HKIE Transactions

ISSN: 1023-697X (Print) 2326-3733 (Online) Journal homepage: http://www.tandfonline.com/loi/thie20

Equilibrium adsorption isotherm study of binary

basic dyes on to bamboo derived activated carbon

L S Chan, W H Cheung, S J Allen & G McKay

To cite this article: L S Chan, W H Cheung, S J Allen & G McKay (2017) Equilibrium adsorption
isotherm study of binary basic dyes on to bamboo derived activated carbon, HKIE Transactions,
24:4, 182-192, DOI: 10.1080/1023697X.2017.1375434

To link to this article: https://doi.org/10.1080/1023697X.2017.1375434

Published online: 26 Dec 2017.

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 HKIE TRANSACTIONS, 2017
VOL. 24, NO. 4, 182–192
https://doi.org/10.1080/1023697X.2017.1375434

Equilibrium adsorption isotherm study of binary basic dyes on to bamboo

derived activated carbon
L S Chana,b† , W H Cheung b , S J Allena and G McKay b

a School of Chemistry and Chemical Engineering, Queen’s University of Belfast, Northern Ireland, the UK; b Department of Chemical and
Biological Engineering, The Hong Kong University of Science and Technology, Hong Kong, People’s Republic of China

ABSTRACT ARTICLE HISTORY

In the present study, a high surface area activated carbon (HSA1) is produced from waste bam- Received 14 March 2017
boo scaffolding by low temperature chemical activation with phosphoric acid. The single and Accepted 3 August 2017
binary component adsorption capacities of basic dyes, namely, Basic Yellow 11 (BY11) and Max- KEYWORDS
ilon Red GRL 200% (MR), were conducted on HSA1 and a commercially available carbon, Calgon Activated carbon; bamboo;
Filtrasorb® 400 (F400). HSA1 showed up to five times higher adsorption capacities for both dyes in adsorption; basic dye;
single and binary systems than F400. The adsorption capacity of the individual dyes in the binary
Downloaded by [Australian National University] at 01:47 31 December 2017

isotherm modelling
system was lower than in the single component system. The equilibrium adsorption data for
the binary-component system were analysed. Extended single-component equilibrium isotherm
models were used to predict the experimental data. The extended Freundlich model was over-
all the best fitted to the experimental data for both activated carbons, suggesting significant
non-ideal effects and heterogeneous surfaces for the basic dye binary adsorption system with
activated carbons.

Nomenclature KL Langmuir isotherm constant (L/g)

0
KL,i Single component Langmuir constant
a0 L,i Single component Langmuir constant
for component i (L/g)
for component i (L/mmol)
KR Redlich-Peterson constant (L/g)
a0 R,i Single component Redlich-Peterson 0
KR,i Single component Redlich-Peterson
constant for component i (L/mmol)
constant for component i (L/g)
a12 , a21 Correlative constants for extended Fre-
KS Sips isotherm constant (L/g)
undlich isotherm (L/mmol)
m Mass of sorbent (g)
aL Langmuir constant (L/mmol) n Number of data points (Dimension-
aR Redlich-Peterson constant (L/mmol) less)
aS Sips constant (L/mmol) nF Freundlich exponent constant
bS Single component Sips constant (Dimensionless)
(Dimensionless) n 1 , n2 Freundlich exponent constant for com-
Ce Concentration of adsorbate at equilib- ponents 1 and 2 (Dimensionless)
rium (mmol/L) n11 , n12 , Correlative constants for extended
Ce,i , Ce,1 , Ce,2 Concentration of adsorbate at equi- n21 , n22 Freundlich isotherm (Dimensionless)
librium for components i, 1 and 2 p Number of parameters (Dimension-
(mmol/L) less)
C0 Initial concentration of adsorbate in P P Factor correlation coefficient
aqueous phase (mmol/L) (Dimensionless)
Ct Liquid phase concentration at time t qe Solid phase concentration at equilib-
(mmol/L) rium (mmol/g)
dP Particle diameter (mm) qei,cal Calculated amount of adsorbate
k Dye concentration calibration con- adsorbed at equilibrium (mmol/g)
stant (Dimensionless) qei,meas Experimental amount of adsorbate
KF Freundlich isotherm constant (L/g) adsorbed at equilibrium (mmol/g)
0 , K0
KF,1 Single component Freundlich constant
F,2 qe,i Amount of adsorbate adsorbed at equi-
for components 1 and 2 (L/g) librium for component i (mmol/g)

CONTACT W H Cheung alex.wh.cheung@wsp.com

† The author was 35 years old or younger at the time of his/her paper submission.

