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Activated Carbons from Waste Biomass by Sulfuric Acid Activation and Their
Use on Methylene Blue Adsorption

Article  in  Bioresource Technology · October 2008

DOI: 10.1016/j.biortech.2007.12.019 · Source: PubMed

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Bioresource Technology 99 (2008) 6214–6222

Activated carbons from waste biomass by sulfuric acid activation

and their use on methylene blue adsorption
Selhan Karagöz a,*, Turgay Tay b, Suat Ucar a, Murat Erdem b
a
Chemistry Program, Izmir Vocational School, Dokuz Eylül 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 sunflower oil cake by sulphuric acid activation with different 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 effects 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 fit 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 (RL) revealed the favorable nature of
the isotherm of the MB activated carbon system.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Waste biomass; Activated carbon; Adsorption; Methylene blue

1. Introduction as support for catalyst (Karagoz et al., 2002). There are

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
effective 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
*
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. Karagöz).
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.;
ZnCl2 (Yalcin and Sevinc, 2000), H3PO4 (Nakagawa
et al., 2007), HCl (Alvarez et al., 2007), and H2SO4 (Gercßel
and Gercßel, 2007) or with basic reagents KOH (Guo and
Lua, 2007), K2CO3 (Carvalho et al., 2004), NaOH (Lillo-
Ródenas et al., 2007), and Na2CO3 (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, significant efforts 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 effluents.
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 Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.12.019
 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222 6215

surface area (Gercel et al., 2007). However, as well-known, Table 1

fossil fuels are finite. Thus, the production of activated car- Proximate, ultimate and component analyses of waste biomass
bon from renewable sources is indeed of importance from Type of waste biomass Sunflower oil cake
the view point of economic and environmental aspects. Proximate analysis (as received, wt%)
Methylene blue dye serves as a model compound for Moisture 9.84
adsorption of organic contaminants from aqueous solu- Volatile matter 67.36
Fixed carbon 17.62
tions (Hameed et al., 2007a, 2007b; Kavitha and Namasi- Ash 5.18
vayam, 2007).
Ultimate analysis (dry basis, wt%)
The present investigation assesses the issues with the
C 46.55
activated carbon production from waste biomass and its H 6.087
adsorption capacity on methylene blue. The equilibrium N 4.488
and kinetic data of the adsorption process of methylene S 0.486
blue molecules onto the prepared activated carbons were Oa 42.389
also studied. GCVb (kcal/kg) 4546
Component analysis (dry basis, wt%)
2. Experimental Extractivesc 13.01
Hemicellulose 36.47
Lignin 15.77
2.1. Materials
Cellulose 30.08
a
By difference.
Waste biomass (Sunflower oil cake) sample was b
Gross calorific value.
obtained from Altinyag Oil Company, Izmir, Turkey and c
Toluene/alcohol (2/1) (v/v).
used as received. The proximate, ultimate and component
analyses of sunflower oil cake are shown in Table 1. Deter-
mination of each component of sunflower oil cake was 600 °C under nitrogen (N2) flow of 30 mL min1 at a heat-
done using the method given in the literature (Li et al., ing rate of 5 °C min1. (v) After carbonization, the sample
2004). Sodium hydroxide, sodium carbonate, sodium bicar- had been cooled down under N2 gas flow, the carbonized
bonate, barium chloride, hydrochloric acid (37 wt%), ethyl sample was washed several times with hot water, and
alcohol, and toluene were obtained from Aldrich and used finally with cold water to remove residual chemicals. The
as received. Sulfuric acid (98 wt%) obtained from Aldrich washing and filtration steps were repeated until the filtrate
was used as an activating reagent. Methylene blue (MB) became neutral. The washed sample was dried at 110 °C for
was obtained from Merck and used as an adsorbate in this 24 h to prepare the activated carbon. The activated carbons
work. were denoted as AC1 with the impregnation ratio of 0,
AC2 with the impregnation ratio of 0.85, and AC3 with
2.2. Preparation of the activated carbons the impregnation ratio of 1.90. The activated carbons were
prepared and characterized and used as adsorbents for the
The preparation of activated carbons from waste bio- removal of methylene blue (MB) from aqueous solutions.
mass was carried out in six stages: (i) Waste biomass was The experimental impregnation ratio was estimated from
treated with sulfuric acid (H2SO4) solutions. (ii) The acidi- the following equation:

