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Activated carbons from waste biomass by sulfuric acid activation

and their use on methylene blue adsorption


Selhan Karago z
a,
*
, Turgay Tay
b
, Suat Ucar
a
, Murat Erdem
b
a
Chemistry Program, Izmir Vocational School, Dokuz Eylu l University, 35160 Buca, Izmir, Turkey
b
Department of Chemistry, Faculty of Science, Anadolu University, 26470 Eskisehir, Turkey
Received 28 August 2007; received in revised form 3 December 2007; accepted 6 December 2007
Available online 18 January 2008
Abstract
Preparation of the activated carbons from sunower oil cake by sulphuric acid activation with dierent impregnation ratios was car-
ried out. Laboratory prepared activated carbons were used as adsorbents for the removal of methylene blue (MB) from aqueous solu-
tions. Liquid-phase adsorption experiments were conducted and the maximum adsorption capacity of each activated carbon was
determined. The eects of various process parameters i.e., temperature, pH, initial methylene blue concentration, contact time on the
adsorption capacity of each activated carbon were investigated. The kinetic models for MB adsorption onto the activated carbons were
studied. Langmuir isotherm showed better t than Freundlich isotherm for all activated carbon samples. The rates of adsorption were
found to conform to the pseudo-second-order kinetics with good correlation. The separation factor (R
L
) revealed the favorable nature of
the isotherm of the MB activated carbon system.
2007 Elsevier Ltd. All rights reserved.
Keywords: Waste biomass; Activated carbon; Adsorption; Methylene blue
1. Introduction
Evaluation of waste biomass is getting increased atten-
tion in all over the world as it is renewable, widely avail-
able, cheap, and environmental friendly. One of the
eective uses of waste biomass is the production of acti-
vated carbon by thermochemical conversion. The activated
carbon has been produced from variety of biomass i.e.,
wood (Hared et al., 2007), rice husk (Kumagai et al.,
2007), cellulose (Ling et al., 1999), lignin (Carrott and Car-
rott, 2007), coconut shells and palm shells (Daud and Ali,
2004). There have been many reports on the production of
activated carbon to use as adsorbent for removing hazard-
ous compounds from industrial waste gases (Nagano et al.,
2000) or wastewater (Guo and Lua, 2000), and in catalysis
as support for catalyst (Karagoz et al., 2002). There are
two basic processes to activate carbon materials; physical
and chemical. Chemical activation can be accomplished
in a single step by carrying out thermal decomposition of
raw material with chemical reagents. Chemical activation
processes have been carried out with acidic reagents i.e.;
ZnCl
2
(Yalcin and Sevinc, 2000), H
3
PO
4
(Nakagawa
et al., 2007), HCl (Alvarez et al., 2007), and H
2
SO
4
(Gerc el
and Gerc el, 2007) or with basic reagents KOH (Guo and
Lua, 2007), K
2
CO
3
(Carvalho et al., 2004), NaOH (Lillo-
Ro denas et al., 2007), and Na
2
CO
3
(Hayashi et al., 2000).
Synthetic dyes are indispensable to the textile and dye-
ing industries. The use of dyes, as most chemicals, can be
hazardous. Therefore, signicant eorts are devoted to
color removal from the textile wastewaters by adsorption
techniques with the activated carbon to reduce environ-
mental problems associated with textile industry euents.
The most commonly used adsorbent for the removal of
dyes by adsorption is namely commercial coal-based acti-
vated carbon due to its high adsorption capacity and high
0960-8524/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.12.019
*
Corresponding author. Tel.: +90 232 420 48 93; fax: +90 232 420 51
81.
E-mail addresses: selhan.karagoz@deu.edu.tr, selhankaragoz@
yahoo.com (S. Karago z).
Available online at www.sciencedirect.com
Bioresource Technology 99 (2008) 62146222
surface area (Gercel et al., 2007). However, as well-known,
fossil fuels are nite. Thus, the production of activated car-
bon from renewable sources is indeed of importance from
the view point of economic and environmental aspects.
Methylene blue dye serves as a model compound for
adsorption of organic contaminants from aqueous solu-
tions (Hameed et al., 2007a, 2007b; Kavitha and Namasi-
vayam, 2007).
The present investigation assesses the issues with the
activated carbon production from waste biomass and its
adsorption capacity on methylene blue. The equilibrium
and kinetic data of the adsorption process of methylene
blue molecules onto the prepared activated carbons were
also studied.
2. Experimental
2.1. Materials
Waste biomass (Sunower oil cake) sample was
obtained from Altinyag Oil Company, Izmir, Turkey and
used as received. The proximate, ultimate and component
analyses of sunower oil cake are shown in Table 1. Deter-
mination of each component of sunower oil cake was
done using the method given in the literature (Li et al.,
2004). Sodium hydroxide, sodium carbonate, sodium bicar-
bonate, barium chloride, hydrochloric acid (37 wt%), ethyl
alcohol, and toluene were obtained from Aldrich and used
as received. Sulfuric acid (98 wt%) obtained from Aldrich
was used as an activating reagent. Methylene blue (MB)
was obtained from Merck and used as an adsorbate in this
work.
2.2. Preparation of the activated carbons
The preparation of activated carbons from waste bio-
mass was carried out in six stages: (i) Waste biomass was
treated with sulfuric acid (H
2
SO
4