© 2017 The Hong Kong Institution of Engineers


qt Solid phase concentration at time t
(mmol/g)
Q0 Monolayer saturation capacity for Lang-
muir isotherm (mmol/g)
V Volume of dye sample (L)
W Weight of sorbent (g)
Greek Symbols
β Redlich-Peterson constant (Dimensionless)
βi Single component Redlich-Peterson constant for
component i (Dimensionless)
Abbreviations
ARE: Average Relative Error
Downloaded by [Australian National University] at 01:47 31 December 2017
BY: Basic Yellow
HSA: High Surface Area
MR: Maxilon Red
1. Introduction
More than 10,000 different dyes and pigments are used
and over 7 × 105 tonnes of dyestuff produced annually
in the textile industry [1–3], but wastewater treatment
processes are currently capable of removing about half
of the dyes lost in residual liquors [4]. Due to the inef-
ficiency of the dyeing process, typically 30% of dyes are
lost in residual liquors through exhaustion and wash-
ing operations and up to 200,000 tonnes of dyes are
discharged as effluent [2]. Most dyes are resistant to
heat and light and are not biodegradable [5]. Among
all commercially available synthetic dyes, basic dyes
are the brightest class of soluble dyes used by the tex-
tile industry. Basic dyes are in the category of cationic
dyes and carry localised or delocalised positive charge
in their molecules [6]. These dyes are stable due to
the presence of aromatic and various functional groups
which in turn render recalcitrant effect of the dyes [7,8].
Basic dyes are used in textile such as silk, leather, paper,
cotton, mordent with tannin dyeing process as well as
ink and copying paper in office supplies industry [6].
Basic dyes have great tinctorial strength where obvious
colouration can be observed at concentration as low as
1 ppm [8].
Adsorption is one of the most cost effective and effi-
cient technologies used in wastewater treatment pro-
cesses. Activated carbon is the commonly used adsor-
bent because of its high adsorption capacities which
enables adsorption of both cationic and anionic efflu-
ents [9,10]. The high adsorption capacity of an activated
carbon is a result of its high surface area, extensive
porosity in the interior of the particles, and presence of
many different types of surface functional groups. The
characteristics of activated carbon can be appropriately
tailored by selecting adequately the raw material and
HKIE TRANSACTIONS 183
optimised carbonisation and activation process condi-
tions. However, the production cost of the adsorbent
and its regeneration may be limiting factors, especially
in the developing countries. With the global demand
of the activated carbon forecasted to be high with a
predicted worldwide increase of 6% between 2015 and
2020 [11,12], low cost precursors have been the focus
of researchers worldwide. Precursors from wastes and
agricultural by-products such as fruit stones [13], oil-
palm shell [14], rice husk [15], bagasse [16], garlic peel
[17], orange peel [18], de-oiled soya [19,20], indus-
trial wastes [20–23] and waste tyres [24,25] have shown
potential.
In Hong Kong, bamboo is uniquely used in this
region as scaffolding for building and construction
projects [26]. Over 50,000 tonnes of bamboo scaffold-
ing is being dumped as construction waste from Hong
Kong’s building and construction projects each year
[27]. With limiting landfilling space available, there
is a growing interest in the reuse and/or recycling of
this material, as bamboo is a sustainable carbonaceous
material. Waste bamboo scaffolding has the potential
as a raw material for the production of activated car-
bon and carbon char due to its high carbon content
(44%).
A conventional method for the preparation of acti-
vated carbon from lignocellulosic materials is by acti-
vation with phosphoric acid [28]. Phosphoric acid
induces important changes in the pyrolytic decompo-
sition of the lignocellulosic materials as it promotes
depolymerisation, dehydration and redistribution of
constituent biopolymers [29,30]. At present, only lim-
ited research has been carried out on bamboo as a
precursor utilising high temperature physical activa-
tion. BET-nitrogen surface area ranges from 491 to
1038 m2 /g have been reported [31–34].
Previous works focused on the adsorption of single-
component dyes using various adsorbents. Recently,
researchers have been focused on multi-component
dye adsorption as most industrial effluents contain
a mixture of dyes with lignite [35], activated carbon
[36], nano metal/metal oxides particles modified acti-
vated carbon [37–44] and ultrasonic assisted adsorp-
tion [39,40,42,43,45,46].
In the present work, the binary equilibrium study
for the adsorption of mixed basic dyes, namely,
Basic Yellow 11 (BY11) and Maxilon Red GRL
200% (MR), on the activated carbon produced from
waste bamboo scaffolding by low temperature chem-
ical activation with phosphoric acid was investigated
and compared with a commercially available carbon,
Calgon Filtrasorb® 400 (F400). Parameters obtained
from the single component isotherm models were
used for the prediction of the binary system using
the following isotherm models: extended Langmuir
isotherm, Jain and Snoeyink modified extended Lang-
muir model, P-factor, interaction factor, extended
 184 L S CHAN ET AL.

Freundlich isotherm, and extended Redlich-Peterson Table 2. Physical and chemical properties of the dyes.
isotherm. Dye

Basic Maxilon Red GRL

2. Materials and methodology Yellow 11 200% (Basic Red 46)
Colour index 48,055 110,825
2.1. Chemical activation of bamboo Abbreviation BY11 MR
Molecular weight (g/mol) 372.9 501
The production of activated carbon from bamboo Dye content (%) 20 73
scaffolding was reported in details elsewhere [47]. In Chromophore Methine Monoazo
Maximum wavelength, λmax (nm) 412 530
summary, the received waste bamboo scaffolding was Charge +1 +1
washed with water and reduced to size by hammer Width (Å) 15 13
Depth (Å) 15 15
milling to a particle size range from 500 μm to 710 μm Thickness (Å) 4 6
and then pre-treated by soaking and saturating with
ortho-phosphoric acid, H3 PO4 , (BDH Chemicals, the
UK) at acid to bamboo ratio (Xp) of 2.41, in alu- dimensions of dye molecules were estimated using the
mina containers. The mixture was stirred thoroughly to software, ChemSketch (ACD, Inc., Canada).
ensure homogenous mixing of the bamboo and H3 PO4 .
Then, the samples were subjected to a two-step heat- 2.4. Dye adsorption equilibrium capacity test
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ing process at 150°C for two hours and then at 600˚C

in a furnace under flowing nitrogen for four hours.
After heating, samples were cooled, washed and dried.
The high surface area activated carbon (HSA1) was
obtained.
2.2. Carbon characterisation test
Properties of HSA1 are shown in Table 1 with the prop-
erties of the commercial activated carbon (F400). The
apparent surface area of the activated carbon was deter-
mined from N2 adsorption at 77 K in a SA 3100 anal-
yser (Beckman Coulter, Inc., the USA) using the BET
equation [48]. The micropore volume was estimated
by applying the Horvath Kawazoe (HK) method [49]
which assumes slit pore shapes on the nitrogen adsorp-
tion isotherms. Mesopore volume was estimated using
the Kelvin equation [50]. The total pore volumes were
calculated by converting the nitrogen gas adsorbed at a
relative pressure 0.98 to the volume of liquid adsorbate.
2.3. Basic dyes
An equilibrium adsorption study of each individual dye
was conducted to determine the parameters for binary
equilibrium isotherm models.
2.4.1. Single dye system
A fixed mass of activated carbon, 0.020 g was weighed
into 80 mL glass bottles and brought into contact with
50 mL of dye solution with predetermined initial dye
concentrations ranged from 20 mmol to 500 mmol of
dye/L. The bottles were sealed and agitated continu-
ously at 200 rpm in the thermostatic shaker bath and
maintained at a temperature of 25°C ± 1°C until equi-
librium was reached. At time t = 0 and equilibrium, the
dye concentrations of the solutions were measured by a
Cary 1E UV-Vis Spectrophotometer (Varian Australia
Pty Ltd., Australia). These data were used to calculate
the adsorption capacity (qe ) of the adsorbent. The qe of
each activated carbon were determined by:
V
qe = (C0 − Ce ), (1)
m

