Width (Å) 1.25E+01 2.91E+01
Depth (Å) 1.02E+01 2.02E+01
t-Plot mesopore

Thickness(Å) 2.53E+00 4.01E+00

volume (cc/g)

where kA1 , kB1 , kA2 and kB2 are the calibration constants for com-
0.391
0.697
1.657
0.519
0.345
0.328
0.433
0.386
0.743
ponents A and B at the two wavelengths 1 and 2 , respectively.
The optical density values for the acid dyes at two different
surface area (m2 /g)

wavelengths are shown in Table 3.

t-Plot micropore

3. Theory

3.1. Single isotherm modelling

260
394
31
383
270
201
346
277
414

The experimental data were fitted into the Langmuir [19], Fre-
t-Plot micropore
volume (cc/g)

undlich [20], RP [21] and LF [22] equations listed below:

KL Ce
Langmuir isotherm : qe = (4)
0.143

0.193

0.177
0.146
0.213
0.202
0.011

0.105
0.104

1 + aL Ce
and
Average pore
diameter (Å)

KL
Qmono = (5)
aL
53.98
48.52
70.62
48.64
60.63
40.85
48.57
53.67
48.55

where qe is the solid phase sorbate concentration at equilibrium

(mmol/g), Ce is the aqueous phase sorbate concentration at equilib-
rium (mmol/L), KL is the Langmuir isotherm constant (L/g), aL is the
volume (cc/g)

Langmuir isotherm constant (L/mmol) and Qmono is the Langmuir

Total pore

monolayer capacity.
0.534
0.899
1.698
0.712

0.432

0.532
0.956
0.45

0.61

Freundlich isotherm : qe = aF CebF (6)

where aF is the Freundlich constant (L/g) and bF is the heterogeneity

BET surface
area (m2 /g)

factor.
KR Ce
380
741
962
586
368
297
503
396
788

Redlich–Peterson isotherm : qe = (7)

1 + aR Ce bR
Time

where KR is the Redlich–Peterson isotherm constant (L/g), aR is the

4.5
(h)

3
6
6
6
3
3

3
6

Redlich–Peterson isotherm constant (L/mmol) and bR is the expo-

Temperature

nent which lies between 0 and 1.

n
KLF Ce LF
Langmuir–Freundlich isotherm : qe = (8)
nbLF
(◦ C)

1 + aLF Ce
950
950
950
900
950
900
925
900
900

where KLF is the LF model isotherm constant (L/g), aLF the LF con-
Preparation condition and physical properties of activated carbon.

concentration (M)

stant (L/mmol) and nLF the LF model exponent.

3.2. Multicomponent isotherm studies

Acid

Multicomponent equilibrium modelling has gone through many

1
3
1
1
3
3
2
1
3

stages of development since the beginning of this century when

Demineralisation

none of the multicomponent equilibrium studies dealt with com-

petitive adsorption and a few only were concerned with the
time (h)

Table 3
24
24
6
24
6
24
15
6
6

Constants for the calculation of dye concentrations in mixtures from optical density
values in mg/L.
ratio (mL/g)
Acid/char

Wavelength (nm) Wavelength (nm)

−1 −2
17.5
30
30
5
5
5
5

30
30

Name of Dye 601 438

−1 k11 k12
Sample

Acid Blue 25 0.0295 0.0011

Table 1

−2 k21 k22
C1
C2
C3
C4
C5
C6
C7
C8
C9

Acid Yellow117 0.00007 0.0557

 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170 165

selectivity of adsorption processes, several widely used predictive
and correlative models listed in the following section are used to
fit the experimental data.
3.2.1. Extended Langmuir isotherm
Extended Langmuir isotherm [23,24],
o C
KL,i e,i
qe,i =  (9)
1+ aoL,i Ce,i
where qe,i is the solid phase sorbate concentration at equilib-
rium (mmol/g) for component i, Ce,i is the aqueous phase sorbate
concentration at equilibrium (mmol/L) for component i, KL,i o is
the single-component Langmuir isotherm constant (L/g) for com-
ponent i, aoL,i is single-component Langmuir isotherm constant
(L/mmol) for component i. It should be noted that the extended
Langmuir isotherm provides reasonable estimates for multicom-
ponent system as long as the qe values for each solute obtained
from single isotherm model are close to each other.
3.2.2. Extended Langmuir–Freundlich equation
The extended Langmuir–Freundlich equation [25,26] is shown
in Eq. (9)
o C 1/bLF ,i
KLF,i e,i
qe,i =  1/bLF ,j
(10)
1+ aoLF,j Ce,j
where qe,i is solid phase sorbate concentration in equilibrium
(mmol/g) for component i, Ce,i is the liquid phase sorbate con-
centration in equilibrium (mmol/L) for component i, KLF,i o is the
Langmuir–Freundlich isotherm constant (L/mmol) for component
i, aoLF,i is the Langmuir–Freundlich isotherm constant (L/g)for com-
ponent i and 1/bLF is the Langmuir–Freundlich isotherm exponent.
3.2.3. Extended Redlich–Peterson isotherm
The extended Redlich–Peterson equation [27] is expressed as,
o C
KR,i e,i
qe,i =  (11)
ˇo
1+ aoR,i Ce,ii
where qe,i is solid phase sorbate concentration in equilibrium
(mmol/g) for component i, Ce,i is liquid phase sorbate concentration
o is Redlich–Peterson
in equilibrium (mmol/L) for component i, KR,i
o
isotherm constant (L/g) for component i, aR,i is Redlich–Peterson
isotherm constant (L/mmol) for component i and ˇi is the
Redlich–Peterson isotherm constant, dimensionless, for compo-
nent i.
3.2.4. Extended Freundlich isotherm
The extended Freundlich isotherm [28] has the following for-
mula for binary mixtures:
for systems with significant non-ideal effects and heterogeneous
surfaces.
3.2.5. P-factor
It is an easy-to-use method based on introducing a “lumped”
capacity factor Pi [31] and is expressed as,
(KLi /aLi )single solute
Pi = (14)
(KLi /aLi )multisolute
This model assumes the form of Langmuir isotherm; hence
for each component i, the multicomponent isotherm equation is
described as:
o
1 KLi Cei,single
qei,multi = (15)
Pi 1 + aoLi Cei,single
3.2.6. Interaction factor
Schay et al. [32] proposed the interaction factor, i for the ith
component in a system of N components.  is specific to each com-
ponent i and is a function of all other components in solution. The
calculation of the interaction factor is based on minimising the error
function. Incorporating this approach with the Redlich–Peterson
isotherm, Mathews [33] presented the following,
Ki (Ce /i )
qe,i = (16)