ðweight of sample after impregnationÞ  ðweight of waste biomassÞ

Exp: impregnation ratio ¼
ðweight of waste biomassÞ

fied 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
fixed bed design of stainless steel with 6 cm diameter and
21 cm height. The impregnated sample was carbonized at
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:

ðweight of sample before washingÞ  ðweight of sample after washingÞ

Chemical recovery ¼  100
ðweight of impregnated chemicalÞ
6216 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222

Chemical recoveries were found to be 0.79 and 0.81 wt% the assumption that NaOH neutralizes carboxylic, lactonic,
for AC2 and AC3, respectively. The yield of the activated and phenolic groups; Na2CO3, carboxylic and lactonic
carbon was calculated based on the weight of waste bio- groups NaHCO3, only carboxylic group.
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, 2.4. Adsorption experiments
AC2, and AC3, respectively.
The adsorption experiments were carried out by 10 mL
2.3. Characterization of the activated carbons of a 25 ppm MB solution with 20 mg of the activated car-
bon and the pH was carefully adjusted between 3 and 10
A measurement of specific surface areas of the activated with adding a small amount of dilute HCl or NaOH solu-
carbons produced from the waste biomass has been made tion using a pH meter (Hanna Instruments HI 8314). The
by N2 adsorption (at 77 K), using a surface analyzer MB solutions were stirred using a mechanical magnetic
(Quantachrome Inst., Nova 2200e). The micropore volume stirrer in a 50 mL Erlenmeyer sealed with parafilm to avoid
(Vmicro) was determined by using t-plot method. The results evaporation. The optimum pH was then determined as 6
were obtained by using Novawin 2 software. The mesopore and used throughout further adsorption experiments,
volume (Vmeso) was calculated by subtracting Vmicro from which were conducted at various time (from 0 min to
Vtotal (Vmeso = Vtotal  Vmicro). Proximate analyses of the 1440 min) intervals and temperatures (15, 25, 35, and
activated carbons were done according to ASTM D3174- 45 °C) in order to determine the adsorption equilibrium
04 for ash analysis and ASTM D3175-89a for volatile time and the maximum removal of MB. The solutions were
matter. The activated carbons were analyzed for carbon, centrifuged and then subjected to quantitative analyses.
nitrogen, hydrogen, sulfur, and oxygen (by difference) The equilibrium concentrations of each solution were
abundances using a LECO CHNS 932 Elemental Analyzer determined from the absorbance of the solution measured
according to ASTM D5291-96. The characteristics of the by a spectrophotometer (Shimadzu UV-2450PC) at the
activated carbons are presented in Table 2. kmax value, which is 665 nm for methylene blue. The
The surface functional groups of the activated carbons amount of MB adsorbed onto the activated carbon surface
(AC1, AC2, and AC3) were characterized according to was determined by the difference between the initial and
Boehm method (Boehm, 1966).The weighed amounts of remaining concentrations of MB solution. The amount of
the activated carbon samples (about 1.00 g) were placed adsorbed MB at equilibrium, qe (mg g1) was calculated by
in 50 mL vials of the following solutions: 0.1 N of NaOH, ðC o  C e ÞV
NaHCO3, and Na2CO3, respectively. The vials were sealed qe ¼
W
and allowed to equilibrate with agitation for 48 h at room
temperature and then the activated carbon samples were where Co and Ce (mg L1) are the liquid-phase initial and
separated by filtration. After filtration, the liquids were equilibrium concentrations of the dye, respectively. V is
titrated by back titration of the acidic solutions with the volume of the solution (L), and W is the mass of dry
0.1 N of standard HCl aqueous solution. The amount of adsorbent used (g). The adsorption of MB onto the acti-
acidic groups on the activated carbon is calculated under vated carbon was also evaluated at constant temperature