) solutions. (ii) The acidi-
ed waste biomass was mixed for 24 h under continuous
agitation (1000 rpm). (iii) This mixture was dried at
110 C for 24 h to prepare the impregnated sample. (iv)
The impregnated sample was set in a reactor which was a
xed bed design of stainless steel with 6 cm diameter and
21 cm height. The impregnated sample was carbonized at
600 C under nitrogen (N
2
) ow of 30 mL min
1
at a heat-
ing rate of 5 C min
1
. (v) After carbonization, the sample
had been cooled down under N
2
gas ow, the carbonized
sample was washed several times with hot water, and
nally with cold water to remove residual chemicals. The
washing and ltration steps were repeated until the ltrate
became neutral. The washed sample was dried at 110 C for
24 h to prepare the activated carbon. The activated carbons
were denoted as AC1 with the impregnation ratio of 0,
AC2 with the impregnation ratio of 0.85, and AC3 with
the impregnation ratio of 1.90. The activated carbons were
prepared and characterized and used as adsorbents for the
removal of methylene blue (MB) from aqueous solutions.
The experimental impregnation ratio was estimated from
the following equation:
Theoretical ratios were selected as 1.35 and 2.20 for AC2
and AC3, respectively. Experimental impregnation ratios
were found to be 0.85 and 1.90 for AC2 and AC3,
respectively.
The chemical recovery (%) was estimated using the
following equation:
Exp: impregnation ratio
weight of sample after impregnation weight of waste biomass
weight of waste biomass
Chemical recovery
weight of sample before washing weight of sample after washing
weight of impregnated chemical
100
Table 1
Proximate, ultimate and component analyses of waste biomass
Type of waste biomass Sunower oil cake
Proximate analysis (as received, wt%)
Moisture 9.84
Volatile matter 67.36
Fixed carbon 17.62
Ash 5.18
Ultimate analysis (dry basis, wt%)
C 46.55
H 6.087
N 4.488
S 0.486
O
a
42.389
GCV
b
(kcal/kg) 4546
Component analysis (dry basis, wt%)
Extractives
c
13.01
Hemicellulose 36.47
Lignin 15.77
Cellulose 30.08
a
By dierence.
b
Gross caloric value.
c
Toluene/alcohol (2/1) (v/v).
S. Karago z et al. / Bioresource Technology 99 (2008) 62146222 6215
Chemical recoveries were found to be 0.79 and 0.81 wt%
for AC2 and AC3, respectively. The yield of the activated
carbon was calculated based on the weight of waste bio-
mass on a dry basis. The yields of the activated carbons
were found to be 34.40, 42.65, and 39.68 wt% for AC1,
AC2, and AC3, respectively.
2.3. Characterization of the activated carbons
A measurement of specic surface areas of the activated
carbons produced from the waste biomass has been made
by N
2
adsorption (at 77 K), using a surface analyzer
(Quantachrome Inst., Nova 2200e). The micropore volume
(V
micro
) was determined by using t-plot method. The results
were obtained by using Novawin 2 software. The mesopore
volume (V
meso
) was calculated by subtracting V
micro
from
V
total
(V
meso
= V
total
V
micro
). Proximate analyses of the
activated carbons were done according to ASTM D3174-
04 for ash analysis and ASTM D3175-89a for volatile
matter. The activated carbons were analyzed for carbon,
nitrogen, hydrogen, sulfur, and oxygen (by dierence)
abundances using a LECO CHNS 932 Elemental Analyzer
according to ASTM D5291-96. The characteristics of the
activated carbons are presented in Table 2.
The surface functional groups of the activated carbons
(AC1, AC2, and AC3) were characterized according to
Boehm method (Boehm, 1966).The weighed amounts of
the activated carbon samples (about 1.00 g) were placed
in 50 mL vials of the following solutions: 0.1 N of NaOH,
NaHCO
3
, and Na
2
CO
3
, respectively. The vials were sealed
and allowed to equilibrate with agitation for 48 h at room
temperature and then the activated carbon samples were
separated by ltration. After ltration, the liquids were
titrated by back titration of the acidic solutions with
0.1 N of standard HCl aqueous solution. The amount of
acidic groups on the activated carbon is calculated under
the assumption that NaOH neutralizes carboxylic, lactonic,
and phenolic groups; Na
2
CO
3
, carboxylic and lactonic
groups NaHCO
3
, only carboxylic group.
2.4. Adsorption experiments
The adsorption experiments were carried out by 10 mL
of a 25 ppm MB solution with 20 mg of the activated car-
bon and the pH was carefully adjusted between 3 and 10
with adding a small amount of dilute HCl or NaOH solu-
tion using a pH meter (Hanna Instruments HI 8314). The
MB solutions were stirred using a mechanical magnetic
stirrer in a 50 mL Erlenmeyer sealed with paralm to avoid
evaporation. The optimum pH was then determined as 6
and used throughout further adsorption experiments,
which were conducted at various time (from 0 min to
1440 min) intervals and temperatures (15, 25, 35, and
45 C) in order to determine the adsorption equilibrium
time and the maximum removal of MB. The solutions were
centrifuged and then subjected to quantitative analyses.
The equilibrium concentrations of each solution were
determined from the absorbance of the solution measured
by a spectrophotometer (Shimadzu UV-2450PC) at the
k
max
value, which is 665 nm for methylene blue. The
amount of MB adsorbed onto the activated carbon surface
was determined by the dierence between the initial and
remaining concentrations of MB solution. The amount of
adsorbed MB at equilibrium, q
e
(mg g
1
) was calculated by
q
e

