Journal of Industrial and Engineering Chemistry 18 (2012) 780–784

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Journal of Industrial and Engineering Chemistry

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

Treatment of pollutants in wastewater: Adsorption of methylene blue onto

olive-based activated carbon
Mónica Berrios, Marı́a Ángeles Martı́n *, Antonio Martı́n
University of Cordoba (Spain), Department of Inorganic Chemistry and Chemical Engineering, Campus Universitario de Rabanales, Edificio Marie Curie (C3),
Planta Baja, 14071 Cordoba, Spain

A R T I C L E I N F O A B S T R A C T

Article history: This study used olive stone-based activated carbon for the removal of methylene blue from wastewater in
Received 16 May 2011 order to evaluate the adsorption capacity of the carbon. The equilibrium and kinetics of adsorption were
Accepted 5 August 2011 examined at 258, 308, 358 and 40 8C and several agitation speeds. Type III adsorption isotherms
Available online 12 November 2011
corresponding to physical adsorption in a multilayer system were used for the methylene blue system.
The equilibrium data for methylene blue adsorption showed a good fit to the Freundlich equation. The
Keywords: kinetic data was analysed to determine kinetic constants and order of reaction. Kinetics was evaluated by
Activated carbon
means of an n-order model, showing that the reaction was a first-order reaction. The results indicated
Adsorption isotherms
that olive stone-based activated carbon could be used as a low-cost alternative to commercial activated
Kinetics studies
Methylene blue carbon for the removal of organic compounds from wastewater. However, due to its microporosity, the
Olive stones application of this type of activated carbon was found to be suitable for molecules smaller than
methylene blue.
ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
The textile industry requires large amounts of water and
produces highly polluted wastewater containing different types of
dyes [1]. The main problem involved in decontaminating textile
wastewaters is the removal of colour, since no single process is
currently capable of generating adequate effluents [2]. Most dyes
have an adverse impact on the environment as they are considered
toxic and have carcinogenic properties, which make the water
inhibitory to aquatic life [3].
Biological treatment processes are reported to be efficient in
chemical oxygen demand reduction, but are largely ineffective in
removing colour from wastewater. Hence, research has been
conducted on physico-chemical methods for colour removal in
textile effluent. These studies include the use of coagulants,
oxidising agents, photocatalysis, ultrafiltration, electrochemical
and adsorption techniques [4,5].
Among the various treatment technologies available, adsorp-
tion onto activated carbon has proven to be one of the most
effective and reliable physico-chemical treatments. However,
commercially available activated carbons are very expensive [6].
The carbon derived from agricultural wastes is gaining importance
* Corresponding author. Tel.: +34 957 21 86 24; fax: +34 957 21 86 25.
E-mail address: iq2masam@uco.es (M.n).
due to its low price and suitability for the removal of organic and
inorganic pollutants from wastewater [7]. Although, these
agricultural wastes can be also used as biosorbents directly [8–
10]. In this sense, Nieto et al. [11] studied the ability of crude olive
stones, a residue of the olive-oil industry, for the adsorption of iron
present in the industrial wastewaters. Researchers have studied
the production of activated carbon from palm-tree cobs, plum
kernels, cassava peel, bagasse, jute fiber, rice husks, date pits,
nutshells, wood, maize cob, cotton seed shell, rubber seed coat,
apricot stone, almond shell, pongam seed coat, coconut shell,
orange peel, walnut stone, bamboo dust, sunflower seed hull and
peach stone as has been detailed in the literature [6,7,12–18]. Little
information has been reported about the particular case of
activated carbon from olive stones [19–21]. In Mediterranean
countries, olive stones and residues are a cheap and quite abundant
agricultural waste [21].
Activated carbon has a porous structure with a large internal
surface area. Four consecutive mass transport steps are associated
with the adsorption of solute from solution by porous adsorbent as
follows: the adsorbate migrates through the solution to the
exterior surface of the adsorbent particles, molecular diffusion
takes place in the boundary layer, solute is moved from the particle
surface into the interior site by pore diffusion and finally the
adsorbate is adsorbed into the active sites at the interior of the
adsorbent particle. This phenomenon takes relatively long contact
time [6,21].