of 25 °C for the adsorption isotherms.
The procedures for the kinetic experiments were basi-
Table 2
Characteristics of the activated carbons cally identical to those of equilibrium tests. The aqueous
samples were taken at present time intervals, and the con-
Type of the activated carbon AC1 AC2 AC3
centrations of MB were similarly measured. The amount of
Proximate analysis
adsorption at time t, qt (mg g1), was calculated by
Volatile matter 13.23 17.54 22.62
Fixed carbon 68.47 69.03 62.47 ðC o  C t ÞV
Ash 18.30 13.43 14.91 qt ¼
W
Elemental analysis (wt%)
C 59.24 58.79 60.59
where Co and Ct (mg L1) are the liquid-phase concentra-
H 2.445 1.710 1.551 tions of MB at initial and any time t, respectively. V is the
N 4.625 5.647 6.461 volume of the solution (L), and W is the mass of dry adsor-
S 0.042 6.168 7.713 bent used (g).
O* 33.648 27.685 23.685
Typical properties 3. Results and discussion
Specific surface area (m2 g1) 8.8 240.02 114.77
Total pore volume (cm3 g1) 0.0063 0.116 0.073
Micropore area (m2 g1) 8.268 230.80 89.68
3.1. The influence of impregnation ratio on characteristics of
Micropore volume (cm3 g1) – 0.111 0.044 the activated carbons
Mesopore volume (cm3 g1) 0.0063 0.005 0.029
Average pore diameter (Å) 28.67 19.38 25.53 The characteristics of the activated carbons prepared at
*
By difference. 600 °C using different impregnation ratios of H2SO4 are
 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222
shown in Table 2. For comparison purpose, the character-
istics of the activated carbon (AC1) prepared at 600 °C
without H2SO4 activation was also shown in Table 2.
AC1 prepared at the carbonization temperature without
H2SO4 activation had a surface area of 8.8 m2 g1. Using
H2SO4, as the activating reagent, the maximum surface 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 m2 g1. There
are also significant 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 ZnCl2 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 affects 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 influence 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. Effect of pH
The effect 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 effect of pH on the adsorption
of methylene blue onto the activated carbons. The pH of
solution appears to be a key factor affecting the adsorption
characteristics of MB onto the activated carbons. As can be
8 temperatures were investigated (Gercel et al., 2007) and it
6 was achieved at pH 6. In this study, the maximum adsorp-
AC1
qe (mg g-1)
4
AC2
AC3
2
0 3.3. Effect of contact time
2 4 6 8 10 12
pH
Fig. 1. Effect of pH for the adsorption of methylene blue onto the
activated carbons (Co = 25 ppm, mAC = 20 mg, t = 1440 min, V = 10 mL,
T = 25 °C).
6217
Table 3
Surface acidic groups of the activated carbons
Surface acidic groups Phenolic Lactonic Carboxylic Total
(meq g1) 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
seen from Fig. 1, it is evident that increasing the pH of
solution serves to increase the adsorption capacity with a
significant 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 affects 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 affect 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
(pHIEP) or point of zero charge (pHPZC) of the activated
carbon (Radovic et al., 1997; Savova et al., 2003). Cationic
adsorption is favored at pH > pHPZC (e.g. on COO
groups) and anionic adsorption is favored at pH < pHPZC
(e.g. on Lewis-base–type 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 (pHPZC) 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 H2SO4 activation for the removal of methylene blue
from aqueous solutions at various contact times, pHs and
was found that the maximum methylene blue removal
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.
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 (0–1440 min) was studied.
6218 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222