Basic Yellow 11 (BY11) and Maxilon Red GRL 200% where qe = the dye concentration on the adsorbent at
(MR, a commercial grade Basic Red 46) were used for equilibrium (mmol/g); C0 = the initial dye concentra-
the dye equilibrium adsorption study. BY11 was sup- tion in the liquid phase (mmol of dye/L); Ce = the
plied by Sigma-Aldrich Chemical Company (the USA) liquid-phase dye concentration at equilibrium (mmol
while MR was supplied by The Hong Kong Polytechnic of dye/L); V = the total volume of dye-activated car-
University; both were used without further purifica- bon mixture (L); m = mass of activated carbon used
tion. Both dyes are generally used in the textile indus- (g). Finally, qe was plotted against Ce .
try. Table 2 shows the properties of the dyes. The
2.4.2. Binary dyes system
Similar to the single dye system, 0.02 g of activated car-
Table 1. Physical properties of the carbon used for equilibrium bon was weighed into 80 mL glass bottles and brought
basic dyes adsorption study. into contact with 50 mL of mixed dyes solution with
Properties HSA1 F400 predetermined initial dye concentrations ranged from
BET surface area (m2 /g) 2471 747 0.02 mmol to 0.9 mmol of dye/L. All solutions were
Micropore area (m2 /g) 2172 673 prepared with a dye solution of equal molar concentra-
External surface area (m2 /g) 245 74
Average pore diameter (Å) 22.20 25.18 tions. The bottles were sealed and agitated continuously
Total pore volume (cc/g) 1.341 0.470 at 200 rpm in the thermostatic shaker bath and main-
Micropore volume (cc/g) 1.023 0.348
tained at a temperature of 25°C ± 1°C until equilibrium

