Chemical Engineering Journal 181–182 (2012) 289–299

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Chemical Engineering Journal

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Application of Response Surface Methodology for Methylene Blue dye removal

from aqueous solution using low cost adsorbent
Soumasree Chatterjee a , Atul Kumar a , Srabanti Basu b , Susmita Dutta a,∗
a
Department of Chemical Engineering, National Institute of Technology, Durgapur, Durgapur 713209, West Bengal, India
b
Department of Biotechnology, Heritage Institute of Technology, Kolkata 700107, India

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

Article history: The adsorptive removal of Methylene Blue (MB) dye using a low cost adsorbent, prepared from Parthe-
Received 18 September 2011 nium hysterophorus, has been investigated. Response Surface Methodology has been employed to model
Received in revised form statistically and optimize the process variables for preparation of adsorbent, removal of MB and recovery
20 November 2011
of adsorbed dye using Design Expert software. During optimization of carbonizing condition, weight ratio
Accepted 21 November 2011
of activating agent to parthenium (1.0–1.5), temperature (450–550 ◦ C) and time of carbonization (1–2 h)
have been considered as input parameters and decolorizing power (DP) of prepared sample is regarded
Keywords:
as response. The carbonization at 550 ◦ C for 1 h, with a weight ratio of activating agent to parthenium at
Adsorption
Response Surface Methodology
1.05:1 has been found to be optimum condition. The sample thus obtained is termed as Charred Parthe-
Parthenium hysterophorus nium (CP) and is used for further studies on dye removal. To get the optimum condition for removal of dye
Methylene Blue using CP, four input parameters viz., initial concentration of dye (25–50 mg/L), weight of CP (0.2–0.5 g), pH
Kinetic study (5–9) and temperature (30–40 ◦ C) have been varied according to the experimental design as prescribed
by software considering percentage removal of dye as response. The removal with initial concentration of
MB 25 mg/L, weight of CP 0.22 g at pH 7 and temperature 35 ◦ C has been found to be optimum and 93.4%
removal is achieved. Finally, the spent adsorbent, termed as Spent Charred Parthenium (SCP), obtained
at the optimum condition of dye removal has been taken to assess the recovery of dye. Three parameters
viz., amount of SCP (0.2–0.5 g), pH (5–9) and contact time (1–3 h) have been chosen as input parameters
whereas percentage recovery has been considered as response. The results indicate that pH has a great
influence on the recovery of dye.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction to its simplicity of design, ease of operation and insensitivity to

The effluents coming from different industries such as tex-
tile, pulp and paper, leather, paint, ceramic, pottery etc. that use
synthetic dyes to color their products, may lead to water pollu-
tion if they are not treated properly before their discharge to the
environment [1–20]. Methylene Blue (MB), a common dye used
for dying cotton, silk and wood, has adverse effect on human
health such as eye burns, breathing problem, gastritis, diarrhea,
and vomiting [1–12]. Thus, it is essential to remove MB dye from
effluent before it is discharged. Though several techniques such as
ion exchange, photo-oxidation processes, flocculation, precipita-
tion, microbiological decomposition, and ozonation are available
for dye removal from industrial effluents, every method has its
own limitation. Adsorption process is considered as one of the
most efficient methods to remove pollutants from effluent due
∗ Corresponding author. Tel.: +91 343 2755234; mobile: +91 9830075233;
fax: +91 343 2547375.
E-mail address: susmita che@yahoo.com (S. Dutta).
toxic substances [1–26]. Generally commercial activated carbon
prepared by carbonizing wood, lignite etc. is used for such pur-
pose, but the high initial and regeneration cost of commercial
activated carbon has restricted its use in industrial application.
To curb down the expense and to make the whole process eco-
nomical, researches are now tending towards the preparation of
low cost adsorbent from cheap/waste materials [1–23]. Parthenium
hysterophorus, commonly known as parthenium is an unwanted
hazardous weed and found in the arid region of India. Due to
the presence of toxin parthenin in pollen, it can trigger allergies,
dermatitis and respiratory malfunction in humans, dermatitis in
cattle and other domestic animals. It often becomes a threat to
biodiversity as it overgrows the native species. Parthenium is usu-
ally cut down to check its growth for better crop production and
preservation of biodiversity. The prima-facie objective of present
work is to make over this harmful weed to low cost adsorbent, a
value added product, to be used for abatement of dye from waste
water to minimize environmental pollution. Though few works
have been done in this line [8,14], a comprehensive investigation
consisting of optimization of process condition for carbonization of

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.11.081
290 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299

adsorption of dye at its optimum condition is another aim of the

Nomenclature present investigation.
The effectiveness of an adsorbent is best judged by its removal
A1 time of carbonization given in Eq. (4) (h) ability which in turn depends on its preparation condition. In the
A2 initial concentration of MB as given in Eq. (8) (mg/L) present article carbonization through chemical activation method
A3 weight of SCP as given in Eq. (9) (g) has been used for preparation of low cost adsorbent from P. hys-
B1 temperature of carbonization as given in Eq. (4) (◦ C) terophorus. The weight ratio of activating agent to parthenium,
B2 weight of CP as given in Eq. (8) (g) temperature of carbonization and time of carbonization have been
B3 pH as given in Eq. (9) identified as process variables. As long as the preparation of
C1 weight ratio as given in Eq. (4) (g/g) efficient adsorbent is concerned, optimization of these process vari-
C2 pH as given in Eq. (8) ables is very much crucial. This has also been observed by other
C3 time of contact as given in Eq. (9) (h) scientists [11,24]. The conventional technique for the optimiza-
C0 initial concentration of MB as used in the expression tion of a multivariable system usually defines one factor at a time
of RL [21]. The shortcomings associated with these classical and conven-
KF adsorption equilibrium constant used in tional methods are non-reliability of the results, non-depiction of
Freundlich adsorption isotherm model the combined effect of all the independent variables at a single
(mg adsorbate/g Charred Parthenium) time and greater time consumption due to more number of exper-
(mg adsorbate/L)n iments. These shortcomings can be overcome by optimizing all
KL adsorption equilibrium constant used in Langmuir the affecting parameters collectively using statistical experimen-
isotherm (L/mg adsorbate) tal design method such as Response Surface Methodology (RSM)
kL overall rate constant as used in Eq. (5) (h−1 ) [11,18–21]. RSM is a collection of mathematical and statistical tech-
kP pseudo-second-order rate constant of sorption in niques useful for developing, improving and optimizing processes
Eq. (6) (g mg−1 h−1 ) [18–21,24]. It can be used to define the relationships between the

