Fuel 115 (2014) 804–811

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Production and characterization of activated carbon from sour cherry

stones by zinc chloride
Dilek Angin ⇑
Department of Food Engineering, Sakarya University, Esentepe Campus, 54187 Sakarya, Turkey

h i g h l i g h t s

 Low-cost activated carbon can be produced from sour cherry stones.

 Temperature and impregnation ratio have a stronger effect on pore structure.
 Surface area and pore volume of activated carbon increased at 700 °C.
 Full quadratic model developed by RSM can be used to predict the values.

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

Article history: The purpose of this study is to produce the low-cost activated carbon from the sour cherry (Prunus cerasus
Received 19 February 2013 L.) stones, known as a waste of fruit juice industry, by chemical activation using zinc chloride. The effects
Received in revised form 3 April 2013 of the activation temperature and the impregnation ratio on the surface and chemical properties of acti-
Accepted 20 April 2013
vated carbon were investigated. Also, the mathematical correlation between the activation process vari-
Available online 9 May 2013
ables and outputs such as activated carbon yield and surface area were examined by using the Response
surface methodology. The activation temperatures and impregnation ratios were selected at the range of
Keywords:
500–900 °C and 1:1–4:1, respectively. In the study, it was observed that the optimum conditions for the
Sour cherry stones
Activated carbon
activated carbon production were activation temperature of 700 °C and impregnation ratio of 3:1. The
Chemical activation optimum conditions resulted in an activated carbon with a carbon content of 80.78% and a yield of
Characterization 16.22%, while the Brunauer–Emmett–Teller surface area evaluated using nitrogen adsorption isotherm
Modeling corresponds to 1704 m2 g1, with the total pore volume of 1.566 cm3 g1. The activated carbon was het-
eroporous with the micropore volume contributing to 62.84%. Also, experimental results showed that the
activation temperature and the impregnation ratio have significant effects on the pore structure of the
activated carbon and sour cherry stones seemed to be an alternative precursor for the commercial acti-
vated carbon productions.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Activated carbons have been widely used as adsorbents in the
separation and purification processes for gaseous or aqueous solu-
tion system, and also used as a catalyst or a catalyst support in the
catalytic processes. Thus an activated carbon has played an impor-
tant role in the chemical, pharmaceutical and food industries [1]. Its
textural and surface properties depend on the raw material and on
the method used in its preparation. Nowadays, activated carbon can
be produced from a large number of abundant and low-cost materi-
als, which possess high carbon content and a low inorganic content
[2].
Basically, activated carbon can be prepared by physical and
chemical activation methods and, occasionally, by combination of
⇑ Tel./fax: +90 264 2955927.
E-mail address: angin@sakarya.edu.tr
both types of methods [2]. In the physical activation process, the
precursor is first carbonized at 600–800 °C under an inert atmo-
sphere and activated using steam or carbon dioxide at upper. When
activated carbons are prepared by chemical activation, the precur-
sor is mixed with chemical compounds such as zinc chloride, phos-
phoric acid, potassium hydroxide, sulfuric acid or sodium hydroxide
and carbonized-activated in the same step at various temperatures
[3]. In comparison with physical activation, there are two significant
advantages of chemical activation. One is the lower temperature in
which the process is accomplished. The other is that the global yield
of the chemical activation trends to be greater since burn-off char is
not required [4]. The chemical activation process has been exten-
sively used by many researchers for the preparation of activated
carbons from different agricultural wastes by various chemical re-
agents such as date stones by zinc chloride [5], coconut shell by
phosphoric acid [6], hazelnut bagasse by potassium hydroxide [7],
nutshells by potassium carbonate [1], pomegranate seeds by zinc

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.04.060
 D. Angin / Fuel 115 (2014) 804–811 805

chloride [8], waste tea by phosphoric acid [9], and Paulownia wood Table 1
by zinc chloride [10]. Among the numerous dehydrating agents, zinc Characteristics of the sour cherry stones.