1226-086X/$ – see front matter ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2011.11.125
 M. Berrios et al. / Journal of Industrial and Engineering Chemistry 18 (2012) 780–784
Determinations of surface area can be made by fitting the BET
equation to the isothermal equilibrium data obtained. However,
these values are not a true indication of the adsorption capacity of
an activated carbon applied in liquid-phase adsorption studies. It is
therefore more logical to determine the porous structure by
combining both the gas-phase and the liquid-phase adsorption
equilibrium data. The literature indicates that the adsorption of
phenol, methylene blue, caffeine and iodine from the aqueous
phase is a useful tool for product control in the manufacture of
activated carbon [22–24].
In addition to determining the porous structure of activated
carbon, methylene blue can be employed as a thiazine (cationic
or basic) dye; the most commonly used dye for colouring among
all other dyes of its category. It is generally used for dyeing
cotton, wool, and silk [25] and has a number of biological uses.
However, given that methylene blue has various harmful effects
on human beings, it is of utmost importance to remove it from
wastewater. Methylene blue dissociates in aqueous solution as
electrolytes into methylene blue cation and the chloride ion.
Because the coloured cation is retained at great length by several
adsorbents [3,26], methylene blue was selected as the adsorbate
in this study.
This research study aimed to evaluate the adsorption potential
of olive stone-based activated carbon for methylene blue from a
synthetic wastewater as olive stones are a very abundant and
inexpensive material in Mediterranean countries. The kinetic and
equilibrium data of adsorption studies were processed to
understand the adsorption behaviour of the dye molecules onto
the activated carbon. Although this activated carbon is commer-
cial, it was selected because no data about this behaviour has yet
been reported.
2. Materials and methods
2.1. Materials
Methylene blue (MB) supplied by Panreac (Spain) was used as
an adsorbate and was not purified prior to use. The molecular
weight (g/mol), molecular volume (cm3/mol) and molecular
diameter (nm) of MB are 319.85, 241.9 and 0.8, respectively [27].
Olive stone-based activated carbon (AC) was supplied by Ibérica
de Carbones Activos S.A. Textural characterization of the AC was
carried out by N2 adsorption at 77 K using Micromeritic ASAP 2020
in our laboratory. The BET surface area, total pore volume and
average pore diameter of the AC were found to be 587 m2/g,
0.333 cm3/g and 2.27 nm, respectively.
2.2. Analysis of methylene blue concentration
The MB concentration in the supernatant solution before and
after adsorption was determined using a UV–vis spectrophotome-
ter S-20 (BOECO, Germany) at 664 nm. The calibration curve was
very reproducible and linear over the concentration range used in
this work.
2.3. Equilibrium experiments
The equilibrium tests were performed in 4 Erlenmeyer flasks
(1 L) in which 500 mL of MB solution (initial concentration at
0.5 mg/L) were placed. The agitation speed was fixed at 50 rpm and
the AC doses (0.25, 0.50, 1.00 and 2.00 g) were added to the MB
solutions and kept in an isothermal shaker SI 50 GIRALT (STUART
SCIENTIFIC, UK) at different temperatures (258, 308, 358 and 40 8C).
The contact time to reach equilibrium between the solid phase and
the liquid phase was approximately 11.5 h (that was checked in
previous assays). The aqueous samples (10 mL) were centrifuged at
781
8000 rpm for 5 min and filtered prior to analysis in order to remove
suspended particles of AC.
2.4. Kinetic experiments
The kinetic tests were carried out in a similar way to the
previous equilibrium tests. Several amounts of AC (1, 2, 4 and 8 g)
were added to the MB solutions (initial concentration at 5 mg/L)
and kept in an isothermal shaker SI 50 GIRALT (STUART SCIENTIFIC,
UK) at different temperatures (258, 308, 358 and 40 8C) and
agitation speeds (50, 100, 150, 200 and 250 rpm). The aqueous
samples (10 mL) were taken at time intervals of up to 95 min. The
samples were centrifuged at 8000 rpm for 5 min and filtered prior
to analysis in order to remove suspended particles of AC.
The amount of adsorption or adsorption capacity q (mg/g) was
calculated by
C0V 0  CiV i
q¼ (1)
W
where C0 and Ci (mg/L) are the liquid-phase concentrations of MB
at initial and any time (Ct) or equilibrium (Ce), respectively,
obtaining the amount of adsorption at time (qt) or the amount of
adsorption at equilibrium (qe). V0 is the initial volume of the
solution (0.5 L), Vi is the real volume when sampling and W is the
mass of the AC used (g).
3. Results and discussion
3.1. Adsorption equilibrium
The adsorption of dyes from the liquid to solid phase can be
considered a reversible reaction with equilibrium established
between the two phases [28]. The adsorption isotherm (qe vs. Ce)
indicates how the adsorption molecules distribute between the
liquid phase and the solid phase when the adsorption process
reaches an equilibrium state. The analysis of the equilibrium data of
the isotherm models is very important for the use of adsorbents [12].
Fig. 1 shows the adsorption isotherms at four temperatures for
the MB solution and olive stone-based AC system. According to
Brunauer et al. [29] and Hinz [30], the adsorption isotherms have
the same shape that the type III isotherms or S1 isotherms (Giles
classification), which correspond to physical adsorption in a
multilayer system where no difference is noticed between the