kM rate constant of intraparticle transport as used in Eq. response and the independent variables with a minimum number
(7) (mg g−1 h−1/2 ) of trails according to special experimental designs based on fac-
N total number of experiments torial designs [18]. The main advantages of RSM lie in the fact that
n number of variables this method is less expensive and time consuming than the classical
nF adsorption equilibrium constant used in Freundlich methods [18]. Though use of RSM is quite common for optimization
adsorption isotherm model of chemical processes, only very few investigators [11,12,23–26]
nc center point have used it for optimization of carbonizing condition for prepara-
qt solid phase concentration of adsorbate at time t tion of adsorbent. As far the knowledge of present research group
(mg/g) no comprehensive study on optimization of process condition for
qe solid phase concentration of adsorbate at equilib- carbonization of parthenium for preparation of low cost adsorbent
rium (mg/g) has been made by any statistical method. Therefore, in the present
q0 solid phase concentration of adsorbate for complete study RSM has been employed to model and to optimize the process
monolayer formation (mg/g) condition for carbonization of parthenium. The charred sample pre-
R1 decolorizing power, (mg MB removed/g charred pared at optimum condition as designated by software is termed as
sample) Charred Parthenium (CP) and further studies have been made with
R2 percentage removal of MB (%) this CP. To examine the efficacy of prepared adsorbent, a detailed
R3 percentage recovery of MB (%) kinetic and equilibrium study of MB removal with CP has been
RL separation factor made. RSM has also been applied to assess the interactive effect of
t time (h) different process variables for getting the insight and to optimize
Xi independent variables called factors the process condition for removal of MB using CP. Finally, recovery
Y response of the system of MB from Spent Charred Parthenium (SCP), obtained by adsorb-
ˇ0 constant coefficient ing MB on CP at optimum condition as designated by software, has
ˇi linear coefficient been meticulously studied using RSM considering weight of SCP, pH
ˇii quadratic coefficient and time of contact as operating parameters and percentage recov-
ˇij interaction coefficient ery as output variable. As far as known, no comprehensive study
on recovery of dye as well as regeneration of spent adsorbent has
been made by any statistical tool so far. Thus, the recovery study
using RSM may be a novel approach in this field.
parthenium; optimization of removal condition of Methylene Blue
by prepared adsorbent and furthermore, optimization of recovery
of dye and regeneration of adsorbent was in need. Thus, in the 2. Materials and methods
present article, a systematic study has been made to meet all the
aforementioned shortcomings in great details. The optimization of 2.1. Optimization of carbonization condition and preparation of
all these processes has been done using Response Surface Method- Charred Parthenium (CP)
ology to elucidate the effect of more than one process parameters
at a time. Design Expert software 8.0.5 is used for such purposes. Experimental
As far the knowledge of present research group, no optimization The parthenium weeds were collected from the nearby areas. It
work on these processes specifically on recovery of dye and regen- was then washed with water to get rid of dust particles and dried in
eration of adsorbent has been made so far. Thus, assessment of the sunlight for 2–3 days. Dried parthenium was cut into small pieces
efficacy of adsorbent prepared by carbonizing parthenium at its of 2–3 cm and was fed to a mixer and grinder and thus ground.
optimum condition as a dye removing agent is not the sole aspire The mass was sieved to assort the particles having the size less
of the present study but to establish the optimum condition for than 90 ␮m. Initially three activating agents viz., ortho-phosphoric
recovery of dye and regeneration of spent adsorbent obtained after acid (85% Pure, MERCK), zinc chloride (MERCK) and sulfuric acid
 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299
(98% Pure, MERCK), have been chosen to be tested for use in the
preparation of adsorbent. Thus, requisite amount of any one of the
abovementioned activating agents was mixed with the dried pow-
dered parthenium of size less than 90 ␮m. This was then carbonized
in a muffle furnace by heating at an elevated temperature for cer-
tain period of time. The charred material was cooled and washed
firstly with dilute ammonia solution (A.R. Grade, SARA Fine Chem-
icals Pvt. Limited) in order to remove any unconverted activating
agent from carbonaceous material and then with distilled water.
Washing was continued until the pH of the filtrate was found to be
exactly 7. The charred material left on the filter paper was placed
on a petridish and left for drying overnight in an ambient condition.
The dried samples were crushed and fractionated into different
size fractions (135–275 ␮m). The decolorizing power (DP, mg MB
removed/g charred sample) of each sample was then tested.
RSM was used to optimize carbonization condition for prepara-
tion of adsorbent. Design Expert software 8.0.5 was used for this
purpose. Initially four parameters viz., types of activating agent,
weight ratio of activating agent to parthenium, temperature and
time of carbonization were considered as independent variables
or factors and DP as response. According to the software, out of
these four factors the first one was classified as categoric factor
whereas other three factors are sorted as numeric factors. The
experimental runs were designed statistically using RSM consid-
ering those categoric and numeric factors. Analysis revealed that
total sixty experiments were necessary to be performed. To reduce
the number of experimental runs, the number of categoric fac-
tors was limited to zero by selecting the best activating agent.
This was done by examining the DP of charred sample obtained
by carbonizing parthenium using each activating agent separately.
Experimentation revealed that ortho-phosphoric acid was the best
among all other activating agents. Thereby, numbers of experi-
mental runs were reduced to twenty. Finally, experiments were
designed statistically by varying three numeric factors viz., weight
ratio of activating agent to parthenium (1.0–1.5), temperature of
carbonization (450–550 ◦ C), and time (1–2 h) suitably.
Design of experiments
Response Surface Methodology is a statistical method that uses
experimental data obtained from specified experimental design
to model and optimize any process in which response of interest
is influenced by several variables [5,21]. Primarily, this optimiza-
tion is done by following three major steps viz., performing the
statistically designed experiments, estimating the coefficients in a
mathematical model and predicting the responses and examining
the adequacy of the model [27]. RSM helps to enumerate the rela-
tionships between output variables called responses (Y) and input
variables called factors (Xi s) [21].
Y = f (X1 , X2 , X3 , . . . , Xn )
A standard RSM design called Central Composite Design (CCD)
was applied in the present work. This method is suitable for fitting a
quadratic surface and it helps to optimize the effective parameters
with a minimum number of experiments, as well as to analyze the
interaction between the parameters [5]. Generally, the CCD consists
of a 2n factorial runs with 2n axial runs and nc central runs [5].
The centre points are utilized to evaluate the experimental error
and the reproducibility of the data. Thus, for carbonization process
having three independent parameters (n = 3), the total number of
experiments required is
N = 2n + 2n + nc = 23 + (2 × 3) + 6 = 20
The experimental sequence was randomized in order to mini-
mize the effects of uncontrolled factors [5,21]. The outcome of each
experimental run was analyzed and the response was correlated
291
with three input factors for carbonization of parthenium for prepa-
ration of adsorbent through an empirical second degree polynomial
equation as given by the following equation