Table 3. Calibration constants of each dye in the binary
systems.
λ, Wavelength (nm)
Dye (A) 412
(A) Basic Yellow 11 KA1 , 0.0177 KA2 , 5 × 10−5
(B) Maxilon Red GRL 200% KB1 , 4 × 10−5 KB2 , 0.0963
was reached. At time t = 0 and equilibrium, the dye
concentrations of the solutions were measured by a
Cary 1E UV-Vis Spectrophotometer (Varian Australia
Pty Ltd., Australia). Dye concentrations were calculated
by the following method. Firstly, the absorbances, d1
and d2 , of dyes A and B of the binary system were mea-
sured at a maximum wavelength of each component.
Then, the respective single component concentrations
of dyes A and B are determined using the following
Downloaded by [Australian National University] at 01:47 31 December 2017
expressions:
(kB2 d1 − kB1 d2 )
CA = , (2a)
(kA1 kB2 − kA2 kB1 )
(kA1 d2 − kA2 d1 )
CB = , (2b)
(kA1 kB2 − kA2 kB1 )
where kA1 , kA2 , kB1 and kB2 are the calibration con-
stants for dyes A and B at the two maximum wave-
lengths, λA and λB , respectively.
The calibration constants for the two dyes at two
different wavelengths are shown in Table 3.
3. Multi-component isotherms
Most of the single-component isotherms can be
extended to describe a multi-component adsorption
system.
3.1. Extended Langmuir isotherm
Butler and Ockrent [51,52] developed the Lang-
muir model for competitive adsorption. This model
assumed: (1) a homogeneous surface with respect to
the energy of adsorption; (2) no interaction between
adsorbed species; and (3) all adsorption sites are equally
available to all adsorbed species.
0 C
KL,i e,i
qe,i =  0 , (3)
1 + aL,i Ce,i
where qe,i is the solid phase sorbate concentration
at equilibrium (mmol/g) for component i; Ce,i is
the aqueous phase sorbate concentration at equilib-
rium (mmol/L) for component i; KL,i 0 is the single-
component Langmuir isotherm constant (L/g) for
component i; a0L,i is the single-component Langmuir
isotherm constant (L/mmol) for component i. It should
be noted that the extended Langmuir isotherm pro-
vides reasonable estimates for multi-component system
HKIE TRANSACTIONS 185
as long as the qe values for each solute obtained from the
single isotherm model are close to each other.
For example, using components 1 and 2:
(B) 530
0 C
KL,1
e,1
qe,1 = , (4)
1 + a0L,1 Ce,1 + a0L,2 Ce,2
0 C
KL,2 e,2
qe,2 = . (5)
1 + a0L,1 Ce,1 + a0L,2 Ce,2
3.2. Jain and Snoeyink modified extended
Langmuir model
Jain and Snoeyink [53] investigated competitive sorp-
tion on activated carbon from aqueous bi-component
solutions of organic sorbates and developed a model
that predicts sorption equilibria in such non-ideal sys-
tems. According to Jain and Snoeyink, the Langmuir
theory for binary sorbates systems is based on sorption
without competition. Therefore, in order to account
for the competition in the Langmuir theory, the Jain-
Snoeyink (JS) model proposed to add an addition term
in the extended Langmuir equation:
(Q0m,1 − Q0m,2 )a0L,1 Ce,1
qe,1 =
1 + a0L,1 Ce,1
Q0m,2 a0L,1 Ce,1
+ , (6)
1 + a0L,1 Ce,1 + a0L,2 Ce,2
Q0m,2 a0L,1 Ce,1
qe,2 = . (7)
1 + a0L,1 Ce,1 + a0L,2 Ce,2
The first term in the right hand side in Equation (6)
refers to the amount of component 1 adsorbed without
competition with component 2, while the second term
gives the amount of component 1 adsorbed in compe-
tition with component 2 as described by applying the
competition on the Langmuir model. The additional
term of Equation (6) is the Langmuir expression for
the number of molecules of component 1 which sorbed
without competition on the surface area and the term
is proportional to (Qm,1 –Qm,2 ), where Qm,1 is greater
than Qm,2 . By Equation (7), the number of molecules of
component 2 sorbed on the sorbent surface is propor-
tional to Qm,2 in competition with component 1, can be
calculated from the extended Langmuir equation.
3.3. P-factor
This is another correlative technique that has been
developed [54] and applied to dye/carbon systems.
It is an easy-to-use method based on introducing a
 186 L S CHAN ET AL.
“lumped” capacity factor, Pi :
(KLi /aLi )single-solute
Pi = , (8)
(KLi /aLi )multi-solute
where (KLi /aLi )multi-solute is the sorbent monolayer
capacity for component i in a multi-solute system,
while (KLi /aLi )single-solute is that in the single-solute sys-
tem. This model assumes a Langmuir isotherm; hence
for each component i, the multi-component isotherm
equation is described as:
1 KLi 0C
ei,multi
qei,multi = . (9)
Pi 1 + aLi Cei,multi
0
3.4. Interaction factor
The interaction factor is a correlative method based
Downloaded by [Australian National University] at 01:47 31 December 2017
on combining single and multicomponent data to pro-
duce correlative factors. These are back substituted in
the extended isotherm formulae to produce generalised
multicomponent isotherms. It assumes that the value of
the interaction factor cannot be a negative value.
Sorbent-sorbate interactions and competition will
change the diffusivity of each component and alter its
sorption energy leading to changes in sorption capac-
ities, which appear difficult to be predicted. Different
interactions in the solution and on the surface of the
sorbent lead to a different loading; to incorporate these
effects into a correlative model, an interaction term,
η, has been introduced. Schay et al. [55] proposed the
interaction factor, ηi for the ith component in a sys-
tem of n components. η is specific to each component i
and is a function of all other components in solution.
The calculation of the interaction factor is based on
minimising the error function.
Yon and Tumock [56] incorporated η in their sys-
tems of gases adsorbing on molecular sieves. Success-
ful results were obtained. Incorporating this approach
with the Redlich-Peterson isotherm, Mathews [57] pre-
sented the following:
Ki (Ce /ηi )
qe,i = . (10)
n
1+ aj (Ce,j /ηj )
j=1
Seidel and Gelbin [58] applied Equation (10) for
the binary mixtures of phenol and indol on the acti-
vated carbon. McKay and Al-Duri [59], Al-Duri and
McKay [60] adopted this approach with dye/carbon and
dye/pith systems, respectively, and obtained a signifi-
cant improvement to the extended Langmuir equation.
Although it has given good results for systems whose
components have similar sorbent affinities, this model
has not been widely applied, due to: firstly, the interac-
tion factor η does not have a strong theoretical foun-
dation; secondly, Equation (10) does not include the
constant K for other components, where K refers to the
sorbent capacity and adsorption energy. This implies
that η is deficient in excluding the adsorption con-
stants of other components and neglects their presence
to some extent. However, it is one of the “simpler” and
relatively more accurate approaches.
3.5. Extended Freundlich isotherm
The extended Freundlich isotherm has been proposed
by Fritz and Schlunder [61] for binary mixtures of phe-
nolic substitutes on the activated carbon. The model has
the following formula for binary mixtures:
0 Cn1 +n11
KF,1 e,1
qe,1 = n11 n12 , (11)
Ce,1 + a12 Ce,2
0 Cn2 +n22
KF,2 e,2
qe,2 = , (12)
n22 n21
Ce,2 + a21 Ce,1
where n11 , n12 , n22 , n21 , a12 and a21 are correlative
constants obtained by experimental binary data of com-
ponents 1 and 2, respectively. Glover [62] adopted
this model to describe accurately the binary adsorp-
tion of gold and zinc cyanides onto strong base anion
exchange resin. Furthermore, Young et al. [63] success-
fully applied it for gold cyanide and ethyl xanthane
adsorption on activated carbon G210. McKay and Al-
Duri [64] adopted the method, modifying the evalua-
tion of correlation factors so as to reduce the extensive
calculation procedure. They obtained excellent agree-
ment between experiment and theory for dye/carbon
and dye/peat systems [64,65]. It is a method highly
recommended for systems with significant non-ideal
effects and heterogeneous surfaces.
3.6. Extended Redlich-Peterson isotherm
Butler and Ockrent [51,52] were the first to develop
the Langmuir model for competitive adsorption. The
extended Redlich-Peterson equation may be applied
in the same manner and based on similar assump-
tions as the extended Langmuir equation. Therefore,
this model also assumed (i) no interaction between
adsorbed species and (ii) all adsorption sites are equally
available to all adsorbed species.
It is expressed as:
0 C
KR,i e,i
qe,i =  0 βi0 , (13)
1 + aR,i Ce,i
where qe,i is the solid phase sorbate concentration in
equilibrium (mmol/g) for component i; Ce,i is the liquid
phase sorbate concentration in equilibrium (mmol/L)
0 is the Redlich-Peterson isotherm
for component i; KR,i
constant (L/g) for component i; a0R,i is the Redlich-
Peterson isotherm constant (L/mmol)bS for component
i; and β i is the Redlich-Peterson isotherm constant,
dimensionless, for component i.
 HKIE TRANSACTIONS 187