C
o
C
e
V
W
where C
o
and C
e
(mg L
1
) are the liquid-phase initial and
equilibrium concentrations of the dye, respectively. V is
the volume of the solution (L), and W is the mass of dry
adsorbent used (g). The adsorption of MB onto the acti-
vated carbon was also evaluated at constant temperature
of 25 C for the adsorption isotherms.
The procedures for the kinetic experiments were basi-
cally identical to those of equilibrium tests. The aqueous
samples were taken at present time intervals, and the con-
centrations of MB were similarly measured. The amount of
adsorption at time t, q
t
(mg g
1
), was calculated by
q
t

C
o
C
t
V
W
where C
o
and C
t
(mg L
1
) are the liquid-phase concentra-
tions of MB at initial and any time t, respectively. V is the
volume of the solution (L), and W is the mass of dry adsor-
bent used (g).
3. Results and discussion
3.1. The inuence of impregnation ratio on characteristics of
the activated carbons
The characteristics of the activated carbons prepared at
600 C using dierent impregnation ratios of H
2
SO
4
are
Table 2
Characteristics of the activated carbons
Type of the activated carbon AC1 AC2 AC3
Proximate analysis
Volatile matter 13.23 17.54 22.62
Fixed carbon 68.47 69.03 62.47
Ash 18.30 13.43 14.91
Elemental analysis (wt%)
C 59.24 58.79 60.59
H 2.445 1.710 1.551
N 4.625 5.647 6.461
S 0.042 6.168 7.713
O
*
33.648 27.685 23.685
Typical properties
Specic surface area (m
2
g
1
) 8.8 240.02 114.77
Total pore volume (cm
3
g
1
) 0.0063 0.116 0.073
Micropore area (m
2
g
1
) 8.268 230.80 89.68
Micropore volume (cm
3
g
1
) 0.111 0.044
Mesopore volume (cm
3
g
1
) 0.0063 0.005 0.029
Average pore diameter (A

) 28.67 19.38 25.53


*
By dierence.
6216 S. Karago z et al. / Bioresource Technology 99 (2008) 62146222
shown in Table 2. For comparison purpose, the character-
istics of the activated carbon (AC1) prepared at 600 C
without H
2
SO
4
activation was also shown in Table 2.
AC1 prepared at the carbonization temperature without
H
2
SO
4
activation had a surface area of 8.8 m
2
g
1
. Using
H
2
SO
4
, as the activating reagent, the maximumsurface area
was obtained for the activated carbon AC2. Interestingly,
with increasing impregnation ratio from 0.85 to 1.90, sur-
face area decreased from 240.02 to 114.77 m
2
g
1
. There
are also signicant reductions in micropore and total pore
volumes with increasing the impregnation ratio. In the
study of the preparation of the activated carbon from cat-
tle-manure by ZnCl
2
activation (Qian et al., 2007), it was
found that while the impregnation ratio was higher than
1.5 in the activation process, both BET surface area and
micropore volume of the activated carbon resulted in
decrease. Experimental results suggest that impregnation
ratio strongly aects characteristics of the activated carbon
and appropriate impregnation ratio should be selected for
the production of the activated carbons with the highest
surface area and pore volume. In addition, the composi-
tions of lignocellulosic materials inuence the structure of
the activated carbons in terms of porosity. If lignocellulosic
materials contain comparatively large percentage of lignin
content, the BET surface areas of the activated carbons
increase. Gergova et al. (Gergova et al., 1994) produced
the activated carbons from grape seed and cherrystone
and attributed the predominantly mesopore and macropore
structures of the activated carbons formed to the high lignin
content in the raw materials.
3.2. Eect of pH
The eect of the pH of the solution for the adsorption of
methylene blue onto the activated carbons was studied at
constant initial concentration of 25 ppm MB and the
amount of adsorbent (20 mg) at 150 rpm agitation speed
and at 25 C. The range of the pH was adjusted between
3 and 10. Fig. 1 shows the eect of pH on the adsorption
of methylene blue onto the activated carbons. The pH of
solution appears to be a key factor aecting the adsorption
characteristics of MB onto the activated carbons. As can be
seen from Fig. 1, it is evident that increasing the pH of
solution serves to increase the adsorption capacity with a
signicant enhancement in the adsorption process occur-
ring as the pH increased from 3 to 6. The pH of solutions
is one of the most important factors which aects on
methylene blue adsorption as it controls the electrostatic
interactions between the adsorbent and the adsorbate.
The surface properties of the carbon change with an
increase of pH. The surface acidity of the activated carbons
might aect the pH of the solution for the adsorption of
methylene blue onto the activated carbons. Table 3 shows
the surface acidic groups of the activated carbons. The
total acidity of the AC2 was the lowest whereas it was
found to be the highest in the case of AC1. The amphoteric
nature of carbon depends on not only the surface func-
tional groups of the carbon but also the isoelectric point
(pH
IEP
) or point of zero charge (pH
PZC
) of the activated
carbon (Radovic et al., 1997; Savova et al., 2003). Cationic
adsorption is favored at pH > pH
PZC
(e.g. on COO