n
1+ aj (Ce,j /i )
j=1
3.2.7. Ideal adsorbed solution theory (IAST)
The IAST proposed by Myers and Prausnitz is a multicompo-
nent adsorption model; it provides a thermodynamically consistent
and practical method for predicting binary sorption isotherms
using single component isotherm data alone [34] and was subse-
quently extended to adsorption from aqueous solutions by Radke
and Prausnitz [35].
In order to use the IAST to predict multicomponent adsorption
equilibria using the single component data alone, it is necessary to
determine values for two variables – the solid-phase mole fractions
and the spreading pressure simultaneously. The solution method
presented below incorporates two different isotherm equations;
they are the Langmuir and Langmuir–Freundlich equations.
From the mass balance for each non-volatile component i, the
sum of the material in the solid phase and the liquid phase at equi-
librium must be equal to its initial solution phase concentration,
i.e.
M
C0,i = Ce,i + q (17)
V e,i
where M is the mass of adsorbent and V is the volume of the solu-
tion. From the overall mass balance, the sum of the mole or mass
fractions in each phase must be exactly equal to unity, i.e. for the
solid phase:

o C 1
KF,1
n +n11 
n

qe,1 =
e,1
(12) si = 1 (18)
n n
11
Ce,1 + a12 Ce,2
12
i=1

o C 2
KF,2
n +n22 The IAST dictates that the spreading pressure should be constant
e,2
qe,2 = n n (13) for each component in a given system:
22
Ce,2 + a21 Ce,1
21

1 = 2 = ··· = n (19)
where n11 , n12 , n22 , n21 , a12 and a21 are correlative constants
obtained by experimental binary data of components 1 and 2, 3.2.7.1. Langmuir isotherm in IAST. Using the Langmuir isotherm as
respectively. McKay and Al-Duri adapted the method and modified a basis, the spreading pressure, , can be evaluated by McKay and
the evaluation of correlation factors so as to reduce the exten- Al-Duri [18]
sive calculation procedure. They obtained excellent agreement  Ce
A qe KL
between the experimental and theoretical results for dye/carbon = = dCe = ln(1 + aL Ce ) (20)
and dye/peat systems [29,30]. It is a method highly recommended RT 0
Ce aL
166 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170

Hence, transforming each of the terms in Eq. (17) into those 1

based on single-component data gives the following for one com- 0.9
ponent of a multicomponent system: 0.8
⎡ ⎞−1 ⎤ ⎛ 0.7
⎢ o m⎝ 
n
⎠ ⎥

Qe(mmol/g)

sj 0.6 C5 AB25
C0,i = ⎣Ce,i + ⎦ si (21)
V qo e,j 0.5
C7 AB25
j=1
C9 AB25
0.4
o C5 AY117
Ce,i = Ce,i si (22) 0.3
C7 AY117
⎛ ⎞−1 0.2 C9 AY117

n
sj 0.1
qe,i = si qT = si ⎝ o
⎠ (23)
qe,j 0
j=1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Rearranging Eqs. (4) and (20) allows the following to be sub- Ce(mmol/l)
stituted into Eq. (21) to obtain the equivalent pure component
Fig. 1. The experimental data of single component isotherm C5, C7, C9.
fluid and adsorbed-phase concentrations at the specified spreading
pressure:
more interested in the data fitting of monolayer concentration, it is
exp( (aoL,i /KL,i
o )) − 1
appropriate to use this error analysis method here.
o
Ce,i = (24)
aoL,i
o     4. Results and discussion
KL,i aoL,i
qoe,i = 1 − exp − (25)
aoL,i o
KL,i 4.1. Single dye adsorption equilibrium