chloride in particular is the widely used chemical agent in the prep- Characteristics Methods Sour cherry stones
aration of activated carbon. Knowledge of different variables during Moisture content (wt.%) ASTM D 2016 2.67
the activation process is very important in developing the porosity
Proximate analysis (wt.%)
of carbon sought for a given application. Impregnation with ZnCl2 Volatile Matter ASTM E 872 78.50
causes degradation of the cellulosic material and, on carbonization, Ash ASTM D1102 0.17
dehydration. These processes result in charring and aromatization Fixed carbon By difference 21.33
of the carbon skeleton and creation of the pore structure [2]. Chem- Ultimate analysis (wt.%)
ical activation by zinc chloride (ZnCl2) improves the pore develop- Carbon CARLO ERBA Instrument 48.72
ment in the carbon structure and because of the effect of Hydrogen 6.41
Nitrogen 1.85
chemicals; the yields of carbon are usually high [11]. Sulphur n.d.
The most important characteristics of an activated carbon is its Oxygen By difference 43.02
surface area and adsorption capacity, which are highly influenced Surface properties
by the activated carbon preparation conditions. This is because BET surface area (m2 g1) 41.54
activated carbon preparation variables such as activation tempera- Total pore volume (cm3 g1) 0.0975
ture, activation time and chemical impregnation ratio will influ-
n.d.: not detection.
ence the pore development and surface characteristics of the
activated carbon produced. Therefore, the challenge in activated
carbon production is to produce very specific carbons which are
to the removal of inorganic components from lignocellulosic mate-
suitable for certain applications. Response surface methodology
rials) and washed with distilled water until pH value was 6–7
(RSM) has been found to be a useful tool to study the interactions
eventually reached in the residual liquid [2]. The results of
of two or more variables [12]. Modeling of experimental conditions
proximate and ultimate analysis of sour cherry stones are given
using RSM was widely applied in various processes. Some of the
in Table 1.
previous studies found in applying RSM in preparation of activated
carbons used precursors such as olive-waste cakes [13], Tamarind
2.2. Preparation of the activated carbons
wood [4], Turkish lignite [3] and coconut shell [6].
One of the main challenges in the commercial manufacture of
In the current study, chemical activation of sour cherry stones
activated carbons is to identify new precursors that are cheap,
was performed using zinc chloride (ZnCl2). The impregnation ratio
accessible and available in abundant quantity which has potential
was calculated as the ratio of the weight of ZnCl2 in solution to the
for significant economic benefits. A number of raw lignocellulosic
weight of the used sour cherry stones. The impregnation ratio var-
materials such as wood, fruit shells and stones, has been utilized
ied between 1:1 and 4:1. Twenty to eighty grams of ZnCl2 were dis-
for the preparation of activated carbons with varied degree of suc-
solved in 250 mL of distilled water, and then 20 g of sour cherry
cess over the years [14]. Processing of fruits produces a solid waste
stones were mixed with the ZnCl2 solution and stirred at approxi-
of peel/skin, stones or seeds which can be used as precursor for the