groups) and anionic adsorption is favored at pH < pH


PZC
(e.g. on Lewis-basetype basal plane sites) (Radovic
et al., 1997; Savova et al., 2003). The percentage of adsorp-
tion increased as the pH of the solution was increased. This
result might show that the zero point of charge (pH
PZC
) for
the activated carbon lies between pH 2.5 and 5.5. The total
or external surface charges are positive at a lower solution
of pH. Thus, lower adsorption of MB took place at a lower
solution of pH. When the pH value increased, the surface
of the activated carbon was negatively charged more. Thus,
the adsorption of the MB with positive charge was reached
maximum at pH 6.
The activated carbon obtained from Euphorbia Rigida
by H
2
SO
4
activation for the removal of methylene blue
from aqueous solutions at various contact times, pHs and
temperatures were investigated (Gercel et al., 2007) and it
was found that the maximum methylene blue removal
was achieved at pH 6. In this study, the maximum adsorp-
tion capacity was also obtained at pH 6 which is in good
agreement with the result of that study (Gercel et al.,
2007). Thus, pH 6 was selected as the optimum pH value
for all further experiments in this study.
3.3. Eect of contact time
A series of contact time experiments for MB have been
carried out at the initial concentration of MB (25 ppm) and
temperature of 25 C. The amount of adsorbed MB onto
the activated carbon versus time (01440 min) was studied.
0
2
4
6
8
2 4 6 8 10 12
pH
q
e
(
m
g

g
-
1
)
AC1
AC2
AC3
Fig. 1. Eect of pH for the adsorption of methylene blue onto the
activated carbons (C
o
= 25 ppm, m
AC
= 20 mg, t = 1440 min, V = 10 mL,
T = 25 C).
Table 3
Surface acidic groups of the activated carbons
Surface acidic groups
(meq g
1
)
Phenolic Lactonic Carboxylic Total
acidity
Activated carbons
AC1 0.2625 0.0875 0.5750 0.9250
AC2 0.1875 0.1875 0.3125 0.6875
AC3 0.3625 0.1250 0.3250 0.8125
S. Karago z et al. / Bioresource Technology 99 (2008) 62146222 6217
The maximum adsorption capacities for methylene blue
onto the activated carbons (AC1 and AC2) were observed
at 900 min. However, longer contact time (1440 min) was
needed for the maximum adsorption capacities for methy-
lene blue onto AC3. The adsorption of methylene blue
onto jute ber carbon was investigated (Senthilkumaar
et al., 2005). It was reported that during adsorption of
dyes, initially the dye molecules reach the boundary layer;
then they have to diuse into the adsorbent surface; and
nally, they have to diuse into the porous structure of
the adsorbent. Therefore, this phenomenon will take a rel-
atively longer contact time (Senthilkumaar et al., 2005).
There was no signicant dierence in contact times in
adsorption of MB onto the activated carbons (AC1 and
AC2) between the period of 900 and 1440 min in this study.
Thus, the optimum contact time for all further experiments
was chosen as 1440 min.
3.4. Eect of temperature
To investigate the eect of temperature, the equilibrium
adsorption capacity for MB onto the activated carbons was
studied in the temperature range of 1545 C. The experi-
mental results indicated that the magnitude of adsorption
was proportional to the solution temperature. When the
temperature increased from 15 to 25 C, the adsorption
capacity for MB onto AC1 increased from 3.50 to
3.63 mg g
1
. The maximum adsorption capacity for MB
onto AC2 was 7.02 mg g
1
at 25 C. This result indicated
that the maximum adsorption for MB onto the activated
carbons was obtained at 25 C for all activated carbon
samples.
3.5. Eect of initial MB concentration
The eect of initial MB concentration (between 0 and
250 mg L
1
) on the adsorption of MB onto the activated
carbons was studied. The adsorption capacity for MB
increased with an increase in the initial MB concentration
for the activated carbons (AC1, AC2 and AC3). Increase
in the initial concentration of MB provided a powerful
driving force to overcome the mass transfer resistance
between the aqueous and solid phases. The maximum
adsorption capacities were obtained at the initial MB con-
centration of 250 mg L
1
.
3.6. Adsorption kinetics
To evaluate the kinetic mechanism that controls the
adsorption process, the pseudo-rst-order, pseudo-sec-
ond-order, and intraparticle diusion were tested to inter-
pret the experimental data. The kinetic models for MB
adsorption onto the activated carbons are shown in Figs.
2 and 3 and the results of kinetic parameters are shown
in Table 4. When the values of the correlation coecients
of the pseudo-rst-order and second-order kinetic model
are compared, the R
2
values for pseudo-second-order
kinetic model are higher than that of the values R
2
for
the pseudo-rst-order kinetic model (Table 4) for all acti-
vated carbon samples. This indicates that the kinetic mod-
eling of the MB adsorption onto the activated carbon
adsorbents well followed the pseudo-second-order rate
0
100
200
300
400
0 500 1000 1500
t (min.)
t
/
q
t

(
m
i
n
.