Completing the development of the first equation set. All nine activated carbons, C1–C9 were tested for both Acid Blue
25 and Acid Yellow 117 adsorption. Equilibrium isotherms for three
3.2.7.2. Langmuir–Freundlich isotherm in IAST. By applying the carbon 5, 7, and 9 are plotted in Fig. 1. As shown, it is in a good order
Langmuir–Freundlich isotherm, the spreading pressure, , can be of increasing surface area for tyre activated carbon.
evaluated: The adsorption capacity of AB25 and AY117 is quite differ-
 Ce ent, where the adsorption capacity of the AB25 is higher than the
A qe KLF
= = dCe = ln(1 + aLF Ce bLF ) (26) AY117. AY117 is found to be more difficult to be adsorbed due to its
RT 0
Ce bLF aLF
larger size and the negative charge on both ends, the dye molecule
Similarly, rearranging Eqs. (8) and (26) allows the following to be would be adsorbed flat on the carbon surface, hence blocking some
substituted into Eq. (21) to obtain the equivalent pure component available surface active sites and pores for the dye to penetrate
fluid and adsorbed-phase concentrations at the specified spreading further inward. It is generally accepted that the pore size of the
pressure: adsorbent has to be 1.7 to 2 times of the adsorbate dimension.
 1/bLF,i From Table 1, the average pore size is between 40 and 70 Å, which
exp(( aoLF,i boLF,i )/KLF,i
o )−1
o
Ce,i = (27) means the AY117 could be adsorbed with one end attached to the
aoLF,i carbon surface and the other end point towards outside where
o    negative–negative repulsion will take place that significantly low-
KLF,i (aoLF,i boLF,i ) ered the adsorption capacity.
qoe,i = 1 − exp − (28)
aoLF,i o
KLF,i The difference in adsorption behaviour between the acid dyes
can be attributed to the molecular size of the dyes [36]. By compar-
For both equation sets, an appropriate convergence scheme (e.g. ing the molecular sizes of both acid dyes (Table 2), AB25 is much
Newton–Raphson or secant) can then be used to identify the values smaller than AY117. Hence, it is possible for the smaller dye to
of and Sj by minimising the SSE error between the experimen- penetrate deeper into the interior of the activated carbon with less
tal initial liquid-phase solute concentrations and those predicted steric hindrance.
by the IAS model. Thus, multicomponent equilibrium adsorption It is believed the main mechanism of the adsorption might be
data (21) can be derived using only single-component isotherm the dispersive interactions between the delocalised ␲ electrons in
parameters, system parameter (M and V) and the initial solute con- the carbon basal planes and the free electrons in the dye molecules
centration for each component. (aromatic rings) [37–41]. Many researchers agree that the removal
of the dyes can be related to the carbon surface and porosity char-
3.3. Error analysis acteristics, which determine the accessibility of the dye molecules.
Since the order of magnitude of adsorption capacity is nearly in
In this study, the sum of the squares of the error, SSE, is used the same order of surface area of the carbon, this gave an indica-
for the optimisation to find the parameters of all kinds of isotherm. tion of the strong influence of the physical properties towards the
The sum of the squares of the error method can be represented by adsorption capacity. Fig. 2 shows the effect of total surface area on
the following equation: the dyes adsorption. There is a general adsorption trend of higher
surface areas which will give higher adsorption capacities.
SSE = (qecalc − qeexp )2 (29)
From the literature, the commercial activated carbon Calgon
Although this is the most common error function in use, it has Filtrasorb 400 (F400) is widely used for wastewater and drinking
one major drawback, isotherm parameters derived using this error water treatment, it has an equilibrium capacity of 0.8 mmol/g of
function will provide a better fit as the magnitude of the errors and AB25, 0.12 mmol/g of AY117 [7,11]. Overall, the mesoporous tyre
thus the squares of the errors increase – biasing the fit towards data activated carbons have higher adsorption capacities than the com-
obtained at the high end of the concentration range. Since we are mercial F400, especially in the case of AY117.
 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170 167

1.20E+00

8.24E−02
9.87E−01
9.74E−01
1.72E−01
8.24E−02
4.65E−02
3.73E−01

3.74E−01
9.80E−02
1.00E+00

SSE
y = 0.001x - 0.191
R² = 0.988
Qmono (mmol/g)

8.00E-01

5.29E−01
1.45E−01

1.63E−01

6.41E−01
3.01E−01
5.03E−02

3.09E−02
1.40E−01
8.00E−02
6.00E-01
AB25

nLF
4.00E-01 AY117
y = 0.000x - 0.156
R² = 0.958

aLF (L/mmol)
2.00E-01

6.90E−01
1.00E−02

3.42E+01
5.60E+01
2.82E+00
4.71E+00

1.36E+00
2.51E+00
1.26E+00
Langmuir–Freundlich
0.00E+00
0 200 400 600 800 1000 1200
Surface Area (mmol/L)

5.74E−01
7.75E−01
8.65E−01

7.10E−01
1.77E+01

3.27E+01
3.21E+00
7.36E+00

1.19E+00
KLF (L/g)
Fig. 2. The effect of BET surface area on the adsorption of single AB25 and AY117.