4. Error analysis Table 5. Correlation factors (P) for various dye-carbon systems.
Carbon Dye Q0,single (mmol/g) Q0,multi (mmol/g) P
In the equilibrium isotherm studies, the optimisation
procedure required an error function to be defined in HSA1 BY11 2.099 0.950 2.208
MR 1.891 0.708 2.671
order to evaluate the fit of the isotherm to the experi- F400 BY11 0.457 0.019 24.01
mental equilibrium data. The choice of error function MR 0.507 0.018 27.80
could affect the parameters derived – error functions
based primarily on absolute deviation biased the fit Table 6. Interaction factors using single component parameter
towards high concentration data and this weighting sets.
increased when the square of deviation was used to
Carbon Dye η
penalise extreme errors. This bias could be offset partly
HSA1 BY11 0.709
by dividing the deviation by the measured value in MR 9.507
order to emphasise the significance of fractional devia- F400 BY11 1395
MR 16,860
tion. The average relative error (ARE) [66] function was
used for this study. This error function attempts to min-
imise the fractional error distribution across the entire
The difference is attributed to the smaller size and lower
concentration range.
weight of the BY11 molecules. This demonstrated that
n  
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100   qei,calc − qei,meas  surface area and porosity played important roles in the
n  qei,meas , (14) adsorption of basic dyes. Tables 5 and 6 show param-
i=1 eters for the P-factor and interaction factor obtained
from the single component basic dye system, which are
where qei,calc is the theoretical adsorbed solid phase
going to be used for the binary system prediction.
concentrations of sorbate on sorbent, which have been
As shown in Figures 1 and 2, HSA1 demonstrated
calculated from one of the isotherm equations, and
higher adsorption capacities for both BY11 and MR
qei,meas is the experimentally determined adsorbed sor-
than F400. Again, the adsorption capacity of the indi-
bate concentrations obtained from isotherm equations
vidual dye in the binary system was lower than that
using the experimentally measured equilibrium sorbate
of the single component system. Both basic dyes had
liquid phase concentrations Ce .
similar capacities that the total capacity was similar to
the single dye capacity. This implied the adsorption on
5. Results and discussion to the carbon surface between the dyes was of a com-
Equilibrium isotherm constants for BY11 and MR in petitive nature. A much lower adsorption capacity was
a single component system based on the ARE func- observed for both dyes when F400 was used as the
tion for Langmuir [67], Freundlich [68] and Redlich- adsorbent as F400 had much less microporosity on the
Peterson [69] are shown in Table 4. As shown in Table 4, carbon. In addition, the adsorption capacities between
the Langmuir monolayer saturation capacities of HSA1 the two dyes showed little difference.
for BY11 and MR were four and five times higher than The equilibrium adsorption data for the binary
F400, respectively. Also, BY11 showed a slightly higher basic system were analysed by various Langmuir-
adsorption capacity on to HSA1 than MR, whilst both based multi-component isotherm models, extended
dyes showed similar adsorption capacities on to F400. Freundlich and extended Redlich-Peterson models.
Using the ARE single component isotherm parameters,
among all the Langmuir based multi-component sys-
Table 4. Equilibrium isotherm constants for BY11 and MR in tem, the P-factor provided the most successful equation
single component system based on the ARE function analysis.
to the experimental data by correlating the single and
Carbon Dye binary systems Langmuir isotherm for dye-HSA1 sys-
Langmuir KL (L/g) aL (L/mmol) Q0 (L/g) tem as shown in Table 7. As shown in Table 5, the
HSA1 BY11 1.539E + 03 8.340E + 02 2.099 Q0,single as well as the Q0,multi of BY11 and MR had
MR 9.983E + 03 4.133E + 03 1.891 similar magnitude which was due to the similar adsorp-
F400 BY11 2.746E + 02 6.004E + 02 0.457
MR 4.347E + 03 8.569E + 03 0.507 tion capacities of both dyes on HSA1. Therefore, the
Freundlich KF (L/g) nF correlation factor, P, gave a reasonable value for both
HSA1 BY11 2.425E + 00 1.126E-01
dyes. As a result, the P-factor models were able to pre-
MR 2.985E + 00 2.048E-01 dict the data for both dyes in the basic binary adsorp-
F400 BY11 6.275E-01 1.555E-01 tion system for the Langmuir-based isotherm models,
MR 6.560E-01 1.280E-01
which are shown in Figures 1 and 2. In addition to
Redlich-Peterson KR (L/g) aR (L/mmol) bR
the Langmuir-based models, prediction using the non-
HSA1 BY11 7.278E + 07 3.011E + 07 8.877E-01
MR 1.235E + 04 4.787E + 03 9.469E-01 Langmuir-based models, the extended Freundlich and
F400 BY11 5.523E + 02 9.869E + 02 9.058E-01 extended Redlich-Peterson models are conducted. The
MR 1.912E + 04 3.144E + 04 9.090E-01
extended Freundlich became the best models which
 188 L S CHAN ET AL.

2.5

2.0

qe (mmol/g)
1.5

1.0

0.5

0.0
0.00 0.05 0.10 0.15 0.20 0.25

Ce (mmol/L)
Experimental data Extended Langmiur
Downloaded by [Australian National University] at 01:47 31 December 2017

Jain and Snoeyink modified extended Langmuir P-factor

Interaction factor Extended Freundlich

Extended Redlich-Peterson

Figure 1. Different isotherm equation plots for BY11 in binary system (BY11 + MR) with HSA1.
2.5

2.0

1.5
qe (mmol/g)

1.0

0.5

0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30

-0.5
Ce (mmol/L)
Experimental data Extended Langmuir
Jain and Snoeyink modified extended Langmuir P-factor
Interaction factor Extended Freundlich
Extended Redlich-Peterson

Figure 2. Different isotherm equation plots for MR in binary system (BY11 + MR) with HSA1.

Table 7. The ARE function values for different multi-component isotherm equations using the ARE single component isotherm
parameters.
Jain and Snoeyink
Extended modified extended Extended Extended Redlich
Carbon Dye Langmuir Langmuir P-factor Interaction Freundlich and Peterson
HSA1 BY11 68.84 106.3 30.71 47.80 11.66 118.6
MR 194.9 194.9 29.79 35.47 7.310 91.62
F400 BY11 235.3 106.7 21.14 55.69 5.223 33.65
MR 3351 2518 33.65 66.40 11.08 2277

gave an ARE value of only 11.66, as shown in Table 7, The P-factor gave the best fitted model for the basic
suggested significant non-ideal effects and heteroge- dyes binary adsorption system with F400 among all
neous surfaces for the basic dye binary adsorption four Langmuir-based multi-component equations and
system with the high surface area carbon. were shown in Figures 3 and 4. From Table 7, the
 HKIE TRANSACTIONS 189

0.07

0.06

0.05

0.04

qe (mmol/g)
0.03

0.02

0.01

0
0 0.05 0.1 0.15 0.2 0.25
-0.01

-0.02

-0.03
Ce (mmol/L)
Experimental data Extended Langmiur
Jain and Snoeyink modified extended Langmuir P-factor
Interaction factor Extended Freundlich
Downloaded by [Australian National University] at 01:47 31 December 2017

Extended Redlich-Peterson

Figure 3. Different isotherm equation plots for BY11 in binary system (BY11 + MR) with F400.

0.6

0.5

0.4
qe (mmol/g)

0.3

0.2

0.1

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Ce (mmol/L)
Experimental data Extended Langmuir
Jain and Snoeyink modified extended Langmuir P-factor
Interaction factor Extended Freundlich
Extended Redlich-Peterson

Figure 4. Different isotherm equation plots for MR in binary system (BY11 + MR) with F400.