n

n 
n 
n−1
Y = ˇ0 + ˇi Xi + ˇii Xi2 + ˇij Xi Xj (3)
i=1 i=1 i=1 j=1
where, Y is the predicted response, ˇ0 the constant coefficient, ˇi
the linear coefficients, ˇij the interaction coefficients and ˇii the
quadratic coefficient [11].
ANOVA was used to model the system represented by indepen-
dent parameters and dependent output response and to optimize
the system by estimating the statistical parameters. The minimum
(−1) and maximum (+1) level of the weight ratio of activating agent
to parthenium, temperature and time of carbonization were 1 and
1.5, 450 ◦ C and 550 ◦ C and 1 h and 2 h respectively. The statisti-
cal experimental design as specified by the software is shown in
Table 1. The experiments were performed according to this design
and responses were analyzed. Carbonization for 1 h at 550 ◦ C tem-
perature with 1.05:1 weight ratio of activating agent to parthenium
has been found to be optimum condition as indicated by the soft-
ware. The sample thus obtained is termed as Charred Parthenium
(CP) and is used for further studies on dye removal.
2.2. Characterization of Charred Parthenium (CP)
The physico-chemical characterization of Charred Parthenium
was done following standard protocol [22]. The properties mea-
sured include solid density, bulk density, ash content, moisture
content, etc. Surface area of CP was determined by BET method
using Quantachrome Instruments (©1994–2007, version 10.01,
USA). Pore volume of CP was measured using Mercury Intrusion
Method. Quantachrome make Poremaster 60 (USA) was used for
such purposes. In all of these experiments, particles having the size
less than 90 ␮m were used to get consistent results.
2.2.1. Scanning Electron Microscopy (SEM)
SEM study of CP was done to get its topographical characteriza-
tion. The sample was mounted on brass stubs using double-sided
adhesive tape. SEM photograph was taken with scanning electron
microscope (HITACHI – S-3000 N, Japan) at the required magnifi-
cation at room temperature. The working distance of 25 mm was
maintained and acceleration voltage used was 15 kV, with the sec-
ondary electron image (SEI) as a detector.
2.2.2. FTIR study
FTIR study of CP and SCP were conducted with the help of Fourier
Transform Infra Red machine (Nicolet iS10, Thermo Fischer Scien-
tific, USA). For FTIR study, 2 mg of finely ground sample was mixed
(1) well with approximately 40 mg of KBr (MERCK) for the preparation
of transparent pellets, from which functional groups were deter-
mined.
2.3. Removal of MB using CP
2.3.1. Kinetic study
To assess the mechanism of dye removal using CP and to deter-
mine the kinetic parameters useful for designing a continuous
contactor, kinetic study was done. A definite amount of MB (AR
grade, MERCK) was dissolved in distilled water to prepare a stock
solution of MB to be used for kinetic study. Different concentra-
(2) tion of MB solution was obtained by diluting the stock solution
with definite amount of distilled water. The dye solution of spe-
cific concentration was contacted with specific amount of CP in a
batch contactor. To eliminate the mass transfer resistance due to
bulk diffusion, the solution was stirred continuously. The operating
292 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299

Table 1
Experimental design for preparation of Charred Parthenium.

Run Time (A1 , h) Temperature (B1 , ◦ C) Weight ratio (C1 , g/g) Decolorizing power (R1, mg/g)

1 1.5 500.0 1.25 37.8

2 1.5 415.9 1.25 30.5
3 1.5 500.0 0.83 32.4
4 2.3 500.0 1.25 46.7
5 1.0 450.0 1.5 23.2
6 1.5 500.0 1.25 37.9
7 1.5 584.1 1.25 48.6
8 1.5 500.0 1.25 37.9
9 2.0 450.0 1.0 39.1
10 2.0 550.0 1.0 42.4
11 1.5 500.0 1.67 41.3
12 0.6 500.0 1.25 29.6
13 1.5 500.0 1.25 37.9
14 1.0 550.0 1.5 44.2
15 1.0 450.0 1.0 33.1
16 2.0 550.0 1.5 49.5
17 1.0 550.0 1.0 32.2
18 2.0 450.0 1.5 32.5
19 1.5 500.0 1.25 37.9
20 1.5 500.0 1.25 37.9