mately 80 °C for 24 h to ensure a complete reaction between ZnCl2
production of activated carbon. There are lots of fruits containing
and sour cherry stones. The mixtures were then filtered and the
considerable amounts of stones [8]. One of these fruits is sour cherry
remaining solids were dried at 105 ± 3 °C for about 24 h.
(Prunus cerasus L.). Turkey is the largest producer of sour cherry (P.
Carbonization of the impregnated samples was carried out in a
cerasus L.) in the world with an annual production of 192,705 tones.
316 stainless steel tubular reactor with a length of 90 mm and an
Poland ranks second, with an annual production of 189,200 tones,
internal diameter of 105 mm (Protherm PTF 12) under nitrogen
followed by Russia (170,000 tones) and the USA (160,118 tones).
flow. About 10 g of the impregnated sample was placed on a
Forty percent of the total sour cherry crop in Turkey is processed
ceramic crucible in the reactor and heated up to the final activation
into juice due to consumer preferences for this type of juice [15].
temperature under the nitrogen flow (100 cm3/min) at heating rate
In Turkey, a great quantity of sour cherry stones is yearly generated
of 10 °C/min and held for 2 h at this final temperature. The final
as a waste in the industrial production of cherry juice. Therefore,
activation temperature varied from 500 to 900 °C. The resulting
this study has focused on the production of activated carbon from
solids after carbonization were boiled at about 90 °C with 100 mL
sour cherry stones by chemical activation with ZnCl2. The effects
of 1 N hydrochloric acid (HCl) solution for 30 min to leach out
of process variables such as the activation temperature and impreg-
the activating agent, filtered and rinsed by warm distilled water
nation ratio on the product yields, pore structures (specific surface
several times until the pH value was 6–7. Finally, they were dried
area, pore volume, and pore size distribution), and chemical proper-
at 105 ± 3 °C for 24 h. The yield of activated carbon was calculated
ties of the activated carbons were investigated. Additionally, in this
from the following equation:
study, mathematical correlation between the activation process
variables (temperature and impregnation ratio) and process out- Yield of activated carbon ðwt%Þ
puts such as activated carbon yield and surface area were re-
Final weight of activated carbon
searched using the Response surface methodology (RSM) method. ¼  100 ð1Þ
Initial weight of sour cherry stones
2. Materials and methods All the yields of activated carbon were expressed as the average
yields of three experiments by ±standard deviations.
2.1. Materials
2.3. Characterization of the activated carbons
Sour cherry stones were supplied by the ASYA Fruit Juice and
Food Ind. Inc. (Isparta, Turkey), and they were first air dried, then The contents of carbon, hydrogen, nitrogen and sulpur of the
crushed and finally sized, the fraction of particle sizes between 1 sour cherry stones and activated carbons were measured using a
and 2 mm was chosen for subsequent studies. Then, sour cherry LECO CHNS 932 Elemental Analyzer with ±0.4% accuracy (LECO
stones were contacted with dilute a 5 vol.% sulfuric acid (H2SO4) Instruments, USA). The oxygen contents were calculated by
solution for 24 h (i.e. H2SO4 is a drying agent that also contributes difference.
806 D. Angin / Fuel 115 (2014) 804–811