filling of the first layer and the other layers.
The Freundlich isotherm is the earliest known relationship
describing the adsorption equation. This fairly satisfactory
1.0
C0 (MB) = 0.508 mg/L
0.8
0.6
qe (mg/g)
0.4
25ºC
30ºC
0.2
35ºC
40ºC
0.0
0.06 0.08 0.10 0.12
Ce (mg/L)
Fig. 1. Adsorption isotherms for the MB solution and olive stone-based AC system.
782 M. Berrios et al. / Journal of Industrial and Engineering Chemistry 18 (2012) 780–784
Table 1
Freundlich constants for the MB solution and olive stone-based AC system at
different temperatures.
Temperature (8C)
25 30 35
KF  103 (mg/g)(L/g)1/n 936.9 734.1 1744.1
n 0.165 0.163 0.150
r2 0.999 0.999 0.998
empirical isotherm can be used for non-ideal adsorption that
involves heterogeneous surface energy systems and is expressed
by the following equation:
1=n
qe ¼ K F Ce
where KF is a rough indicator of the adsorption capacity and (1/n) is
the adsorption intensity. In general, the KF value increases as the
adsorption capacity of adsorbent for a given adsorbate increases.
The magnitude of the exponent (1/n) indicates easy uptake of
adsorbate from aqueous solution. A value for (1/n) below one
indicates a normal Langmuir isotherm, while (1/n) above one is
indicative of cooperative adsorption [12].
The Freundlich constants (KF and n) were calculated by
nonlinear regression using Sigmaplot1 11.0 software. The results
and the regression coefficients are shown in Table 1.
As can be observed in the regression coefficients, the adsorption
of MB from wastewater on olive stone-based AC follow the
Freundlich isotherm at all tested temperatures. According to
Hameed et al. [12], our (1/n) values above 1 were indicative of
cooperative adsorption. This means that the binding of a MB
molecule to one site on AC influences the affinity of other sites.
Similar values of n were found by Avom et al. [24] for palm tree
cobs-based AC, indicating the heterogeneity of the AC surface.
When the temperature increased, the MB amount in solid phase
decreased in the equilibrium (Fig. 1). Hence, the effectiveness of
the adsorption process decreased at a high temperature because
the desorption process took place at higher temperatures.
Therefore, the MB concentration in liquid phase increased.
Based on the experimental data, an empirical equation was
obtained to relate qe to temperature (T) and Ce for the olive stone-
based AC. This relationship is shown in the three-dimensional
graph in Fig. 2.
Fig. 2. Three-dimensional graph of the relationship between qe, temperature (T) and
Ce .
It is believed that adsorption of organics onto AC depends on
both the pore structure and surface chemical properties of carbon
as well as the adsorbate. Dye adsorption tests help to determine
the capacity of carbon to adsorb molecules of a particular size. The
40 MB molecule has a minimum molecular diameter of 0.8 nm and
132.7
cannot enter pores with a diameter of less than 1.3 nm [28,31].
0.172 Therefore, it can only enter the larger micropores, but most of it is
0.997 likely to be adsorbed in mesopores. Despite the high surface area of
olive stone-based AC (587 m2/g) as other authors have reported for
olive stone-based activated carbon [32], the adsorption capacity of
MB in aqueous solution (for example qe = 0.858 mg/g at 25 8C with
an AC dose of 0.5 g/L) was poor due to the molecular diameter of
MB and the AC pore size distribution as described in Section 2.
Although this AC has a high surface area, its application could be
(2) more suitable for molecules smaller than MB due to the high
microporosity of AC.
3.2. Adsorption kinetics
The kinetic adsorption data was evaluated to understand the
dynamics of the adsorption process. The MB molecules must
overcome three stages before coming into contact with the active
sites of AC. These stages are the migration of the solute through the
solution to the exterior surface of the adsorbent particles,
molecular diffusion in the boundary layer and solute movement
from particle surface into the interior site by pore diffusion.
Adsorption itself could be considered almost instantaneous if the
phenomenon was purely a physical process, while mass transfer
could be minimized by means of suitable agitation speeds.
In order to evaluate the influence of agitation speed (rpm) on
the external mass transfer, several experiments were carried out in
the range of 50–250 rpm for all the temperature conditions and AC
doses selected. Fig. 3 shows the influence of agitation speed on the
adsorption capacity at 25 8C and an AC dose of 8 g/L. As can be
observed, no differences were detected between 100 and 250 rpm.
However, when the agitation speed was increased from 50 to
100 rpm, the adsorption capacity (q) was enhanced. This increase
highlighted that the mass transfer through the solution and in the
boundary layer did not limit the adsorption process when an
agitation speed of 100 or higher was selected.
Once the external mass transfer did not limit the adsorption
process, the kinetics was evaluated at 100 rpm. As can be observed
in Fig. 4, the q vs. t plots for all temperatures and AC doses were
found to rise exponentially to the maximum for an AC dose of 4 g/L.
Temperature did not significantly influence the adsorption
0.6
0.5
0.4
q (mg/g)
50 rpm
100 rpm
150 rpm
25ºC, 8 g AC/L 200 rpm
250 rpm
0.0
0 20 40 60 80 100
time (min)
Fig. 3. Effect of agitation speed on the adsorption capacity at 25 8C, 8 g AC/L and an
initial MB concentration of 5 mg/L.
 M. Berrios et al. / Journal of Industrial and Engineering Chemistry 18 (2012) 780–784 783