parameters viz., initial concentration of dye, weight of adsorbent,
size of adsorbent were varied in the range of 10–50 mg/L, 0.1–0.5 g
and 135–275 ␮m respectively in a judicial manner. The concen-
tration of residual MB in solution was analyzed in UV–visible
Spectrophotometer (UV 2300, TECHCOM, GERMANY) at 660 nm.
2.3.2. Equilibrium study
For equilibrium study 100 ml MB solution having the concentra-
tion in the range of 10–100 mg/L was contacted with 0.5 g of CP and
the flasks were placed overnight in a BOD incubator with shaker at
a constant temperature of 35 ◦ C. Finally the solutions were cen-
trifuged and the clear liquid was analyzed spectrophotometrically
by UV–visible spectrophotometer at 660 nm.
2.3.3. Optimization of MB removal using CP by RSM
Experimental. During kinetic study of MB removal using CP in a
batch contactor, it is seen that the size of CP has negligible effect on
the percentage removal of MB under the size ranges studied. Thus,
during optimization using RSM, size of CP has not been consid-
ered as a numeric factor whereas four other parameters viz., initial
concentration of MB, weight of CP, pH and temperature were con-
sidered as input factors and percentage removal of MB as response.
These four input parameters are the standard ones and selected
by other scientists also [11]. However, ‘time’ may be considered as
another parameter but from kinetic study, the variation of percent-
age removal with time has already been observed. Therefore, only
four parameters have been selected instead of five to reduce the
number of experiments from 50 to 30. Kinetic study reveals that
the percentage removal of MB has reached to its saturation value
within 45 min in all the cases irrespective of the parameters studied.
Thus, during optimization study of process variables for removal of
MB using CP, run time has been fixed to 8 h. Volume of solution
was maintained 200 ml in each case. The operating conditions viz.,
initial concentration of MB, weight of adsorbent, pH and tempera-
ture were maintained according to the design as made by Design
Expert software. The concentration of residual MB in solution was
measured spectrophotometrically.
Design of experiments. RSM was employed to model, optimize and
assess the interactive effect of various process variables for removal
of MB using CP. The maximum (+1) and minimum (−1) level of
these process variables viz., initial concentration of MB, weight of
CP, pH and temperature were 50 mg/L and 25 mg/L, 0.5 g and 0.2 g,
9 and 5 and 40 ◦ C and 30 ◦ C respectively. The statistical experimen-
tal design as specified by the software along with the values of
response is shown in Table 2. According to the analysis of ANOVA,
the optimum condition for MB removal is obtained when ini-
tial concentration of MB, weight of CP, pH and temperature have
the values of 25 mg/L, 0.22 g, 7, 35 ◦ C respectively. The solid mass
obtained after filtration of slurry acquired by carrying out removal
of MB using CP at the optimum condition is termed as Spent Charred
Parthenium (SCP). Studies on recovery of dye and regeneration of
spent adsorbent was made using SCP.
2.4. Recovery of MB from SCP
Recovery of MB as well as regeneration of SCP was studied by
contacting SCP with buffer solution having different pH for particu-
lar period of time. Volume of solution was maintained at 100 ml in
each case. RSM is used to model, optimize and assess the interactive
effect of process variables for the recovery of dye. Three operating
parameters viz., weight of SCP, pH and time of contact were con-
sidered as input parameters and percentage recovery as response.
Temperature could have also been selected as a parameter. But vari-
ation of temperature during recovery incurs cost to the process. To
make the recovery process cost-effective, temperature has not been
selected as a parameter. The values of maximum (+1) and minimum
(−1) of these parameters viz., weight of SCP, pH and time of contact
were 0.5 and 0.2 g, 9 and 5 and 3 h and 1 h respectively. The statis-
tical experimental design as specified by the software is shown in
Table 3.
3. Results and discussion
3.1. Optimization of carbonization condition and preparation of
Charred Parthenium (CP)
Three operating parameters for carbonization of parthenium
viz., weight ratio of activating agent to parthenium, temperature
of carbonization and time of carbonization have been optimized
by RSM using Design Expert software considering DP of charred
sample as response. DP of each charred sample obtained at dif-
ferent experimental conditions as designed by software is shown
in Table 1. A regression analysis has been performed to fit the
responses. As suggested by the software no transformation was
required and 2FI model was chosen to fit the data. Final equation
 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299 293

Table 2
Experimental design for removal of Methylene Blue.

Run Initial concentration of Weight of CP (B2 , g) pH (C2 ) Temperature (D2 , ◦ C) Percentage removal of
Methylene Blue (A2 , mg/L) Methylene Blue (R2, %)

1 50 0.2 9 40 93.1
2 37.5 0.35 7 45 96.3
3 37.5 0.35 7 35 97.7
4 50 0.2 9 30 92.5
5 25 0.2 9 30 96.9
6 50 0.2 5 30 85.8
7 37.5 0.35 7 25 96.5
8 25 0.5 5 40 94.7
9 37.5 0.35 7 35 97.7
10 37.5 0.35 11 35 97.6
11 25 0.5 5 30 93.5
12 37.5 0.35 7 35 97.7
13 25 0.2 5 30 85.8
14 25 0.2 9 40 94.3
15 37.5 0.35 7 35 95.7
16 25 0.5 9 40 95.9
17 37.5 0.35 3 35 84.5
18 50 0.5 9 30 97.6
19 50 0.5 5 30 92.9
20 25 0.5 9 30 97.6
21 50 0.5 9 40 97.8
22 37.5 37.5 7 35 97.4
23 37.5 37.5 7 35 97.7
24 37.5 37.5 7 35 97.7
25 37.5 37.5 7 35 81.0
26 62.5 62.5 7 35 96.5
27 50 50 5 40 94.5
28 50 50 5 40 86.2
29 25 25 5 40 87.1
30 12.5 12.5 7 35 97.4

Table 3
Experimental design for recovery of Methylene Blue from Spent Charred Parthenium.