g

m
g
-
1
)
AC1
AC2
AC3
Fig. 3. Pseudo-second-order kinetic plot for the adsorption of methylene
blue onto the activated carbons.
0
0.2
0.4
0.6
0 0.05 0.1 0.15 0.2
1/t (min
-1
)
1
/
q
t

(
g

m
g
-
1
)
AC1
AC2
AC3
Fig. 2. Pseudo-rst-order kinetic plot for the adsorption of methylene
blue onto the activated carbons.
Table 4
Kinetic parameters for the adsorption of methylene blue onto the
activated carbons at 25 C
Type of the activated
carbon
AC1 AC2 AC3
Pseudo-rst-order
k
1
(min
1
) 3.596 11.67 8.420
q
1
(mg g
1
) 3.077 4.904 5.647
r
2
1
0.6191 0.6935 0.7819
Pseudo-second-order
k
2
(g mg
1
min
1
) 7.897 10
3
1.84 10
3
3.141 10
3
q
2
(mg g
1
) 3.713 7.400 7.158
r
2
2
0.9989 0.9968 0.9986
Intraparticle diusion
k
p
(mg g min
1/2
) 0.0745 0.2604 0.2101
C 1.8248 1.0084 2.2248
r
2
p
0.9914 0.9914 0.9348
6218 S. Karago z et al. / Bioresource Technology 99 (2008) 62146222
model with the correlation coecients of higher than 0.99
for all activated carbons in the present work. In many
cases, the pseudo-second-order kinetic model provided bet-
ter results for the adsorption of MB onto the activated car-
bons from various biomasses (Tan et al., 2007; Kavitha
and Namasivayam, 2007).
The rst order kinetic model equation (Kannan and
Sundaram, 2001) is:
1
q
t

1
q
1

k
1
q
1
1
t

where q
1
and q
t
are the amounts of the dye adsorbed at
equilibrium and at time t, in mg g
1
, and k
1
is the rst-or-
der rate constant (min
1
). Values of k
1
from the slope of
the plots of 1/q
t
versus 1/t (Fig. 2) are given in Table 4.
The pseudo-second-order kinetic model (Ho and
McKay, 1998) is expressed as:
t
q
t

1
k
2
q
2
2

1
q
2
t
where q
2
is the maximum adsorption capacity (mg g
1
) for
the pseudo-second-order adsorption, k
2
is the equilibrium
rate constant for the pseudo-second-order adsorption
(g mg
1
min
1
). Values of k
2
and q
2
were calculated from
the plot of t/q
t
against t (Fig. 3). The kinetic data for the
adsorption of methylene blue onto the activated carbons
under various conditions were calculated from the related
plots and are summarized in Table 4.
The intraparticle diusion (Crank, 1933) can be written
by following equation:
q
t
k
p
t
1=2
C
where C is the intercept and k
p
is the intraparticle diusion
rate constant (mg g
1
min
1/2
). According to this model,
the plot of the uptake, q
t
, versus the square-root of time,
t
1/2
is linear. If intraparticle diusion is involved in the
adsorption process and if the line passes through the origin,
the intraparticle diusion is the rate-controlling step (Kan-
nan and Sundaram, 2001; Bhattacharyya and Sharma,
2004; Chen et al., 2003). As can be seen from Fig. 4,
AC1 and AC2 are consistent with intraparticle diusion
but AC3 is not. Table 4 shows the correlation coecients
r
2
p
for the intraparticle diusion model are also lower
than the pseudo-second-order kinetic model. Similar re-
sults have been reported in a previous study which con-
cerned the production of the activated carbon from
Euphorbia Rigida by H
2
SO
4
activation (Gercel et al., 2007).
3.7. Adsorption isotherms
The adsorption data were analyzed with help of the fol-
lowing linear forms of Langmuir and Freundlich isotherms
(Adamson, 1960).
Langmuir isotherm:
C
e
q
e

1
q
max
K
L

C
e
q
max
where q
e
is the equilibrium MB concentration on the acti-
vated carbon (mg g
1
), C
e
is the equilibrium MB concen-
tration in the solution (mg L
1
), q
max
is the monolayer
adsorption capacity of the activated carbon (mg g
1
), K
L
is the Langmuir adsorption constant (L mg
1
).
The plots of C
e
/q
e
versus C
e
for the adsorption of
methylene blue onto the activated carbons are shown in
Fig. 5.
Freundlich isotherm:
log q
e
log K
F

1
n
log C
e
where q
e
is the equilibrium MB concentration on the acti-
vated carbon (mg g
1
), C
e
is the equilibrium MB concen-
tration in the solution (mg L
1
), K
F
(L g
1
) and n are the
Freundlich adsorption isotherm constants. The plots of
log q
e
versus log C
e
for the adsorption of methylene blue
onto the activated carbons are shown in Fig. 6. The Fre-
undlich isotherm endorses the heterogeneity of the surface
and assumes that the adsorption occurs at sites with dier-
ent energy of adsorption. The Langmuir and Freundlich
isotherm parameters for the MB adsorption of the acti-
vated carbons are given in Table 5. The results indicate that
the Langmuir isotherm ts better than the Freundlich iso-
therm. Thus according to a linear regression method, the
0
2
4
6
8
0 10 20 30
t
0.5
(min
0.5
)
q
t