The experimental data of the dye systems adsorbed on the car-

8.23E−02
9.87E−01
9.74E−01
1.72E−01
8.24E−02
4.65E−02
3.73E−01
9.27E−02
3.74E−01
bons are substituted into four equilibrium isotherm models namely
Langmuir, Freundlich, Redlich–Peterson, Langmuir–Freundlich

SSE
isotherms, respectively and the best-fit model for the sorption
system has been determined with minimised SSE. The adsorption

9.65E−01
9.21E−01
9.52E−01
9.75E−01
9.47E−01
9.86E−01

9.53E−01
1.00E+00

1.00E+00
parameters are shown in Tables 4 and 5. It shows that the adsorp-
tion of AB25 behaved in a more Langmuir type, while the adsorption

bR
of AY117 can be better described with the Langmuir–Freundlich
model.

aR (L/mmol)

8.19E+02
7.14E+04

3.46E+05
1.53E+02
3.24E+02
9.05E+02

1.09E+03
2.08E+03
4.00E+02
4.1.1. Binary component system

Redlich–Peterson
Three of the tyre activated carbon C5, C7 and C9 with increasing
in the order of surface area and total pore volume were further

1.23E+02
7.59E+02

3.55E+02
5.15E+02
1.83E+05
5.72E+01
3.12E+02
1.09E+03
4.08E+04
tested for the binary dye adsorption behaviour with the binary

KR (L/g)
system. Although there are other activated carbons with similar
surface area, these three carbons have a higher yield compared with
other carbon with similar surface area. Fig. 3 shows the experimen-

8.25E−02
9.87E−01
9.75E−01
1.72E−01
8.24E−02
4.65E−02
3.73E−01
9.48E−02
3.80E−01
tal adsorption data for the binary system of AB25 and AY117 on C5,
C7 and C9.
SSE

It can be seen from Fig. 3 that the adsorption capacity of AB25 is

higher than the AY117 onto all three carbons. It is expected since
2.68E−02
4.22E−02

3.76E−02
5.85E−02
1.43E−02
4.29E−02
1.15E−01
1.10E−01
5.03E−02
from the single component adsorption studies, all the tyre acti-
vated carbons have a higher capacity for AB25, while comparatively
bF

less adsorption capacity for the larger AY117 molecule is observed.

Freundlich

Therefore, in the binary system, the chance is high that the smaller
3.13E−01
8.42E−01

5.74E−01

2.48E−01
5.28E−01
3.76E−01
3.30E−01
1.40E+00

1.04E+00
aF (L/g)

dye AB25 will be adsorbed onto the carbon first, because it can
move and diffuse faster. As a result, the carbon shows a domi-
nant adsorption for AB25, the saturation capacity of the AB25 in
the binary system is just a bit lower than that in the single compo-
Qmono (mmol/g)

nent system. Similar results were reported by other workers that

8.27E−01

5.26E−01
3.17E−01
2.36E−01
5.18E−01
3.74E−01
8.99E−01
3.08E−01

the adsorption capacity of the individual solute in a multicompo-

1.14E+00

nent system was lower than the capacity in a single component

8.23E−02
9.87E−01
9.79E−01
1.74E−01
8.25E−02
4.68E−02
3.73E−01
9.27E−02
3.76E−01

0.9

0.8
SSE

0.7

0.6
aL (L/mmol)
Qe(mmol/g)

C5 AB25
3.32E+02
2.15E+03
5.24E+02
2.75E+02
1.13E+03
1.53E+02
2.28E+02
1.50E+02
4.00E+02

0.5 C5 AY117
Modelling parameters for AB25.

0.4 C7 AB25
0.3 C7 AY117

0.2 C9 AB25
Langmuir

1.23E+02
1.24E+02
3.78E+02
1.13E+03
1.66E+02

5.85E+02
5.72E+01
6.50E+01

2.05E+02
KL (L/g)

C9 AY117
0.1

0
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40
Table 4

AB25

Ce(mmol/L)
C1
C2
C3
C4
C5
C6
C7
C8
C9

Fig. 3. Experimental data for binary acid dye system with C5, C7 and C9.
168 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170

4.56E−03

7.97E−02

9.41E−03
9.49E−03
1.64E−03
3.99E−02
2.20E−02

3.09E−03
1.70E−03
0.9
AB25
0.8

SSE
Single
y = 0.001x
0.7 R² = 0.972 AY117

Qe(mmol/g)
y = 0.000x

3.33E−01
7.21E−01
1.43E−01
3.84E−01
2.13E−01

6.32E−01
9.06E−01

2.50E−01
0.6 Single

1.11E+00
R² = 0.998
0.5 AB25

nLF
0.4 Binary
y = 0.000x
0.3 AY117
R² = 0.872
aLF (L/mmol)
Binary
0.2

4.72E−01

9.79E−01
1.00E−03
4.71E+01

1.99E+01

7.89E+02
4.77E+00

5.57E+00

8.50E+01
y = 0.000x
Langmuir–Freundlich

0.1 R² = 0.839
0
0 200 400 600 800 1000
Surface Area (m2/g)
6.98E−01

6.95E−01

2.25E−01

3.22E−01
1.83E+01

1.38E+00

4.24E+00

3.30E+02
8.40E+00
KLF (L/g)