ARE values of 21.14 and 33.65 for BY11 and MR, 6. Conclusions
respectively, were obtained for the dye – F400 sys-
Adsorption studies of binary basic dyes were conducted
tem. On the other hand, the extended Langmuir and
using HSA1 produced from waste bamboo scaffolding
Jain and Snoeyink modified extended Langmuir totally
with phosphoric acid. HSA1 showed higher adsorp-
failed to predict the isotherm results. Therefore, it
tion capacities than the commercial carbon, F400, in
suggested great competition between the two differ-
both single and binary dye adsorption systems. Due
ent dyes for the pore sites on the carbon. Overall, the
to its smaller molecule size, higher adsorption capac-
extended Freundlich gave an excellent fit to the data for
ities for BY11 than MR were observed for HSA1. The
both dyes in which the ARE values were the smallest
extended Freundlich model was overall the best fitted
which again suggested multi-layer adsorption for this
to the experimental data for both activated carbons,
system.
 190 L S CHAN ET AL.
suggesting significant non-ideal effects and heteroge-
neous surfaces for the basic dye binary adsorption sys-
tem with activated carbons. The P-factor model was the
best for the Langmuir-based isotherm models.
Acknowledgements
The authors would like to acknowledge the support of the
Research Grant Council – University Grants Committee, the
Innovation and Technology Fund of the HKSAR Govern-
ment, The Hong Kong University of Science and Technology
and Green Island International Ltd.
Funding
This work was supported by The Hong Kong University of
Science and Technology; Innovation and Technology Com-
mission; Green Island International Ltd; Research Grants
Council – University Grants Committee.
Downloaded by [Australian National University] at 01:47 31 December 2017
Notes on contributors
Ir L S Chan, BEng, MPhil, CEng,
MIChemE, MHKIE. Ir Chan is a Char-
tered Chemical Engineer with 11 years
of post-graduation experience in envi-
ronmental consultancy and process engi-
neering. She previously worked in The
Hong Kong University of Science and
Technology (HKUST), conducting
research works for identifying the dye
adsorptive capability of the bamboo produced activated car-
bon, which is a potential technology for wastewater treat-
ment. Ir Chan was awarded the First Runner-Up in the 2011
Environmental Paper Award of the HKIE Environmental
Division.
Dr W H Cheung, BSc, Ph.D., MIET,
MIEAust, MRACI, CChem. Dr Che-
ung is a Chartered Chemist and spe-
cialises in wastewater treatment, waste
management, and environmental risk
management. As a co-author, he has
been shortlisted in the HKIE Outstand-
ing Paper Award for Young Engineers /
Researchers 2012 and awarded the First
Runner-Up in the 2011 Environmental Paper Award of the
HKIE Environmental Division and Certificate of Merit in the
2012 Environmental Paper Award of the HKIE Environmen-
tal Division.
Emeritus Prof S J Allen, BSc, Ph.D.,
FIChemE. Prof Allen is the DuPont
Professor of Process Engineering of
the School of Chemistry and Chemical
Engineering at the Queen’s University of
Belfast in Northern Ireland. He held the
post of the Head of School of Chemical
Engineering for a term of eight years. His
areas of research are focused on adsorp-
tion and the environment with specific interests in the mod-
ification of adsorbents with different functional groups; nat-
ural adsorbents for the removal of pollutants from aqueous
solution and from gaseous systems; adsorbent surface chem-
istry in the mechanism of dye adsorption; the development
of mass transfer and diffusion models to describe the adsorp-
tion processes. He is also the Editor of Chemical Engineering
Journal.
Prof G McKay, BTech, Ph.D., DSc,
CChem, CEng, CEnv, FIChemE, FIE,
FInstPetrol, FIQA, FRSC, FHKIE. Prof
McKay has almost 40 years of experi-
ence in the academia and industry. He
is currently a Professor of Sustainable
Development at the Hamad Bin Khalifa
University. Prior to this, he was the Head
of Department and Professor in Chem-
ical and Biological Engineering at the HKUST. During his
time in Hong Kong, he was the Chairman of the Chemi-
cal Discipline Advisory Panel of the HKIE. Prof McKay has
over 400 publications in international refereed journals and
authored eight books about energy, environment and process
design. He co-authored the third most cited paper (6000 cites
to date) ever in the SCI Chemical Engineering sector and has
an h-index of 85.
ORCID
W H Cheung http://orcid.org/0000-0003-3134-5709
G McKay http://orcid.org/0000-0002-6086-2564
References
[1] Robinson T, McMullan G, Marchant R, et al. Remedia-
tion of dyes in textile effluent: a critical review on cur-
rent treatment technologies with a proposed alternative.
Bioresour Technol; 2001;77:247–255.
[2] Ogugbue CJ, Sawidis T. Bioremediation and detoxifica-
tion of synthetic wastewater containing triarylmethane
dyes by Aeromonas hydrophila isolated from industrial
effluent. Biotechnol Res Int. 2011;2011:Article 967925,
11 pages. DOI:10.4061/2011/967925.
[3] Zollinger H. Synthesis, properties of organic dyes and
pigments, in color chemistry. New York: VCH Publish-
ers; 1987. p. 92–102.
[4] Kumar MNVR, Sridhari TR, Bhavani KD, et al. Trends
in color removal from textile mill effluents. Colourage.
1998;45:25–34.
[5] Couto SR. Dye removal by immobilised fungi. Biotech-
nol Adv. 2009;27:227–235.
[6] Hunger K. Important chemical chromophores of dye
classes. In: Hunger K, editor. Industrial dyes: chemistry,
properties and applications. Weinheim: Wiley-VCH,
2003. p. 13–112.
[7] Marungrueng K, Pavasant P. High performance biosor-
bent (Caulerpa lentilifera) for basic dye removal. Biore-
sour Technol. 2007;98:1567–1572.
[8] Mao J, Won SW, Min J, et al. Removal of Basic Blue
3 from aqueous solution by Corynebacterium glutam-
icum biomass: biosorption and precipitation mecha-
nism. Korean J Chem Eng. 2008;25:1060–1064.
[9] Al-Degs Y, Khraisheh MAM, Allen SJ, et al. Effect of car-
bon surface chemistry on the removal of reactive dyes
from textile effluent. Water Res. 2000;34:927–935.
[10] Gupta VK, Saleh TA. Sorption of pollutants by porous
carbon, carbon nanotubes and fullerene – An overview.
Environ Sci Pollut Res. 2013;20:2828–2843.
[11] Roskill. The economics of activated carbon. 8th ed.
London (the UK): Roskill Information Services; 2008.
[12] The Freedonia Group. World activated carbon. Cleve-
land, OH (the US): The Freedonia Group; 2016. p. 423.
[13] Puziy AM, Poddubnaya OI, Martinez-Alonso A, et al.
Surface chemistry of phosphorus-containing carbons of
lignocellulosic origin. Carbon N Y. 2005;43:2857–2868.