(
m
g

g
-
1
)
AC1
AC2
AC3
Fig. 4. Intraparticle diusion plot for the adsorption of methylene blue
onto the activated carbons.
0
10
20
30
0 50 100 150 200 250
C
e
(mg L
-1
)
C
e
/
q
e

(
g

L
-
1
)
AC1
AC2
AC3
Fig. 5. Langmuir plots for the adsorption of methylene blue onto the
activated carbons.
S. Karago z et al. / Bioresource Technology 99 (2008) 62146222 6219
dye uptake is due to monolayer coverage of solute particles
onto the surface of the activated carbon.
A Langmuir isotherm assumes monolayer adsorption
onto a surface containing a nite number of adsorption
sites of uniform strategies of adsorption with no transmi-
gration of adsorbate in the plane of surface (Adamson,
1960). While a Freundlich isotherm model assumes hetero-
geneous surface energies, in which the energy term in the
Langmuir equation varies as a function of the surface cov-
erage (Adamson, 1960). Table 6 is presented to provide a
comparison for the maximum monolayer adsorption
capacities of the activated carbons from dierent biomass
sources. The maximum monolayer adsorption capacities
of some of the activated carbons were lower (Aygun
et al., 2003) and some of them were higher (Gercel et al.,
2007; Attia et al., 2003) than those in the present work.
Essential characteristics of the Langmuir isotherms can
be described by a separation factor (R
L
) which is dened
by the following equation (Weber and Chakravorti, 1974):
R
L

1
1 K
L
C
o
where C
o
is the initial concentration of MB (mg L
1
) and
K
L
is the Langmuir adsorption constant (L mg
1
). The
value of separation factor (R
L
) indicates the nature of
the absorption process (Kannan and Sundaram, 2001).
In the present study, the values of separation factor (R
L
)
were in the range of 01. This indicates that the adsorption
process of MB is favorable for all activated carbons
prepared.
3.8. Adsorption thermodynamics
Table 7 shows thermodynamic parameters (DG, DH,
DS) for the adsorption process. The Gibbs free energy
change (DG) indicates the degree of the spontaneity of
the adsorption process. The Gibbs free energy changes
(DG) of adsorption must be negative for a better adsorp-
tion. The values of Gibbs free energy change (DG) of
MB adsorption at the temperature of 298.15 K were deter-
mined as +2.22, 0.62, 0.574 kJ mol
1
for AC1, AC2
and AC3, respectively. These values indicate that the
adsorption process led to a decrease in Gibbs free energy
at 298.15 K for AC2 and AC3 whereas it increased in
Gibbs free energy for AC1. The negative value of DH
suggests the exothermic nature of adsorption for the acti-
vated carbons. Plot of ln K
L
versus 1/T for estimation of
thermodynamic parameters for the adsorption of MB onto
(AC1, AC2 and AC3) is shown in Fig. 7.
Thermodynamic parameters including Gibbs free energy
change (DG), enthalpy change (DH) and entropy change
(DS) were calculated from the following equations;
DG

RT ln K
L
where R is the universal gas constant (8.314 J/mol K), T is
the temperature (K) and K
L
value was calculated using the
following equations:
K
L

q
e
C
e
-1
-0.5
0
0.5
1
1.5
-2 -1 0 1 2 3
log C
e
l
o
g
q
e
AC1 AC2 AC3
Fig. 6. Freundlich plots for the adsorption of methylene blue onto the
activated carbons.
Table 5
Adsorption isotherms constants for the adsorption of methylene blue onto
the activated carbons at 25 C
Type of the activated carbon AC1 AC2 AC3
Langmuir
q
max
(mg g
1
) 10.21 16.43 15.798
K
L
(L mg
1
) 0.337 1.150 0.886
R
L
0.548 0.364 0.418
r
2
L
0.9940 0.9926 0.9915
Freundlich
n 2.217 4.425 2.793
K
F
(L g
1
) 0.917 4.300 2.418
r
2
F
0.965 0.838 0.916
Table 6
Comparison of the maximum monolayer adsorption of MB onto activated carbons from various sources
Activated carbon Maximum monolayer
adsorption capacity (mg g
1
)
References
Activated carbon from Almond shell 1.33 Aygun et al., 2003
Activated carbon from Walnut shell 3.53 Aygun et al., 2003
Activated carbon from Hazelnut shell 8.82 Aygun et al., 2003
Activated carbon from Apricot stones 4.11 Aygun et al., 2003
Activated carbon from Euphorbia rigida 114.45 Gercel et al., 2007
Activated carbon from Pistachio shells 129 Attia et al., 2003
Activated carbon from Sunower oil cake 16.43 Present work
6220 S. Karago z et al. / Bioresource Technology 99 (2008) 62146222
where q
e
and C
e
are the equilibrium concentration of MB
ions on the activated carbon(mg g
1
) and in the solution
(mg L
1
), respectively.
The enthalpy change (DH) and entropy change (DS) of
the adsorption were estimated from the following equation:
ln K
L

DS

R

DH

RT
The enthalpy (DH) and entropy (DS) can be obtained
from the slope and intercept of a Vant Ho equation of
(DG) versus:
DG