Table 2
1.2 Kinetic constants of the n-order model.

AC dose (g/L)
1.0
2 4 8 16

0.8 K̄ (1/min) 0.020  0.002 0.030  0.009 0.057  0.004 0.050  0.003
q (mg/g)

0.6

Table 2. These kinetic constants were similar to the results

0.4 obtained by Santhy and Selvapathy [7] for the adsorption of
25ºC reactive dyes. The kinetic constant increased from 0.020 to 0.030
30ºC
0.2 and 0.057 (1/min) for AC doses of 2, 4 and 8 g/L, respectively. At
4 g AC/L, 100 rpm 35ºC
40ºC higher AC doses, the kinetic constant remained approximately
0.0 stable, indicating that the adsorption rate did not increase when
the AC dose was higher than 8 g/L.
0 20 40 60 80 100
time (min)
4. Conclusions
Fig. 4. Fitting of experimental data to exponential function at 100 rpm and AC dose
of 4 g/L.
This study showed that olive stone-based activated carbon can
be used for the removal of organic compounds from aqueous
solution under a wide range of conditions. Type III adsorption
capacity in the range studied for temperature and time (25–40 8C isotherms were used for the MB system. These isotherms
and 100 min). correspond to physical adsorption in a multilayer system where
Several mathematical expressions explain the increase in MB no difference is noticed between the filling of the first layer and
concentration in a dose of AC with greater adsorption time. Most the other layers. Adsorption behaviour was described by the
studies (i.e. Langergen and Svenska) use first- and second-order Freundlich isotherm with n values that demonstrate the
kinetic equations to model adsorption capacity [12]. Lee [33] heterogeneity of the AC surface. Kinetics was evaluated by means
applied pseudo second-order kinetic equations to study the of an n-order model, showing that the reaction was a first-order
adsorption of erythrosine dye from aqueous solution using reaction. The olive stone-based AC characterization showed high
activated carbon. In order to determine the exact order of reaction, microporosity, thus indicating that the poor adsorption capacity
the following generalised kinetic equation was employed: results for MB are due to the molecular properties of this
compound.
dq
¼ Kðqmax  qÞn (3)
dt
Acknowledgements
where K is the kinetic constant and qmax is the maximum
adsorption capacity for each temperature and AC dose. The kinetic The authors are very grateful to Iberica de Carbones and Junta
constant and the order of reaction can be calculated by linearising de Andalucia (PAIDI group RNM-271) for funding this research. We
Eq. (3): also wish to express our gratitude to laboratory technician
  Inmaculada Bellido Padillo for her help.
dq
log ¼ log K þ n log ðqmax  qÞ (4)
dt
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