The maximum adsorption capacities for methylene blue 0.6

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- 0.4

1/qt (g mg-1)
lene blue onto AC3. The adsorption of methylene blue
onto jute fiber carbon was investigated (Senthilkumaar AC1
et al., 2005). It was reported that during adsorption of AC2
0.2
dyes, initially the dye molecules reach the boundary layer; AC3
then they have to diffuse into the adsorbent surface; and
finally, they have to diffuse into the porous structure of
the adsorbent. Therefore, this phenomenon will take a rel- 0
atively longer contact time (Senthilkumaar et al., 2005). 0 0.05 0.1 0.15 0.2
1/t (min-1)
There was no significant difference in contact times in
adsorption of MB onto the activated carbons (AC1 and Fig. 2. Pseudo-first-order kinetic plot for the adsorption of methylene
AC2) between the period of 900 and 1440 min in this study. blue onto the activated carbons.
Thus, the optimum contact time for all further experiments
was chosen as 1440 min.
400
3.4. Effect of temperature

300
To investigate the effect of temperature, the equilibrium t/qt (min. g mg-1)
adsorption capacity for MB onto the activated carbons was
studied in the temperature range of 15–45 °C. The experi-
200
mental results indicated that the magnitude of adsorption
was proportional to the solution temperature. When the AC1
temperature increased from 15 to 25 °C, the adsorption 100
AC2
capacity for MB onto AC1 increased from 3.50 to
3.63 mg g1. The maximum adsorption capacity for MB AC3
onto AC2 was 7.02 mg g1 at 25 °C. This result indicated 0
that the maximum adsorption for MB onto the activated 0 500 1000 1500
t (min.)
carbons was obtained at 25 °C for all activated carbon
samples. Fig. 3. Pseudo-second-order kinetic plot for the adsorption of methylene
blue onto the activated carbons.
3.5. Effect of initial MB concentration
Table 4
The effect of initial MB concentration (between 0 and Kinetic parameters for the adsorption of methylene blue onto the
250 mg L1) on the adsorption of MB onto the activated activated carbons at 25 °C
carbons was studied. The adsorption capacity for MB Type of the activated AC1 AC2 AC3
increased with an increase in the initial MB concentration carbon
for the activated carbons (AC1, AC2 and AC3). Increase Pseudo-first-order
in the initial concentration of MB provided a powerful k1 (min1) 3.596 11.67 8.420
driving force to overcome the mass transfer resistance q1 (mg g1) 3.077 4.904 5.647
between the aqueous and solid phases. The maximum r21 0.6191 0.6935 0.7819
adsorption capacities were obtained at the initial MB con- Pseudo-second-order
centration of 250 mg L1. k2 (g mg1 min1) 7.897  103 1.84  103 3.141  103
q2 (mg g1) 3.713 7.400 7.158
r22 0.9989 0.9968 0.9986
3.6. Adsorption kinetics
Intraparticle diffusion
To evaluate the kinetic mechanism that controls the kp (mg g min1/2) 0.0745 0.2604 0.2101
C 1.8248 1.0084 2.2248
adsorption process, the pseudo-first-order, pseudo-sec- r2p 0.9914 0.9914 0.9348
ond-order, and intraparticle diffusion were tested to inter-
pret the experimental data. The kinetic models for MB
adsorption onto the activated carbons are shown in Figs. kinetic model are higher than that of the values R2 for
2 and 3 and the results of kinetic parameters are shown the pseudo-first-order kinetic model (Table 4) for all acti-
in Table 4. When the values of the correlation coefficients vated carbon samples. This indicates that the kinetic mod-
of the pseudo-first-order and second-order kinetic model eling of the MB adsorption onto the activated carbon
are compared, the R2 values for pseudo-second-order adsorbents well followed the pseudo-second-order rate
 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222 6219

model with the correlation coefficients 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 first order kinetic model equation (Kannan and
Sundaram, 2001) is:
 