Run Weight of Spent Charred pH (B3 ) Time (C3 , h) Percentage recovery of

Parthenium (A3 , g) Methylene Blue (R3, %)

1 0.35 7 2 16.9
2 0.2 5 3 24.2
3 0.35 10.36 2 10.1
4 0.5 9 1 12.4
5 0.2 9 1 10.9
6 0.35 3.64 2 31.9
7 0.35 7 3.68 19.5
8 0.35 7 2 16.9
9 0.35 7 0.32 12.1
10 0.35 7 2 16.9
11 0.35 7 2 16.9
12 0.2 5 1 23.7
13 0.5 5 3 29.9
14 0.6 7 2 19.9
15 0.5 5 1 27.1
16 0.35 7 2 16.9
17 0.2 9 3 11.5
18 0.5 9 3 14.8
19 0.35 7 2 16.9
20 0.1 7 2 12.9

in terms of coded factors is shown below.
R1 = 37.62 + 4.35 × A1 + 5.19 × B1 + 1.29 × C1 + 0.03 × A1 × B1
− 0.2 × A1 × C1 + 4.46 × B1 × C1
where, R1 = decolorizing power (mg MB removed/g of charred
sample), A1 = time of carbonization (h), B1 = temperature of car-
bonization (◦ C) and C1 = weight ratio of activating agent to
parthenium. According to ANOVA, the conjugate effect of weight
ratio of activating agent to parthenium and temperature of car-
bonization has been found to be significant. Thus, the response
surface diagram of the combined effect of these two parameters on
decolorizing power at constant time of carbonization (A1 = 1.5 h)
is shown in Fig. 1. It is evident from the figure that tempera-
ture has direct effect on the extent of carbonization. Decolorizing
(4) power of charred sample increases with increase in temperature
of carbonization at constant values of weight ratio. Decolorizing
power of charred sample increases from 35.3 mg/g to 37.4 mg/g
and 29.6 mg/g to 48.4 mg/g when temperature of carbonization
increases from 450 ◦ C to 550 ◦ C at constant weight ratio of 1.0 and
1.5 respectively. This may be attributed to the fact that higher tem-
perature favors carbonization process. On the other hand it is seen
that at lower temperature of 450 ◦ C, weight ratio of activating agent
to parthenium has negligible effect on the carbonization process
294 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299
Fig. 1. Combined effect of temperature of carbonization and weight ratio on decol-
orizing power for preparation of CP.
whereas at higher temperature of 550 ◦ C, weight ratio has signif-
icant effect on the same. At 550 ◦ C, decolorizing power increases
from 37.4 mg/g to 48.4 mg/g when weight ratio is increased from
1.0 to 1.5. This may be due to the incomplete carbonization at lower
temperature even with higher weight ratio of 1.5. Maximum decol-
orizing power (48.4 mg/g) is obtained at 550 ◦ C with weight ratio
of 1.5. Similar trend is observed while examining the conjugate
effect of time of carbonization and weight ratio on decolorizing
power (figure not shown). Decolorization power increases with
increase in either time of carbonization or weight ratio. This is
obvious because more time as well as higher weight ratio of activat-
ing agent to parthenium favor carbonization process. Decolorizing
power increases from 31.9 mg/g to 40.8 mg/g and from 34.9 mg/g
to 43.0 mg/g when time of carbonization increases from 1 h to 2 h
at constant weight ratio of 1.0 and 1.5 respectively. Therefore, it
can be concluded that time of carbonization has more pronounced
effect on carbonization process than the weight ratio under the
ranges studied. Similar surveillance is obtained when conjugate
effect of time of carbonization and temperature of carbonization
on decolorizing power of charred sample at constant weight ratio
is analyzed (figure not shown). Both time and temperature of
carbonization have direct effect on carbonization process. Further-
more, carbonization at 550 ◦ C for 2 h provides the sample having
maximum (49.5 mg/g) decolorizing power whereas carbonization
at 450 ◦ C for 1 h produces the sample having minimum decoloriz-
ing power (23.2 mg/g). This is quite obvious as at lower temperature
and time, carbonization cannot be completed.
The fit of models are evaluated by determination of coefficients
(R2 ) and adjusted R2 (Radj2 ) [18]. Actual responses are obtained
by performing the experiments whereas predicted responses are
estimated from the model as proposed by the software. The R2
is calculated by the ratio between the variation explained by the
model and the total variation of the experimental data [18]. Higher
value of R2 is desirable as it is interpreted as the percentage of vari-
ability in the response explained by statistical model [18]. Thus,
the present values of R2 (0.9477) and Radj 2 (0.9236) are good [18].
Furthermore, it is also observed that all the three parameters have
synergistic effect on carbonization process. Decolorizing power of
charred sample increases with increase in any of these three param-
eters, but these incur cost to the process. The primary objective of
the present study is to prepare a low cost adsorbent from P. hys-
terophorus. To fulfill this objective the following criteria have been
set during optimization of carbonization condition: time of car-
bonization: ‘minimize’, temparature of carbonization: ‘in range’,
Fig. 2. Scanning electron micrograph of CP.
weight ratio of activating agent to parthenium: ‘minimize’ and
response: ‘maximize’. According to ANOVA, the best sample is
obtained when weight ratio, temperature and time of carboniza-
tion are 1.05:1.0, 550 ◦ C and 1 h respectively. The sample obtained
at the said condition is termed as Charred Parthenium (CP) and used
for further studies on MB removal.
3.2. Characterization of Charred Parthenium (CP)
Physicochemical characterization of CP has been done in terms
of bulk density, solid density, moisture content, ash content,
BET surface area and pore volume. The values are: bulk density
1068 kg/m3 , solid density 1750 kg/m3 , moisture content 15.23%,
ash content 9.72%, BET surface area 150.68 m2 /g and pore volume
1.1 cc/g. The high value of solid density of Charred Parthenium
indicates efficient carbonization of parthenium at the aforesaid
condition. Ash content of CP is measured by taking the weight of
residue left in the crucible after combusting the sample in a spec-
ified manner. Ash is generally considered as impurity and has no
use in adsorption process. Thus, low value of ash content signifies
CP as a good adsorbent. Furthermore, as adsorption process is a
surface phenomenon, it depends profoundly on available surface
area. Moderately higher value of BET surface area of CP indicates
its reasonably good adsorptive property.
3.2.1. Scanning Electron Microscopy (SEM)
The scanning electron microscope (SEM) image of CP is shown in
Fig. 2. It represents the topographical characterization of CP which
is porous in nature. The adsorptive capability of prepared adsorbent
is due to the presence of these pores.
3.2.2. FTIR study
The FTIR spectra of CP and SCP are used to determine the fre-
quency changes in the functional groups in the adsorbent. The FTIR
spectra of SCP is shown in Fig. 3. The spectra of the adsorbent have
been measured within the range of 500–4000 cm−1 . Two peaks of
SCP are observed at 1459 cm−1 and 1400 cm−1 for C–H and C–C
respectively. An adsorption peak around 3133 cm−1 to 3568 cm−1
representing bonded hydroxyl groups is present in SCP. All these
peaks can be found in FTIR spectra of CP. The peaks at 1637.18 cm−1 ,
1617.99 cm−1 , 1624.37 cm−1 and 1577.74 cm−1 corresponding to
N–H bond and the peaks at 1570.86 cm−1 and 1560.18 cm−1 rep-
resenting nitro compound and the peaks at 1438.06 cm−1 and
1420.29 cm−1 due to C–C bond (in ring) and peak at 1108.17 cm−1
 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299 295