Fig. 4. The plot of Qe vs SBET for acid dye in single and binary system.

system [42–45]. The explanations of the reduction in capacity can

4.57E−03
2.58E−02
7.99E−02
3.89E−03
1.69E−03
9.45E−03
9.74E−03
1.68E−03
3.98E−02

be due to several factors including:

SSE

1. the interaction between the dyes in solution or the hindrance of

the dyes;
9.27E−01
8.64E−01
8.52E−01

8.41E−01
9.33E−01
8.94E−01
8.33E−01
9.75E−01
8.70E−01

2. the change of surface charge of the carbon as a result of adsorp-

tion;
bR

3. the competition between dyes for the available active sites on

the carbon surface during which replacement/displacement of
aR (L/mmol)

4.22E+02
1.64E+03

2.54E+03
4.42E+03
2.15E+03
3.95E+02

4.79E+02
2.08E+07

1.80E+04

the dyes occurred.

Redlich–Peterson

Upon closer examination of the experimental data, the last few

qe values of the AY117 adsorption isotherm dropped from the peak
5.15E+01
7.48E+02
1.47E+07
5.76E+02
6.78E+02
2.21E+02
8.67E+01

2.12E+02
3.05E+03

while that of AB25 kept increasing. An explanation is that at low

KR (L/g)

dye concentrations when all or most of the AB25, i.e. Ce = 0, has

adsorbed on to it, then AY117 begins being adsorbed on to the
remaining unoccupied active sites on the activated carbon. How-
2.74E−02
7.97E−02
4.25E−03
1.69E−03
9.46E−03

1.68E−03
4.33E−02
4.60E−03

1.01E−02

ever, as the C0 of AB25 is increased, the adsorption of AB25 on

the carbon became more and more saturated as more pores on
SSE

the carbon were occupied by the AB25 dye molecules, and thus
even less AY117 molecules could be adsorbed onto the carbon and
1.12E−01
1.56E−01
1.43E−01
1.54E−01
1.65E−01
7.12E−02
1.44E−01
1.68E−01
1.20E−01

hence resulting in a drop from the peak in the adsorption isotherm

as shown in Fig. 3. This further confirms the competitive nature
bF

between the two acid molecules in their binary adsorption system

because the smaller molecule is being adsorbed first.
Freundlich

1.27E−01
4.73E−01
6.94E−01
2.35E−01
1.55E−01

2.29E−01
1.69E−01
5.24E−01
1.03E−01

On the contrary, for both AB25 and AY117, there is an increasing

aF (L/g)

trend in their adsorption capacity from C5 < C7 < C9. These actually
follow the order of their surface area and textural property. From
the plot of Qe vs SBET in Fig. 4, it is clear that there is a very good
Qmono (mmol/g)

linear relationship between both the adsorption of AB25 and AY117

onto three carbons. The slope of the binary dye adsorption is smaller
3.62E−01
5.76E−01
1.93E−01
1.24E−01
9.83E−02
1.94E−01
1.36E−01
4.21E−01
1.10E−01

compared with the single dye system, which shows the effect of the
addition of a competitive dye.
4.86E−03
2.28E−02
1.51E−01
6.94E−03
3.43E−03
9.41E−03
9.73E−03
3.68E−03
4.00E−02

4.1.2. Binary equilibrium isotherm modelling

The equilibrium adsorption data were analysed by various
SSE

multicomponent isotherm models, namely, extended Langmuir,

extended-RP, extended-LF and some empirical models including:
aL (L/mmol)

extended-Freundlich, P-factor and the interaction factor model

2.25E+02
2.45E+02
1.43E+02
1.61E+02
1.81E+02
1.21E+02
1.29E+02
1.47E+02
4.25E+02
Modelling parameters for AY117.

and finally, the IAST-Langmuir and IAST-Langmuir–Freundlich

isotherms. All the Langmuir based multicomponent models were
analysed using single component Langmuir isotherm parameters.
The constants were found by minimising the SSE error function
Langmuir

2.48E+01
8.88E+01
8.24E+01

2.24E+01
1.19E+01

1.79E+02
3.10E+01

2.50E+01
2.00E+01
KL (L/g)

since this method was found to give the best monolayer predic-
tion. Similarly apply to the other models that require the single
component constants.
In the following section, only the predictions of binary AB25
AY117
Table 5

and AY117 adsorption equilibrium isotherms on tyre carbon C9

C1
C2
C3
C4
C5
C6
C7
C8
C9

are plotted in Figs. 5–7, they were grouped according to extended

 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170 169

0.90 Table 6
C9 AB25 EXP
The extended Freundlich coefficients.
0.80
C9 AY117 Exp
AB25+AY117 system
0.70
C9 AB Extended o
K1F o
K2F n1 n2 a12 n12 n21 n22
0.60 Langmuir
Qe(mmol/g)