[14] Lua AC, Guo J. Microporous oil-palm-shell activated
carbon prepared by physical activation for gas-phase
adsorption. Langmuir. 2001;17:7112–7117.
[15] Ahmaruzzaman M, Gupta VK. Rice husk and its ash as
low-cost adsorbents in water and wastewater treatment.
Ind Eng Chem Res. 2011;50:13589–13613.
[16] Valix M, Cheung WH, McKay G. Preparation of acti-
vated carbon using low temperature carbonisation and
physical activation of high ash raw bagasse for acid dye
adsorption. Chemosphere. 2004;56:493–501.
[17] Asfaram A, Fathi MR, Khodadoust S, et al. Removal
of Direct Red 12B by garlic peel as a cheap adsorbent:
kinetics, thermodynamic and equilibrium isotherms
study of removal. Spectrochim Acta A Mol Biomol
Spectrosc. 2014;127:415–421.
[18] Gupta VK, Nayak A. Cadmium removal and recovery
from aqueous solutions by novel adsorbents prepared
from orange peel and Fe2 O3 nanoparticles. Chem Eng
J. 2012;180:81–90.
[19] Mittal A, Krishnan L, Gupta VK. Removal and recovery
Downloaded by [Australian National University] at 01:47 31 December 2017
of malachite green from wastewater using an agricul-
tural waste material, de-oiled soya. Sep Purif Technol.
2005;43:125–133.
[20] Mittal A, Mittal J, Malviya A, et al. Decoloration treat-
ment of a hazardous triarylmethane dye, Light Green
SF (Yellowish) by waste material adsorbents. J Colloid
Interface Sci. 2010;342:518–527.
[21] Jain AK, Gupta VK, Bhatnagar A, et al. A compar-
ative study of adsorbents prepared from industrial
wastes for removal of dyes. Sep Sci Technol. 2003;38:
463–481.
[22] Mittal A, Kaur D, Malviya A, et al. Adsorption stud-
ies on the removal of coloring agent phenol red from
wastewater using waste materials as adsorbents. J Col-
loid Interface Sci. 2009;337:345–354.
[23] Mittal A, Mittal J, Malviya A, et al. Adsorptive removal
of hazardous anionic dye “Congo red” from wastewa-
ter using waste materials and recovery by desorption. J
Colloid Interface Sci. 2009;340:16–26.
[24] Chan OS, Cheung WH, McKay G. Preparation and
characterisation of demineralised tyre derived activated
carbon. Carbon N Y. 2011;49:4674–4687.
[25] Saleh TA, Gupta VK. Processing methods, characteris-
tics and adsorption behavior of tire derived carbons: A
review. Adv Colloid Interface Sci. 2014;211:93–101.
[26] Statistics Unit Environment Protection Department.
Monitoring of solid waste in Hong Kong waste statis-
tics for 2015. Hong Kong: Environmental Protection
Department; 2016.
[27] Choy KKH, Barford JP, McKay G. Production of acti-
vated carbon from bamboo scaffolding waste-process
design, evaluation and sensitivity analysis. Chem Eng J.
2005;109:147–165.
[28] Laine J, Calafat A, Labady M. Preparation and char-
acterization of activated carbons from coconut shell
impregnated with phosphoric acid. Carbon N Y. 1989;
27:191–195.
[29] Jagtoyen M, Derbyshire F. Some considerations of the
origins of porosity in carbons from chemically activated
wood. Carbon N Y. 1993;31:1185–1192.
[30] Jagtoyen M, Derbyshire F. Activated carbons from yel-
low poplar and white oak by H3 PO4 activation. Carbon
N Y. 1998;36:1085–1097.
[31] Asada T, Ishihara S, Yamane T, et al. Science of bamboo
charcoal: study on carbonizing temperature of bam-
boo charcoal and removal capability of harmful gases.
J Health Sci. 2002;48:473–479.
HKIE TRANSACTIONS 191
[32] Abe I, Fukuhara T, Iwasaki S, et al. Development of a
high density carbonaceous adsorbent from compressed
wood. Carbon N Y. 2001;39:1485–1490.
[33] Kannan N, Sundaram MM. Kinetics and mechanism
of removal of methylene blue by adsorption on var-
ious carbons - a comparative study. Dyes Pigments.
2001;51:25–40.
[34] Wu FC, Tseng RL, Juang RS. Preparation of activated
carbons from bamboo and their adsorption abilities for
dyes and phenol. J Environ Sci Health A Tox Hazard
Subst Environ Eng. 1999;34:1753–1775.
[35] Choy KKH, Allen SJ, McKay G. Multicomponent equi-
librium studies for the adsorption of basic dyes from
solution on lignite. Adsorption. 2005;11:255–259.
[36] Chan LS, Cheung WH, Allen SJ, et al. Separation of
acid-dyes mixture by bamboo derived active carbon.
Sep Purif Technol. 2009;67:166–172.
[37] Agarwal S, Tyagi I, Gupta VK, et al. Rapid adsorption of
ternary dye pollutants onto copper (I) oxide nanoparti-
cle loaded on activated carbon: experimental optimiza-
tion via response surface methodology. J Environ Chem
Eng. 2016;4:1769–1779.
[38] Asfaram A, Ghaedi M, Azqhandi MHA, et al. Statis-
tical experimental design, least squares-support vec-
tor machine (LS-SVM) and artificial neural network
(ANN) methods for modeling the facilitated adsorption
of methylene blue dye. RSC Adv. 2016;6:40502–40516.
[39] Bagheri AR, Ghaedi M, Asfaram A, et al. Comparative
study on ultrasonic assisted adsorption of dyes from sin-
gle system onto Fe3 O4 magnetite nanoparticles loaded
on activated carbon: experimental design methodology.
Ultrason Sonochem. 2017;34:294–304.
[40] Bagheri AR, Ghaedi M, Asfaram A, et al. Modeling and