To determine the surface area and pore structure of activated 30

carbon samples, the nitrogen adsorption–desorption isotherms at 1:1
77 K were measured by an automated adsorption instrument, 25 2:1
Quantachrome, Autosorb-1C with ±0.15% accuracy. The surface 3:1
area, pore volume and pore size distribution were determined from
20 4:1
nitrogen adsorption data by using Quantachrome software. Adsorp-

tion data were obtained over the relative pressure, P/Po, range from
105 to 1. The sample was degassed at 300 °C under vacuum for 3 h.
The apparent surface area of nitrogen was calculated by using the
BET (Brunauer–Emmett–Teller) equation within the 0.01–0.2 rela-
tive pressure range. The micropore volume was determined accord-
ing to the DR (Dubinin–Radushkevich) method. The amount of N2
adsorbed at relative pressures near unity (0.99) corresponds to
the total amount adsorbed in both the micropores and the mesop-
ores; consequently the subtraction of the micropore volume from
the total amount will provide the volume of the mesopores. Pore
size distribution was obtained applying the DFT (Density Functional
Theory) method to the nitrogen adsorption isotherm by using the
software supplied by Autosorb-1C [10].
Surface functional groups were determined by Fourier transform
infrared spectra (FTIR) using SHIMADZU IR Prestige 21. Surface mor-
phologies were studied by scanning electron microscopy (SEM).
SEM images were performed using JEOL-JSM-6060LV Scanning
Electron Microscope.
2.4. Response surface methodology
Response surface methodology (RSM) is an empirical statistical
modeling technique employed for multiple regression analysis by
using quantitative data obtained from properly designed experi-
ments to solve multivariate equations simultaneously. Most appli-
cations of RSM include situations where several input variables
potentially influence some performance measure or quality char-
acteristic (i.e. response) of the system. The purpose of RSM is to
approximate the measures of performance, referred to as response
functions, in terms of the most critical factors (or independent
variables) that influence those responses. In doing this, a response
surface can then be mapped out showing how variations in the in-
put variables called as independent variables affect the responses
[16].
The behavior of the system using RSM is explained by empirical
first-order or second-order polynomial models as follows:
X
k X
k X
k1 X
k
Y ¼ B0 þ Bi X i þ Bii X 2i þ Bij X i X j ð2Þ
i¼1 i¼1 i¼1 j¼2
where Y is the predicted response, Xi, Xj are the real value of the
independent variable, B0 the constant coefficient, Bi the linear coef-
ficient, Bii the quadratic coefficient, Bij the interaction coefficient, k
is the number of factors [4].
Regression analyses were performed on the data obtained from
Yield (%)
15
10
5 Experimental
Predicted
0
450 500 550 600 650 700 750 800 850 900 950
Activation Temperature (°C)
Fig. 1. Effect of activation temperature and impregnation ratio on the yield of
activated carbons.
temperature, the yield of activated carbon decreased as the weight
loss rate is higher primarily due to initial large amount of volatiles
that can be easily released with higher temperature as well as the
loss of moisture to a lesser extent [17]. On the other hand, in each
activation temperature, activated carbon yields decreased with
increasing impregnation ratio. The behavior of the weight loss be-
tween 1:1 and 4:1 impregnation ratios is due to the larger evolution
of volatiles [10]. The zinc chloride impregnation ratio was more
effective on the yield of activated carbon at higher activation tem-
perature (800–900 °C). Ahmed and Theydan [5] and Mahapatra
et al. [18] obtained similar results for the activation of date stones
and food processing industrial sludge under operating conditions
similar to this work. The results showed that activation temperature
and impregnation ratio have a significant effect on the final yield of
activated carbon.
3.2. Ultimate analysis
The results of the elemental analysis of activated carbons ob-
tained at various activation temperatures and impregnation ratios
are shown in Table 2. As can be seen from Table 2, with an increasing
in activation temperature from 500 to 900 °C, the carbon content of
activated carbons increased from 72.21 to 83.36 wt.%; however, the
hydrogen content decreased from 2.52 to 1.45 wt.%, and oxygen
content also showed a similar trend, decreased from 23.58 to
Table 2
Elemental analyses of activated carbons produced at different activation tempera-
tures and impregnation ratios.

the experiments and the experimental data were fitted first-order wt.%
and second-order polynomial models. The studied parameters as Carbon Hydrogen Nitrogen Sulphur Oxygena
independent variables were the activation temperature (X1) and
ZnCl2 impregnation ratio: 3:1
impregnation ratio (X2) and the predicted responses as dependent Activation temperature (°C)
variables were the BET surface area (Y1) and yield (Y2) of activated 500 72.21 2.52 1.69 n.d. 23.58
carbon. Regression analyses were generated by Matlab 7.5. 600 76.47 2.40 1.49 n.d. 19.64
700 80.78 1.87 1.54 n.d. 15.81
800 81.53 1.65 1.38 n.d. 15.44
3. Results and discussion 900 83.36 1.45 1.37 n.d. 13.82
Activation temperature: 700 °C
3.1. Yield of activated carbon Impregnation ratio
1:1 67.16 2.04 1.49 n.d. 29.31
The product yield is an important measure of the feasibility of 2:1 74.39 1.93 1.56 n.d. 22.12
3:1 80.00 1.78 1.22 n.d. 17.00
preparing activated carbon from a given precursor. The effects of
4:1 81.86 1.65 1.38 n.d. 15.11
the activation temperature and impregnation ratio on the yields
a
of activated carbon are shown in Fig. 1. With increasing activation By difference, n.d.: not detection.
 D. Angin / Fuel 115 (2014) 804–811 807