C9 AY Extended C5 87.874 41.186 0.218 0.062 0.012 0.010 0.050 0.245

0.50 Langmuir C7 136.866 64.618 0.227 0.059 0.001 0.041 0.019 1.297
0.40 C9 AB25 Extended RP C9 166.784 180.224 0.125 0.013 0.002 0.014 0.315 0.866

0.30 C9 AY117 Extended RP

0.20 C9 AB25 Extended LF Table 7

P-factor and I-factor for acid dye binary system.
0.10 C9 AY117 Extended LF
AB25 (P-factor, P) AY117 (P-factor, P)
0.00
0.00 0.50 1.00 1.50 C5 1.76 2.00
C7 1.41 1.31
Ce(mmol/l)
C9 1.198 1.801
Fig. 5. The extended single-component equilibrium isotherm models for acid dye
systems. AB25 (I-factor, ) AY117 (I-factor, )

C5 103.70 472.49
C7 12.08 83.40
1.00E+00 C9 0.26 7.77
9.00E-01 C9 AB25 Exp
8.00E-01
7.00E-01
C9 AY117 Exp single-component equilibrium isotherm models, IAST and correla-
Qe(mmol/g)

tive modelling.
6.00E-01 C9 AB25 IAST-L
From the literature, the multicomponent model based on the
5.00E-01
C9 AY117 IAST-L extended Langmuir and the IAST models should provide a good
4.00E-01
prediction of sorption behaviour only if two dyes with similar
3.00E-01 C9 AB25 IAST-LF sizes and properties are used in the binary system, since the
2.00E-01 adsorbate–adsorbate interaction is greatly reduced as they have
C9 AY117 IAST-LF
1.00E-01 similar sorption behaviour. However, in the present case from both
0.00E+00 Figs. 5 and 6, since the adsorption behaviour is so different in the
0.00E+00 5.00E-01 1.00E+00 1.50E+00 single component system, so both models are not a good fit com-
Ce(mmol/l) pared with the empirical models, as the systems are non-ideal
adsorbed solute systems particularly at high solution concentra-
Fig. 6. IAST isotherm for acid dye binary system.
tions.
Table 6 shows the extended Freundlich constants for the binary
Correlave Binary Model dye systems. The plots for acid dyes using the extended Freundlich,
9.00E-01 P-factor and the interaction factor are shown in Fig. 7. In all the
8.00E-01
C9 AB exp
binary systems, good agreement is achieved at an acceptable level
7.00E-01 of accuracy compared with other multicomponent isotherms previ-
C9 AY exp
6.00E-01 ously used, which means the use the experimental data to correlate
Qe(mmol/g)

C9 AB25 Extended-F the model fitting can improve the quality of model fitting consid-
5.00E-01
4.00E-01
C9 AY117 Extended-F erably. The P-factor and I-factor are listed in Table 7.
C9 AY I-factor In order to select the best fit model for the binary dye adsorption
3.00E-01
system, it would be easier to find the minimum SSE. Table 8 shows
2.00E-01 C9 AB I-factor
the SSE for all the models investigated.
1.00E-01 C9 AB P-factor
The empirical extended Freundlich is the best model which
0.00E+00 C9 AY P-factor gives the smallest SSE value of all models used. As the extended
0.00E+00 5.00E-01 1.00E+00 1.50E+00
Freundlich model was the best fit to the experimental data, it
Ce(mmol/L) suggested significant non-ideal effects and heterogeneous surface
Fig. 7. The correlative binary model for acid dye.
properties for the dye binary adsorption system, and the impor-
tance of using the binary data obtained to correlate equilibrium.

Table 8
The SSE for different multicomponent isotherms.

C5 Extended Langmuir Extended R–P Extended L–F Extended Freundlich P-factor Interaction factor IAST Langmuir IAST L–F

AB25 8.54E−02 9.80E−01 6.55E−01 2.90E−03 3.68E−02 8.33E−01 1.73E−02 1.13E−01

AY117 7.31E−03 1.69E−01 8.91E−01 2.72E−04 1.79E−03 6.22E−01 3.55E−02 4.41E−02

C7 Extended Langmuir Extended R–P Extended L–F Extended Freundlich P-factor Interaction factor IAST Langmuir IAST L–F

AB25 3.15E−02 5.39E−01 9.26E−02 2.28E−02 6.07E−02 9.39E−01 9.78E−02 1.34E+00

AY117 6.43E−02 4.33E−01 7.55E−01 2.93E−04 4.31E−03 7.29E−01 2.45E−01 1.02E−01

C9 Extended Langmuir Extended R–P Extended L–F Extended Freundlich P-factor Interaction factor IAST Langmuir IAST L–F