1 1 k1 1
¼ þ
qt q1 q1 t
where q1 and qt are the amounts of the dye adsorbed at
equilibrium and at time t, in mg g1, and k1 is the first-or-
der rate constant (min1). Values of k1 from the slope of
the plots of 1/qt versus 1/t (Fig. 2) are given in Table 4.
The pseudo-second-order kinetic model (Ho and
McKay, 1998) is expressed as:
t 1 1 vated carbon (mg g1), Ce is the equilibrium MB concen-
¼ þ t
qt k 2 q22 q2
where q2 is the maximum adsorption capacity (mg g1) for
the pseudo-second-order adsorption, k2 is the equilibrium
rate constant for the pseudo-second-order adsorption
(g mg1 min1). Values of k2 and q2 were calculated from
the plot of t/qt 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 diffusion (Crank, 1933) can be written
by following equation:
qt ¼ k p t1=2 þ C
where C is the intercept and kp is the intraparticle diffusion
rate constant (mg g1 min1/2). According to this model,
the plot of the uptake, qt, versus the square-root of time,
t1/2 is linear. If intraparticle diffusion is involved in the
adsorption process and if the line passes through the origin,
the intraparticle diffusion 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 diffusion
but AC3 is not. Table 4 shows the correlation coefficients
ðr2p Þ for the intraparticle diffusion 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 H2SO4 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:
Ce 1 Ce
¼ þ
qe qmax K L qmax
where qe is the equilibrium MB concentration on the acti-
tration in the solution (mg L1), qmax is the monolayer
adsorption capacity of the activated carbon (mg g1), KL
is the Langmuir adsorption constant (L mg1).
The plots of Ce/qe versus Ce for the adsorption of
methylene blue onto the activated carbons are shown in
Fig. 5.
Freundlich isotherm:
1
log qe ¼ log K F þ log C e
n
where qe is the equilibrium MB concentration on the acti-
vated carbon (mg g1), Ce is the equilibrium MB concen-
tration in the solution (mg L1), KF (L g1) and n are the
Freundlich adsorption isotherm constants. The plots of
log qe versus log Ce 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 differ-
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 fits better than the Freundlich iso-
therm. Thus according to a linear regression method, the

30
8

6 20
Ce /qe (g L )
-1
qt (mg g-1)

4
AC1 10 AC1
2 AC2
AC2
AC3
AC3
0 0
0 10 20 30 0 50 100 150 200 250
t 0.5 (min0.5) Ce (mg L-1)

Fig. 4. Intraparticle diffusion plot for the adsorption of methylene blue Fig. 5. Langmuir plots for the adsorption of methylene blue onto the
onto the activated carbons. activated carbons.
6220 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222

1.5 et al., 2003) and some of them were higher (Gercel et al.,
2007; Attia et al., 2003) than those in the present work.
1 Essential characteristics of the Langmuir isotherms can
be described by a separation factor (RL) which is defined
0.5 by the following equation (Weber and Chakravorti, 1974):
log qe

1
0 RL ¼
1 þ K LCo
-2 -1 0 1 2 3
-0.5 where Co is the initial concentration of MB (mg L1) and
KL is the Langmuir adsorption constant (L mg1). The
AC1 AC2 AC3
-1 value of separation factor (RL) indicates the nature of
log Ce the absorption process (Kannan and Sundaram, 2001).
In the present study, the values of separation factor (RL)
Fig. 6. Freundlich plots for the adsorption of methylene blue onto the were in the range of 0–1. This indicates that the adsorption
activated carbons.
process of MB is favorable for all activated carbons
prepared.