Fig. 3. FTIR spectra of SCP.

representing C–N bond have been found exclusively in SCP. Thus,
it may be opined that the functional groups observed containing
nitrogen atom and C–C bond (in ring) in Fig. 3 is due to the adsorp-
tion of MB on CP.
3.3. Removal of MB using CP
3.3.1. Kinetic study
To assess the mechanism of adsorptive removal of MB using
CP and to evaluate the kinetic parameters required for designing a
continuous contactor, a detailed kinetic study has been carried out.
Three operating parameters viz., initial concentration of MB, weight
of CP and size of CP have been varied in a prescribed manner during
kinetic study. Fig. 4 represents the percentage removal-time histo-
ries of MB considering initial concentration of MB as a parameter
keeping all other parameters like weight of CP, size of CP, pH and
temperature constant at 0.25 g, 135 ␮m, 7 and 35 ◦ C respectively.
From Fig. 4, it is evident that initially the rate of disappearance
of dye is same for all the solution. This indicates that the removal
process is not dependent on the mass transfer driving force vis-à-
vis the rate of diffusion. After 30 min of operation it is seen that
temperature. Fig. 6 embodies the effect of size of CP on percent-
age removal of MB. In Fig. 6, percentage removal of MB has been
plotted against time for different sizes of adsorbent ranging from
135 ␮m to 275 ␮m keeping other parameters viz., initial concentra-
tion of MB, weight of adsorbent, pH and temperature constant at
25 mg/L, 0.25 g, 7 and 35 ◦ C respectively. Fig. 6 reveals that percent-
age removal of MB is almost constant in all the cases irrespective of
the size of particles. This may be due to the existence of comparable
mass transfer resistance in CP under the size ranges studied. Thus,
during optimization of adsorptive removal of MB by CP using RSM,
size of particles has not been considered as a parameter and it was
kept constant at 135 ␮m.
Three kinetic models viz., Lagergren model, Pseudo Second
Order model (PSOM) and Morris Weber model have been used to
scrutinize the kinetic data obtained experimentally during kinetic
study in a batch contactor. Lagergren first order model suggests a
100
90
80
Percentage removal of MB (%)

the values of percentage removal of MB for solutions having lower

concentration like 10 mg/L and 25 mg/L are nearly identical (96%) 70
whereas removal is less (88%) for solution of higher concentration
(50 mg/L). This may be due to the fact that adsorbent gets satu- 60
rated with the dye at the present operating condition. Maximum
96.7% removal is obtained when 10 mg/L MB solution has been con- 50
tacted with 0.25 g CP having 135 ␮m size at pH 7 and temperature
40
35 ◦ C. It is also evident from the figure that after 45 min of operation
the curves become parallel to abscissa indicating the attainment of 10 mg/L
30
equilibrium condition. To assess the effect of weight of adsorbent 25 mg/L
on the adsorptive removal of MB, percentage removal of MB has 20
been plotted with time for various amount of adsorbent as shown 50 mg/L
in Fig. 5. The initial concentration of MB in solution, size of adsor- 10
bent, pH and temperature are kept constant at 25 mg/L, 135 ␮m,
7 and 35 ◦ C respectively. From Fig. 5, it is seen that higher dose of 0
0 10 20 30 40 50 60 70
adsorbent leads to better removal than the lesser one. This is obvi-
Time (min)
ous as greater amount of adsorbent means greater availability of
surface area and adsorption is a surface phenomenon. Maximum Fig. 4. Time histories of percentage removal of MB with initial concentration of MB
99.9% removal has been achieved when 25 mg/L solution has been as parameter. In all cases weight of CP, particle size of CP, pH and temperature are
contacted with 0.5 g adsorbent having the size 135 ␮m at 35 ◦ C kept constant at 0.25 g, 135 ␮m, 7 and 35 ◦ C respectively.
296 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299

100 Morris Weber model is diffusion rate based model. It has been
assumed that if intraparticle diffusion is engaged in the adsorp-
90 tion process, then the plot of the square root of time versus the
uptake would result in a linear relationship [28,29]. The model can
80
Percentage removal of MB (%)

be portrayed by the following equation:

70  1/2
qt = kM t (7)

60 The kinetic data obtained experimentally during batch study as

shown in Figs. 4–6, have been fitted to the three models as men-
50 tioned above. From the analysis it is seen that PSOM fits more
satisfactorily than any other model. The values of kinetic param-
40
eters are shown in Table 4.
0.1 g
30
0.25g 3.3.2. Equilibrium study
20 0.5g The data obtained during equilibrium study has been fitted to
different adsorption isotherm models viz., Langmuir model (qe =