DH

TDS

where DG is the Gibbs free energy change (J), R the uni-


versal gas constant (8.314 J mol
1
K
1
) and T is the abso-
lute temperature (K).
4. Conclusion
The activated carbon produced from waste biomass
(sunower oil cake) was used for the removal of methylene
blue. The main conclusions are as follows:
The experimental impregnation ratio strongly aected
the adsorption capacity. The optimum impregnation
ratio was found to be 0.85 for the maximum adsorption
capacity for MB.
The maximum adsorption of MB onto the activated car-
bons was obtained at 25 C and pH 6 for the activated
carbons (AC1, AC2, and AC3).
The adsorption capacity for MB increased with increas-
ing in the initial concentration of MB.
The kinetic modeling of the MB adsorption onto the
activated carbon adsorbents well followed the pseudo-
second-order rate model with the correlation coecients
of higher than 0.99.
The adsorption process is favorable for the activated
carbons (AC1, AC2 and AC3).
Adsorption behavior is described by a monolayer Lang-
muir type isotherms for the activated carbons (AC1,
AC2 and AC3).
Consequently, the use of oil cakes for the production of
the activated carbons is very important from the view point
of economic aspects as they are cheap, widely available and
renewable sources.
Acknowledgements
This work was supported by Dokuz Eylu l University
and Anadolu University. The authors would like to thank
Prof. Dr. Hayrettin TU

RK for his valuable discussions.