Table 5 3.8. Adsorption thermodynamics

Adsorption isotherms constants for the adsorption of methylene blue onto
the activated carbons at 25 °C
Table 7 shows thermodynamic parameters (DG°, DH°,
Type of the activated carbon AC1 AC2 AC3 DS°) for the adsorption process. The Gibbs free energy
Langmuir change (DG°) indicates the degree of the spontaneity of
qmax (mg g1) 10.21 16.43 15.798 the adsorption process. The Gibbs free energy changes
KL (L mg1) 0.337 1.150 0.886
(DG°) of adsorption must be negative for a better adsorp-
RL 0.548 0.364 0.418
r2L 0.9940 0.9926 0.9915 tion. The values of Gibbs free energy change (DG°) of
MB adsorption at the temperature of 298.15 K were deter-
Freundlich
n 2.217 4.425 2.793
mined as +2.22, 0.62, 0.574 kJ mol1 for AC1, AC2
KF (L g1) 0.917 4.300 2.418 and AC3, respectively. These values indicate that the
r2F 0.965 0.838 0.916 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°
dye uptake is due to monolayer coverage of solute particles suggests the exothermic nature of adsorption for the acti-
onto the surface of the activated carbon. vated carbons. Plot of ln KL versus 1/T for estimation of
A Langmuir isotherm assumes monolayer adsorption thermodynamic parameters for the adsorption of MB onto
onto a surface containing a finite number of adsorption (AC1, AC2 and AC3) is shown in Fig. 7.
sites of uniform strategies of adsorption with no transmi- Thermodynamic parameters including Gibbs free energy
gration of adsorbate in the plane of surface (Adamson, change (DG°), enthalpy change (DH°) and entropy change
1960). While a Freundlich isotherm model assumes hetero- (DS°) were calculated from the following equations;
geneous surface energies, in which the energy term in the DG ¼ RT ln K L
Langmuir equation varies as a function of the surface cov-
erage (Adamson, 1960). Table 6 is presented to provide a where R is the universal gas constant (8.314 J/mol K), T is
comparison for the maximum monolayer adsorption the temperature (K) and KL value was calculated using the
capacities of the activated carbons from different biomass following equations:
sources. The maximum monolayer adsorption capacities q
KL ¼ e
of some of the activated carbons were lower (Aygun Ce

Table 6
Comparison of the maximum monolayer adsorption of MB onto activated carbons from various sources
Activated carbon Maximum monolayer References
adsorption capacity (mg g1)
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 Sunflower oil cake 16.43 Present work
 S. Karagöz et al. / Bioresource Technology 99 (2008) 6214–6222 6221

Table 7
Thermodynamic parameters calculated from the Langmiur isotherm constant (KL) for the adsorption of MB onto the activated carbons
T (K) Activated carbon
AC1 AC2 AC3
DG° DH° DS° DG° DH° DS° DG° DH° DS°
(kJ mol1) (kJ mol1) (J K1 mol1) (kJ mol1) (kJ mol1) (J K1 mol1) (kJ mol1) (kJ mol1) (J K1 mol1)
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

0.6  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).
0  The adsorption capacity for MB increased with increas-
0.0031 0.0033 0.0035 ing in the initial concentration of MB.
 The kinetic modeling of the MB adsorption onto the
lnKL

-0.6 activated carbon adsorbents well followed the pseudo-

second-order rate model with the correlation coefficients
of higher than 0.99.
-1.2  The adsorption process is favorable for the activated
carbons (AC1, AC2 and AC3).
 Adsorption behavior is described by a monolayer Lang-
-1.8
muir type isotherms for the activated carbons (AC1,
1/T (K-1) AC2 and AC3).
Fig. 7. Plot of ln KL vs. 1/T for estimation of thermodynamic parameters
for the adsorption of MB onto the activated carbons ( = AC1, j = AC2, Consequently, the use of oil cakes for the production of
N = AC3). the activated carbons is very important from the view point
of economic aspects as they are cheap, widely available and
renewable sources.
where qe and Ce are the equilibrium concentration of MB
ions on the activated carbon(mg g1) and in the solution
(mg L1), respectively. Acknowledgements
The enthalpy change (DH°) and entropy change (DS°) of
the adsorption were estimated from the following equation: This work was supported by Dokuz Eylül University
 and Anadolu University. The authors would like to thank
DS DH 
ln K L ¼  Prof. Dr. Hayrettin TÜRK for his valuable discussions.
R RT
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