AB25 2.52E+00 7.41E−01 1.74E−02 4.49E−02 2.64E−01 8.09E−01 5.47E−01 4.68E−01

AY117 2.52E+00 8.12E−01 8.53E−01 5.41E−03 2.41E−02 6.02E−01 2.45E−01 2.55E−01
170 O.S. Chan et al. / Chemical Engineering Journal 191 (2012) 162–170
Overall, none of the predictive binary or IAST models can correlate
the adsorption data really well, this means the general assump-
tion of the ideal system is not applicable. In addition, the deviation
might be strongly related to the properties of the adsorbate. This
demonstrated the difficulty of using single component parameters
to predict multicomponent system equilibrium.
5. Conclusion
The adsorption capacities of the acid dyes were compared with
the available literature value of commercial activated carbon F400.
The best mesoporous tyre activated carbon has a higher capac-
ity than F400, especially for AY117, the adsorption capacity is
nearly four times higher than the F400. Higher surface area will
enhance the adsorption of dyes due to more area for the dyes
to interact with the basal plane of the carbon. The adsorption of
AB25 can be described with Langmuir model, while the adsorp-
tion of AY117 can be better described with Langmuir–Freundlich
model. The binary component adsorption studies are presented and
modelled with various predictive and correlative models. Overall,
none of the predictive binary models can describe the adsorption
data well; this means the general assumption of the ideal sys-
tem is not applicable. In addition, the deviation might be strongly
related to the properties of the adsorbate. The correlative extended
Freundlich model was best fitted to the experimental data. This
suggests the significant non-ideal effects and heterogeneous sur-
faces of the tyre activated carbon. This demonstrated the difficulty
of using single component parameters to predict multicomponent
systems.
References
[1] Anon, The Economics of Activated Carbon, 8th ed., Roskill Information Services
Ltd., London, 2008.
[2] N.K. Hamadi, C. Xiao Dong, M.M. Farid, M.G.Q. Lu, Adsorption kinetics for the
removal of chromium(VI) from aqueous solution by adsorbents derived from
used tyres and sawdust, Chem. Eng. J. 84 (2001) 95–105.
[3] F. Rozada, M. Otero, J.B. Parra, A. Moran, A.I. Garcia, Producing adsorbents from
sewage sludge and discarded tyres: characterization and utilization for the
removal of pollutants from water, Chem. Eng. J. 114 (2005) 161–169.
[4] M. Olivares-Marin, J.A. Fernandez, M.J. Lazaro, C. Fernandez-Gonzalez, A.
Macias-Garcia, V. Gomez-Serrano, F. Stoeckli, T.A. Centeno, Cherry stones as
precursor of activated carbons for supercapacitors, Mater. Chem. Phys. 114
(2009) 323–327.
[5] T. Xu, X. Liu, Peanut shell activated carbon: characterization, surface modifi-
cation and adsorption of Pb2+ from aqueous solution, Chin. J. Chem. Eng. 16
(2008) 401–406.
[6] M. Valix, W.H. Cheung, G. McKay, Sulfur fixation on bagasse activated carbon by
chemical treatment and its effect on acid dye adsorption, Adsorption 15 (2009)
453–459.
[7] L.S. Chan, W.H. Cheung, G. McKay, Adsorption of acid dyes by bamboo derived
activated carbon, Desalination 218 (2008) 304–312.
[8] H. Wang, H. Xu, X. Xuan, Review of waste tire reuse & recycling in China, Adv.
Nat. Sci. 2 (2009) 31–39.
[9] US EPA, Waste - Resource Conservation – Common Wastes & Materials – Scrap
Tires, 2005, www.epa.gov/osw/conserve/materials/tires/index.htm 2011.
[10] E.L.K. Mui, D.C.K. Ko, G. McKay, Production of active carbons from waste tyres
– a review, Carbon 42 (2004) 2789–2805.
[11] E.L.K. Mui, W.H. Cheung, M. Valix, G. McKay, Mesoporous activated carbon from
waste tyre rubber for dye removal from effluents<!–, Microporous Mesoporous
Mater. 130 (2010) 287–294.
[12] J. Zhu, B. Shi, L. Chen, D. Liu, H. Liang, Production, characterization and prop-
erties of chloridized mesoporous activated carbon from waste tyres, Waste
Manag. Res. 27 (2009) 553–560.
[13] J.F. Gonzalez, J.M. Encinar, C.M. Gonzalez-Garcia, E. Sabio, A. Ramiro, J.L. Canito,
J. Ganan, Preparation of activated carbons from used tyres by gasification with
steam and carbon dioxide, Appl. Surf. Sci. 252 (2006) 5999–6004.
[14] J. Shah, M.R. Jan, F. Mabood, M. Shahid, Conversion of waste tyres into car-
bon black and their utilization as adsorbent, J. Chin. Chem. Soc. 53 (2006)
1085–1089.
[15] A. Min, A.T. Harris, Influence of carbon dioxide partial pressure and fluidization
velocity on activated carbons prepared from scrap car tyre in a fluidized bed,
Chem. Eng. Sci. 61 (2006) 8050–8059.
[16] H.Y. Lin, C.S. Yuan, C.H. Wu, C.H. Hung, The adsorptive capacity of vapor-phase