10 (KL q0 Ce )/(1 + KL Ce )), Freundlich model (qe = KF Ce 1/nF ). It is seen
that the data fit most satisfactorily to Langmuir model. The Lang-
0 muir constants viz., q0 and KL have been found to be 98.06 mg/g and
0 10 20 30 40 50 60 70 0.985 (L/mg adsorbate) respectively (R2 = 0.99) whereas Freundlich
Time (min) constants viz., KF and nF have been obtained as 0.65 and 1.735
respectively (R2 = 0.95). Value of q0 is comparable to the observa-
Fig. 5. Time histories of percentage removal of MB with weight of CP as parameter.
In all cases initial concentration of MB, particle size of CP, pH and temperature are
tions made by other scientists for removal of MB with low-cost
kept constant at 25 mg/L, 135 ␮m, 7 and 35 ◦ C respectively. adsorbent. The adsorption capacities of different adsorrbents for
removal of MB were: 89.4 mg MB/g of rectorite [6], 60.6 mg MB/g
of acid activated carbon prepared from morinda coreia buch-ham
100
bark [4], 39.68 mg MB/g of adsorbent prepared from parthenium
90 [8], 24 mg MB/g of adsorbent prepared from Denix regia pods [3].
The separation factor (RL ) expressed as (1/(1 + KL C0 )) is an imper-
80 ative feature of Langmuir isotherm model [5,17]. The values of RL
Percentage removal of MB (%)

are determined and it is seen that they lie in the range of zero to
70 one (0 < RL < 1) which points out the favorable adsorption of MB on
CP at this temperature. The decrease of RL with increase in initial
60
concentration indicates that removal is favorable at higher initial
concentration of solution which has also been observed by Hameed
50
et al. [5].
40

135 micron
3.3.3. Optimization of MB removal using CP by RSM
30 Four input parameters viz., initial concentration of MB, weight
215 micron of CP, pH and temperature have been varied according to the exper-
20
275 micron imental design as specified by Design Expert software. Percentage
10
removal of MB has been determined at each experimental condi-
tion and shown in Table 2. They have been analyzed by the software.
0 Quadratic model as suggested by the software has been used to fit
0 10 20 30 40 50 60 70 the response. The final equation in terms of coded factors is given
Time (min) below.

Fig. 6. Time histories of percentage removal of MB with particle size of CP as param- R2 = 97.39 − 0.29 × A2 + 3.15 × B2 + 2.96 × C2 + 0.054 × D2
eter. In all cases initial concentration of MB, weight of CP, pH and temperature are
kept constant at 25 mg/L, 0.25 g, 7 and 35 ◦ C respectively.
+ 0.47 × A2 × B2 − 0.1 × A2 × C2 + 0.29 × A2 × D2

− 1.16 × B2 × C2 + 0.1 × B2 × D2 − 0.5 × C2 × D2

first order kinetic rate based on surface reaction [28,29]. This model − 0.19 × A22 − 2.12 × B22 − 1.66 × C22 − 0.37D22 (8)
can be expressed as follows:
where, R2 = percentage removal of MB (%), A2 = initial concentration
kL t
log(qe − qt ) = log qe − (5) of MB (mg/L), B2 = weight of CP (g), C2 = pH and D2 = temperature
2.303 (◦ C).
Pseudo Second Order model (PSOM) presumes that the adsorp- Analysis by ANOVA reveals that weight of CP and pH have signif-
tion process is of Pseudo Second Order and that the limiting step icant effect on adsorptive removal of MB using CP. The interactive
is of chemisorption nature [28,29]. The mechanism may involve effect of weight of CP and pH is found to be significant. Thus,
valence forces by sharing or through the exchange of electrons the response surface diagram of the combined effect of these two
between sorbent and sorbate [28,29]. This model can be repre- parameters is analyzed in the present discussion.
sented as follows: Fig. 7 represents the three dimensional response surface of the
combined effect of pH and weight of CP on percentage removal
t 1 t
=  2 + (6) of MB keeping other parameters constant (A2 = 37.5 mg/L and
qt kP qe qe
D2 = 35 ◦ C). Figure reveals that percentage removal of MB increases
 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299 297

Table 4
Values of kinetic parameters.

Model equation Parameters varied

Initial concentration of Weight of Charred Parthenium Particle size of Charred

Methylene Blue (mg/L) (g) Parthenium (␮m)

10 25 50 0.1 0.25 0.5 135 215 275


Morris Weber model kM 0.82 2.32 4.2 4.45 2.37 1.29 2.34 2.32 2.29
R2 0.76 0.58 0.67 0.84 0.58 0.33 0.58 0.67 0.69
Lagergren model kL 0.04 0.05 0.06 0.07 0.05 0.02 0.05 0.05 0.05
R2 0.22 0.34 0.39 0.96 0.34 0.02 0.34 0.47 0.58
Pseudo Second Order kP 0.09 0.08 0.03 0.02 0.82 1.28 0.08 0.05 0.04
model R2 0.99 0.99 0.99 0.98 0.99 1.0 0.99 0.99 0.99

objective of the present study is to get the maximum removal at the

lowest cost of the process. Thus, the following criteria have been
set: the initial concentration: ‘in range’, weight of adsorbent: ‘min-
imize’, pH: ‘equal to 7’, temperature: ‘equal to 35 ◦ C’ and response:
‘maximize’. According to the software the optimum condition is
obtained when 25 mg/L solution is contacted with 0.22 g CP at pH
7 and 35 ◦ C temperature. Theoretical percentage removal (93.4%)
at this condition matches vey well with the experimental value
(92.7%). The solid sample obtained after adsorption of MB at this
condition is termed as Spent Charred Parthenium (SCP) and is used
in recovery study.

3.4. Recovery of MB from SCP

To recover dye and to regenerate spent adsorbent, recovery

study has been performed with SCP. Here also RSM is employed
to get the optimum condition for recovery considering weight of
SCP, pH and time of contact as input parameters and percentage
recovery as response. Quadratic model as suggested by the soft-
ware is used to fit the responses. The final equation in terms of
coded factors is presented below.