References
Adamson, A.W., 1960. Physical Chemistry of Surface. Interscience
Publication, New York.
Alvarez, P., Blanco, C., Granda, M., 2007. The adsorption of chro-
mium(VI) from industrial wastewater by acid and base-activated
lignocellulosic residues. J. Hazard. Mater. 144, 400405.
Attia, A.A., Girgis, B.S., Khedr, S.A., 2003. Capacity of activated carbon
derived from pistachio shells by H
3
PO
4
in the removal of dyes and
phenolics. J. Chem. Technol. Biotechnol. 78, 611619.
Aygun, A., Yenisoy-Karakas, S., Duman, I., 2003. Production of granular
activated carbon from fruit stones and nutshells and evaluation of their
physical, chemical and adsorption properties. Microporous Mesopor-
ous Mater. 66, 189195.
Bhattacharyya, K.G., Sharma, A., 2004. Azadirachta indica leaf powder as
an eective biosorbent for dyes: A case study with aqueous Congo red
solutions. J. Environ. Manage. 71, 217229.
Boehm, H.P., 1966. Chemical identication of surface groups. Adv. Catal.
16, 179274.
Carrott, S.J.M., Carrott, M.M.L.R., 2007. Lignin from natural
adsorbent to activated carbon: A review. Bioresour. Technol. 98,
23012312.
Table 7
Thermodynamic parameters calculated from the Langmiur isotherm constant (K
L
) for the adsorption of MB onto the activated carbons
T (K) Activated carbon
AC1 AC2 AC3
DG
(kJ mol
1
)
DH
(kJ mol
1
)
DS
(J K
1
mol
1
)
DG
(kJ mol
1
)
DH
(kJ mol
1
)
DS
(J K
1
mol
1
)
DG
(kJ mol
1
)
DH
(kJ mol
1
)
DS
(J K
1
mol
1
)
288.15 2.26 0.382 0.039
298.15 2.22 6.494 29.89 0.62 6.470 22.23 0.574 6.183 20.45
308.15 2.62 0.53 0.219
318.15 3.11 0.754 0.547
-1.8
-1.2
-0.6
0
0.6
0.0031 0.0033 0.0035
1/T (K
-1
)
l
n
K
L
Fig. 7. Plot of ln K
L
vs. 1/T for estimation of thermodynamic parameters
for the adsorption of MB onto the activated carbons ( = AC1, j= AC2,
N = AC3).
S. Karago z et al. / Bioresource Technology 99 (2008) 62146222 6221
Carvalho, A.P., Gomes, M., Mestre, A.S., Pires, J., Carvalho, B.M., 2004.
Activated carbons from cork waste by chemical activation with
K
2
CO
3
, Application to adsorption of natural gas components. Carbon
42, 672674.
Chen, J.P., Wu, S., Chong, K.H., 2003. Surface modication of a granular
activated carbon by citric acid for enhancement of copper adsorption.
Carbon 41, 19791986.
Crank, G., 1933. The mathematics of diusion. Clarendon Press, London,
New York.
Daud, W.M.A.W., Ali, W.S.W., 2004. Comparison on pore development
of activated carbon produced from palm shell and coconut shell.
Bioresour. Technol. 93, 6369.
Gerc el, O., Gerc el, H.F., 2007. Adsorption of lead (II) ions from aqueous
solutions by activated carbon prepared from biomass plant material of
Euphorbia Rigida. Chem. Eng. J. 132, 289297.
Gercel, O., Ozcan, A., Ozcan, A.S., Gercel, H.F., 2007. Preparation of
activated carbon from a renewable bio-plant of Euphorbia Rigida by
H
2
SO
4
activation and its adsorption behavior in aqueous solutions.
Appl. Surface Sci. 253, 48434852.
Gergova, K., Petrov, N., Eser, S., 1994. Adsorption properties and
microstructure of activated carbons produced from agricultural by
products by steam pyrolysis. Carbon 32, 693702.
Guo, J., Lua, A.C., 2000. Eect of surface chemistry on gas-phase
adsorption by activated carbon prepared from oil-palm stone with pre-
impregnation. Separat. Puricat. Technol. 18, 4755.
Guo, J., Lua, A.C., 2007. Textural and chemical characterizations of
activated carbon prepared from oil-palm stone with H
2
SO
4
and KOH
impregnation. Microporous Mesoporous Mater. 32, 111117.
Hayashi, J., Kazehaya, A., Muroyama, K., Watkinson, A.P., 2000.
Preparation of activated carbon from lignin by chemical activation.
Carbon 38, 18731878.
Hameed, B.H., Din, A.T.M., Ahmad, A.L., 2007a. Adsorption of
methylene blue onto bamboo-based activated carbon: Kinetics and
equilibrium studies. J. Hazard. Mater. 141, 819825.
Hameed, B.H., Ahmad, A.L., Latif, K.N.A., 2007b. Adsorption of basic
dye (methylene blue) onto activated carbon prepared from rattan
sawdust. Dyes Pigments 75, 143149.
Hared, I.A., Dirion, J.L., Salvador, S., Lacroix, M., Rio, S., 2007.
Pyrolysis of wood impregnated with phosphoric acid for the produc-
tion of activated carbon: Kinetics and porosity development studies. J.
Anal. Appl. Pyrolysis 79, 101105.
Ho, Y.S., McKay, G., 1998. Kinetic models for the sorption of dye from
aqueous solution by wood. Process Safety Environ. Protec. 76, 183191.
Kannan, N., Sundaram, M.M., 2001. Kinetics and mechanism of removal
of methylene blue by adsorption on various carbons-A comparative
study. Dyes Pigments 51, 2540.
Karagoz, S., Yanik, J., Ucar, S., Song, C., 2002. Catalytic co-processing of
low-density polyethylene with VGO using metal supported on
activated carbon. Energy Fuels 16, 13011308.
Kavitha, D., Namasivayam, C., 2007. Experimental and kinetic studies on
methylene blue adsorption by coir pith carbon. Bioresour. Technol. 98,
1421.
Kumagai, S., Noguchi, Y., Kurimoto, Y., Takeda, K., 2007. Oil adsorbent
produced by the carbonization of rice husks. Waste Manage. 27, 554
561.
Li, S., Xu, S., Liu, S., Yang, C., Lu, Q., 2004. Fast pyrolysis of biomass in
free-fall reactor for hydrogen-rich gas. Fuel Process. Technol. 85,
12011211.
Lillo-Ro denas, M.A., Marco-Lozar, J.P., Cazorla-Amoros, D., Linares-
Solano, A., 2007. Activated carbons prepared by pyrolysis of mixtures
of carbon precursor/alkaline hydroxide. J. Anal. Appl. Pyrolysis 80,
166174.
Ling, L., Li, K., Liu, L., Miyamoto, S., Korai, Y., Kawano, S., Mochida,
I., 1999. Removal of SO
2
over ethylene tar pitch and cellulose based
activated carbon bers. Carbon 37, 499504.
Nagano, S., Tamon, H., Adzumi, T., Nakagawa, K., Suzuki, T., 2000.
Activated carbon from municipal waste. Carbon 38, 915920.
Nakagawa, Y., Molina-Sabio, M., Rodr guez-Reinoso, F., 2007. Modi-
cation of the porous structure along the preparation of activated
carbon monoliths with H
3
PO
4
and ZnCl
2
. Microporous Mesoporous
Mater. 103, 2934.
Qian, Q., Machida, M., Tatsumoto, H., 2007. Preparation of activated
carbon from cattle-manure compost by zinc chloride activation.
Bioresour. Technol. 98, 353360.
Radovic, L.R., Silva, I.F., Ume, J.I., Menendez, J.A., Leon, C.A., Leon,
Y., Scaroni, A.W., 1997. An experimental and theoretical study of the
adsorption of aromatics possessing electron-withdrawing and electron-
donating functional groups by chemically modied activated carbons.
Carbon 35 (9), 13391348.
Savova, D., Petrov, N., Yardim, M.F., Ekinci, E., Budinova, T.,
Razvigorova, M., Minkova, V., 2003. The inuence of the texture
and surface properties of carbon adsorbents obtained from biomass
products on the adsorption of manganese ions from aqueous solution.
Carbon 41 (10), 18971903.
Senthilkumaar, S., Varadarajan, P.R., Porkodi, K., Subbhuraam, C.V.,
2005. Adsorption of methylene blue onto jute ber carbon: Kinetics
and equilibrium studies. J. Colloid Interface Sci. 284, 7882.
Tan, I.A.W., Hameed, B.H., Ahmad, A.L., 2007. Equilibrium and kinetic
studies on basic dye adsorption by oil palm bre activated carbon.
Chem. Eng. J. 127, 111119.
Weber, T.W., Chakravorti, P.K., 1974. Pore and solid diusion models for
xed bed adsorbent. J. Am. Inst. Chem. Engrs. 20, 228252.
Yalcin, N., Sevinc, V., 2000. Studies of the surface area and porosity
of activated carbons prepared from rice husks. Carbon 38, 1943
1945.
6222 S. Karago z et al. / Bioresource Technology 99 (2008) 62146222