mercury chloride onto powdered activated carbon derived from waste tires, J.
Air Waste Manag. 56 (2006) 1558–1566.
[17] O.S. Chan, W.H. Cheung, G. McKay, Preparation and characterisation of dem-
ineralised tyre derived activated carbon, Carbon 49 (2011) 4674–4687.
[18] G. McKay, B. Al-Duri, Prediction of bisolute adsorption isotherms using single-
component data for dye adsorption onto carbon, Chem. Eng. Sci. 43 (1988)
1133–1142.
[19] I. Langmuir, The constitution and fundamental properties of solids and liquids.
Part I. Solids, J. Am. Chem. Soc. 38 (1916) 2221–2295.
[20] H. Freundlich, Over the adsorption in solution, Z Phys. Chem. 57 (1906)
385–470.
[21] O. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys. Chem. 63 (1959)
1024.
[22] R. Sips, On the structure of a catalyst surface, J. Chem. Phys. 16 (1948) 490–495.
[23] J.A.V. Butler, C. Ockrent, Studies in electrocapillarity. Part III. The surface ten-
sions of solutions containing two surface-active solutes, J. Phys. Chem. 34
(1930) 2841–2859.
[24] J.A.V. Butler, C. Ockrent, Adsorption from solutions containing two solutes,
Nature 125 (1930) 853–854.
[25] E.A. James, D.D. Do, Equilibria of biomolecules on ion-exchange adsorbents, J.
Chromatogr. 542 (1991) 19–28.
[26] K.H. Chu, Removal of copper from aqueous solution by chitosan in prawn shell:
adsorption equilibrium and kinetics, J. Hazard. Mater. 90 (2002) 77–95.
[27] G. McKay, B. Al Duri, Multicomponent dye adsorption onto carbon using
a solid diffusion mass-transfer model, Ind. Eng. Chem. Res. 30 (1991)
385–395.
[28] W. Fritz, E.U. Schluender, Simultaneous adsorption equilibria of organic solutes
in dilute aqueous solutions on activated carbon, Chem. Eng. Sci. 29 (1974)
1279–1282.
[29] B. Al-Duri, G. McKay, Pore diffusion: dependence of the effective diffusivity
on the initial sorbate concentration in single and multisolute batch adsorption
systems, J. Chem. Technol. Biotechnol. 55 (1992) 245–250.
[30] G. McKay, B. Al-Duri, Extended empirical Freundlich isotherm for binary sys-
tems: a modified procedure to obtain the correlative constants, Chem. Eng.
Process. 29 (1991) 133–138.
[31] G. McKay, B. Al Duri, Simplified model for the equilibrium adsorption of dyes
from mixtures using activated carbon, Chem. Eng. Process. 22 (1987) 145–156.
[32] G.J. Schay, F.P. Fejes, J. Szethmary, Adsorption of gases and gas mixtures, Acta
Chim. Acad. Sci. Hung. 12 (1957) 299–308.
[33] A.P. Mathews, Mathematical modelling of multicomponent adsorption in batch
reactors, PhD Thesis, The University of Michigan, 1978.
[34] A.L. Myers, J.M. Prausnitz, Thermodynamics of mixed-gas adsorption, AIChE J.
11 (1965) 121–127.
[35] C.J. Radke, J.M. Prausnitz, Thermodynamics of multi-solute adsorption from
dilute liquid solutions, AIChE J. 18 (1972) 761–768.
[36] Y.C. Wong, Y.S. Szeto, W.H. Cheung, G. McKay, Equilibrium studies for acid dye
adsorption onto chitosan, Langmuir 19 (2003) 7888–7894.
[37] J.J.M. Orfao, A.I.M. Silva, J.C.V. Pereira, S.A. Barata, I.M. Fonseca, P.C.C. Faria,
M.F.R. Pereira, Adsorption of a reactive dye on chemically modified activated
carbons – influence of pH, J. Colloid Interface Sci. 296 (2006) 480–489.
[38] M. Hirata, N. Kawasaki, T. Nakamura, K. Matsumoto, M. Kabayama, T. Tamura, S.
Tanada, Adsorption of dyes onto carbonaceous materials produced from coffee
grounds by microwave treatment, J. Colloid Interface Sci. 254 (2002) 17–22.
[39] C.A. Leon y Leon, J.M. Solar, V. Calemma, L.R. Radovic, Evidence for the proto-
nation of basal plane sites on carbon, Carbon 30 (1992) 797–811.
[40] L.R. Radovic, I.F. Silva, J.I. Ume, J.A. Menendez, C.A. Leon, Y. Leon, A.W. Sca-
roni, An experimental and theoretical study of the adsorption of aromatics
possessing electron-withdrawing and electron-donating functional groups by
chemically modified activated carbons, Carbon 35 (1997) 1339–1348.
[41] C. Moreno-Castilla, Adsorption of organic molecules from aqueous solutions on
carbon materials, Carbon 42 (2004) 83–94.
[42] J. Shore, Advances in direct dyes, Indian J. Fibre Text. Res. 21 (1996) 1–29.
[43] S.J. Allen, G. McKay, K.Y.H. Khader, Multi-component sorption isotherms of
basic dyes onto peat, Environ. Pollut. 52 (1988) 39–53.
[44] S.Y. Lee, J.D. Seader, C.H. Tsai, F.E. Massoth, Multicomponent liquid-phase dif-
fusion and adsorption in porous catalyst particles, Chem. Eng. Sci. 48 (1993)
595–607.
[45] Y. Al-Degs, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, G.M. Walker, Competi-
tive adsorption of reactive dyes from solution: equilibrium isotherm studies in
single and multisolute systems, Chem. Eng. J. 128 (2007) 163–167.