R3 = 16.84 + 1.87 × A3 − 6.73 × B3 + 1.37 × C3 − 0.55 × A3 × B3

+ 0.52 × A3 × C3 − 0.064 × B3 × C3 + 0.14 × A23 + 1.78

Fig. 7. Combined effect of pH and weight of CP on percentage removal of MB.
× B32 − 0.068 × C32 (9)

monotonously with increase either in pH or in weight of adsor-
bent. Maximum 98.5% removal has been obtained when 37.5 mg/L
MB solution has been contacted with 0.5 g CP at 35 ◦ C temperature
and at pH 7.
To assess the effect of temperature on MB removal, combined
effects of temperature with other input parameters on percentage
removal of MB are scrutinized (figures not shown). By analyzing the
three dimensional response surface of combined effect of tempera-
ture and initial concentration, it is seen that the percentage removal
changes from 97.3 to 96.8 and from 96.2 to 96.8 when temperature
changes from 30 ◦ C to 40 ◦ C keeping initial concentration constant
at 25 mg/L and 50 mg/L. Similar trend is observed when the com-
bined effect of temperature and weight on percentage removal of
MB has been analyzed. The percentage removal changes from 91.8
to 91.9 and from 97.9 to 98.2 when temperature changes from 30 ◦ C
to 40 ◦ C keeping weight constant at 0.2 g and 0.5 g. Almost compa-
rable results are obtained when the interactive effect of pH and
temperature on percentage removal of MB has been scrutinized. It
changes from 98.7 to 97.9 and from 91.8 to 92.9 when tempera-
ture changes from 30 ◦ C to 40 ◦ C keeping pH constant at 9 and 5.
Thus, it can be concluded that temperature has negligible effect on
percentage removal of MB.
Predicted response has been obtained by solving the theoret-
ical model as predicted by the software wheras actual response
is obtained by experimentation. The values of coefficients viz., R2
2 have been found to be 0.9668 and 0.9361 respectively. The
and Radj
where, R3 = percentage recovery of MB (%), A3 = weight of SCP (g),
B3 = pH, C3 = time of contact (h). Analysis by ANOVA reveals that all
the three parameters are significant. The quadratic effect of pH is
also found to be significant.
The conjugate effect of pH and weight of SCP on the percent-
age recovery of MB has been shown in Fig. 8 at constant time
(C3 = 2 h). From Fig. 8 it is seen that percentage recovery increases
with increase in weight of SCP. As percentage removal of MB is
favored at high pH as evident from Fig. 7, percentage recovery will
be favored at low pH. Fig. 8 also reveals that the percentage recov-
ery is more influenced by change with pH than that with weight of
SCP. The percentage recovery increases from 10.7 to 23.1 and from
13.3 to 27.7 when pH decreases from 9 to 5 keeping weight of SCP
constant at 0.2 g and 0.5 g. Whereas percentage recovery increases
from 10.7 to 13.3 and from 23.1 to 27.7 when weight of SCP changes
from 0.2 g to 0.5 g at constant values of pH 5 and 9. Thus, it can be
concluded that both the removal and recovery of MB are strong
functions of pH.
The interactive effect of time and weight of SCP on the percent-
age recovery of MB reveals that time has the direct effect on the
desorption process (figure not shown). This is very obvious as more
time of operation means more contact time for transferring mass
from solid to liquid phase until equilibrium is reached. Percentage
recovery increases from 14.2 to 15.9 and from 16.9 to 20.6 when
time of contact increases from 1 h to 3 h at constant weight of SCP
0.2 g and 0.5 g respectively. Percentage recovery also increases with
298 S. Chatterjee et al. / Chemical Engineering Journal 181–182 (2012) 289–299
Fig. 8. Combined effect of pH and weight of SCP on percentage recovery of MB.
increase in weight of SCP of the solution. This may be due to the fact
that more amount of SCP means the contact of more amount of dye
which has already been adsorbed on the solid phase. But this will
be true until the equilibrium is reached.
The statistical parameters obtained by comparing experimental
data with predicted ones using ANOVA are as follows: R2 = 0.9804,
2 = 0.9627. The objective of the studies on recovery is to max-
Radj
imize recovery at lowest price. Thus, the criteria have been set as
follows: weight of SCP: ‘maximize’, pH: ‘equal to 4’ and time: ‘min-
imize’. The optimum condition for maximum recovery (31.7%) is
obtained when amount of SCP, pH and temperature are 0.5 g, 4 and
1 h respectively. The experimental value (30.4%) matches very well
with the theoretical one (31.7%).
To examine the reusability of regenerated adsorbent, 25 mg/L
of simulated solution of MB was contacted with 0.22 g regener-
ated adsorbent, obtained after recovery of the adsorbed dye at
the optimum condition of recovery, at pH 7 and 35 ◦ C temper-
ature in a batch contactor. About 60% removal of MB has been
achieved. Thus, the usability of regenerated adsorbent has been
confirmed.
4. Conclusion
Parthenium, a harmful weed, is carbonized to produce low
cost adsorbent using ortho-phosphoric acid as activating agent.
The carbonization condition is optimized using RSM. The sample
obtained at optimum condition is termed as Charred Parthenium
and used for further studies on MB removal. To assess the effec-
tiveness of CP as an adsorbent, a thorough investigation is made
by varying three input parameters like initial concentration of dye,
weight and size of CP. Maximum 99.9% removal of MB has been
achieved when 25 mg/L solution has been contacted with 0.5 g
adsorbent having the size 135 ␮m at 35 ◦ C temperature. Thus high
removal of dye indicates the high capacity of CP as an adsorbent.
Removal of MB has also been optimized using RSM. The solid sam-
ple obtained at optimum condition of MB removal is termed as
Spent Charred Parthenium (SCP). Recovery study is done with SCP
by contacting it with buffer solution having different pH. Experi-
mentation reveals that both removal and recovery of MB is a strong
function of pH. Thereby, it can be concluded that the prepared
adsorbent can efficiently be used outside the laboratory condi-
tion for the treatment of waste water containing dyes and other
pollutants.
Acknowledgement
We acknowledge DST (Department of Science and Technol-
ogy, Ministry of Science and Technology, Government of India) for
financial support of the project and Ms. Debarati Dutta and Mr.
Subhankar Mishra for their assistance in experimentation.
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