optimization of simultaneous removal of ternary dyes
onto copper sulfide nanoparticles loaded on activated
carbon using second-derivative spectrophotometry. J
Taiwan Inst Chem E. 2016;65:212–224.
[41] Devaraj M, Saravanan R, Deivasigamani R, et al. Fab-
rication of novel shape Cu and Cu/Cu2 O nanoparticles
modified electrode for the determination of dopamine
and paracetamol. J Mol Liq. 2016;221:930–941.
[42] Dil EA, Ghaedi M, Asfaram A. The performance of
nanorods material as adsorbent for removal of azo
dyes and heavy metal ions: application of ultrasound
wave, optimization and modeling. Ultrason Sonochem.
2017;34:792–802.
[43] Dil EA, Ghaedi M, Ghaedi A, et al. Application of artifi-
cial neural network and response surface methodology
for the removal of crystal violet by zinc oxide nanorods
loaded on activate carbon: kinetics and equilibrium
study. J Taiwan Inst Chem E. 2016;59:210–220.
[44] Mazaheri H, Ghaedi M, Asfaram A, et al. Performance
of CuS nanoparticle loaded on activated carbon in the
adsorption of methylene blue and bromophenol blue
dyes in binary aqueous solutions: using ultrasound
power and optimization by central composite design. J
Mol Liq. 2016;219:667–676.
[45] Ansari F, Ghaedi M, Taghdiri M, et al. Application
of ZnO nanorods loaded on activated carbon for
ultrasonic assisted dyes removal: experimental design
and derivative spectrophotometry method. Ultrason
Sonochem. 2016;33:197–209.
[46] Asfaram A, Ghaedi M, Hajati S, et al. Rapid removal of
Auramine-O and methylene blue by ZnS:Cu nanopar-
ticles loaded on activated carbon: A response sur-
face methodology approach. J Taiwan Inst Chem E.
2015;53:80–91.
 192 L S CHAN ET AL.
[47] Chan LS, Cheung WH, Lau KST, et al. Production
of high surface area activated carbons from waste
bamboo scaffolding. HKIE Trans. 2017;3:133–140.
DOI:10.1080/1023697X.2017.1345330.
[48] Brunauer S, Emmett PH, Teller E. Adsorption of
gases in multimolecular layers. J Am Chem Soc.
1938;60:309–319.
[49] Horvath G, Kawazoe K. Method for the calculation of
effective pore-size distribution in molecular-sieve car-
bon. J Chem Eng Jpn. 1983;16:470–475.
[50] Bansal RP, Donnet J, Stoeckli F. Active carbon. New
York: Marcel Dekker; 1988.
[51] Butler JAV, Ockrent C. Studies in electrocapillar-
ity Part III The surface tensions of solutions con-
taining two surface-active solutes. J Phys Chem.
1930;34:2841–2859.
[52] Butler JAV, Ockrent C. Adsorption from solutions con-
taining two solutes. Nature. 1930;125:853–854.
[53] Jain JS, Snoeyink VL. Adsorption from bisolute sys-
tems on active carbon. J Water Pollut Control Fed.
Downloaded by [Australian National University] at 01:47 31 December 2017
1973;45:2463–2479.
[54] McKay G, Al-Duri B. Simplified model for the equilib-
rium adsorption of dyes from mixtures using activated
carbon. Chem Eng Prog. 1987;22:145–156.
[55] Schay GJ, Fejes FP, Szethmary J. Adsorption of gases
and gas mixtures. Acta Chim Acad Sci Hung. 1957;
12:299–308.
[56] Yon CM, Turnock PH. AIChE Symposium Series 67:75,
(1971).
[57] Mathews AP. Mathematical modeling of multicompo-
nent adsorption in batch reactors. [Ph.D.]. The Univer-
sity of Michigan; 1975.
[58] Seidel A, Gelbin D. On applying the ideal adsorbed solu-
tion theory to multicomponent adsorption equilibria
of dissolved organic-components on activated carbon.
Chem Eng Sci. 1988;43:79–88.
[59] McKay G, Al-Duri B. Prediction of multicomponent
adsorption equilibrium data using empirical correla-
tions. Chem Eng J Biochem Eng J. 1989;41:9–23.
[60] Al-Duri B, McKay G. Prediction of binary-system for
kinetics of batch adsorption using basic-dyes onto acti-
vated carbon. Chem Eng Sci. 1991;46:193–204.
[61] Fritz W, Schluend EU. Simultaneous adsorption equi-
libria of organic solutes in dilute aqueous-solutions
on activated carbon. Chem Eng Sci. 1974;29:1279–
1282.
[62] Glover MRL, Young BD, Bryson AW. Modeling the
binary adsorption of gold and zinc cyanides onto a
strong-base anion-exchange resin. Int J Miner Process.
1990;30:217–228.
[63] Young BD, Leroux JD, Bryson AW. The binary
adsorption of gold cyanide and ethyl xanthate onto
activated carbon. Hydrometallurgy. 1991;26:
395–401.
[64] McKay G, Al-Duri B. Extended empirical Freundlich
isotherm for binary systems – a modified procedure
to obtain the correlative constants. Chem Eng Process.
1991;29:133–138.
[65] Al-Duri B, McKay G. Pore diffusion - dependence of
the effective diffusivity on the initial sorbate concentra-
tion in single and multisolute batch adsorption systems.
J Chem Technol Biot. 1992;55:245–250.
[66] Kapoor A, Yang RT. Correlation of equilibrium adsorp-
tion data of condensible vapours on porous adsorbents.
Gas Sep Purif. 1989;3:187–192.
[67] Langmuir I. The constitution and fundamental proper-
ties of solids and liquids. Part I. solids. J Am Chem Soc.
1916;38:2221–2295.
[68] Freundlich H. Concerning adsorption in solutions. Z
Phys Chem. 1906;57:385–470.
[69] Redlich O, Peterson DL. A useful adsorption isotherm.
J Phys Chem. 1959;63:1024–1024.