13.82 wt.% for the impregnation ratio of 3:1. The effects of impreg-
nation ratios on the elemental composition of activated carbons
were similar for 700 °C activation temperature. The carbon contents
of activated carbons obtained at different activation conditions in-
creased when compared to sour cherry stones. This is due to the re-
lease of volatiles during carbonization that results in the
elimination of non-carbon species and enrichment of carbon [19].
This variation in the elemental analysis was found similar in acti-
vated carbons produced from other precursors such as waste tea,
nutshells and fiber textile waste [9,19,20].
3.3. Surface areas and pore size distributions
In the chemical activation, the final activation temperature and
impregnation ratio are important process parameters in determin-
ing the surface area and the pore volume of the activated carbon.
The effects of activation temperature and impregnation ratio on
the surface areas (BET, micropore and mesopore) and pore volumes
(total, micropore, and mesopore) of the activated carbons are shown
in Table 3. When the activation temperature increased from 500 to
700 °C, the Vtotal, Vmicro and SBET values increased significantly and
reached the maxima (1.566 cm3 g1, 0.984 cm3 g1 and
1704 m2 g1, respectively). However, at high temperatures of
800 °C and 900 °C, the trend was reversed. This phenomenon was
due to the release of volatile matters; but the continual decreases
in these properties with increasing temperature from 700 to
900 °C were probably due to the sintering effect of the volatiles
and the shrinkage of the carbon structure, resulting in the narrow-
ing and closing up to some of the pores [17]. It was also showed that
activated carbons prepared at activation temperature of 700 °C and
at impregnation ratio of 3:1 yielded the largest BET surface area and
micropore volume.
The effect of impregnation ratio on BET surface area and total
pore volume can also be seen in Table 3. In a previous study, it
was suggested that ZnCl2 is not only responsible for the develop-
ment of new micropores but also for the enlargement of as-exist-
ing micropores to mesopores [17]. At the same temperature, the
BET surface area as well as the total pore volume enlarged with
the increase in impregnation ratio. At increased impregnation ratio
from 1:1 to 3:1, a large amount of micropore was created, resulting
in the increase of BET surface area and micropore volume. When
impregnation ratio reached to 4:1, the trend was reversed. Effects
of chemical ratio on the pore structure of activated carbon ex-
plained as the first one is the micropore formation which starts
with the addition of chemicals to the raw materials and the second
one is the pore widening which is the result of chemical effect in-
side the opened pores. But, the destructive effect of high ZnCl2 ratio
on the micropore structure of active carbon can be observed in the
second region [21]. Pore size distribution of activated carbon was
calculated by using DFT method. The structures of the porous acti-
vated carbons are classified into three groups as micropore
(<2 nm), mesopore (2–50 nm) and macropore (>50 nm) according
to the International Union of Pure and Applied Chemistry (IUPAC).
The activated carbon produced from sour cherry stones in this
study contains both micropores and mesopores; nevertheless, the
micropore volume is larger than the mesopore volume. The aver-
age pore diameters of activated carbons varied between 1.81 and
2.29 nm, principally denoted micropores and mesoporous charac-
teristics (Table 3). The presence of mesopores in combination with
micropores is expected to play a significant role in the adsorption
of large molecules of adsorbates including dye molecules [22]. Sim-
ilar results were obtained for the activated carbons produced from
waste tea, cherry stones and olive bagasse [9,2,7]. Also, the effects
of activation process variables on the BET surface areas of the acti-
vated carbons are shown in Fig. 2.
The nitrogen adsorption–desorption isotherms and pore size
distributions for the activated carbons obtained at various activa-
tion temperatures and impregnation ratios are shown in Figs. 3
and 4, respectively. The plateau of the isotherms (Figs. 3a and 4a)
commences at high relative pressures (P/Po) and toward the end
of isotherm, steep gradient exist as a result of a limited uptake of
nitrogen, indicating capillary condensation in the mesopores.
These features indicated the development of micro and mesopor-
ous structure on the sour cherry stones during activation process,
further confirmed by the DFT (density functional theory) pore size
distributions. The pore size distributions delineate a model of solid
internal structure, which assumes that an equivalent set of non-
interacting and regularly shaped model pores can represent the
complex void spaces within the real solid. The pore size distribu-
tion is closely related to both kinetic and equilibrium properties
of porous material and perhaps is the most important aspect for
characterizing the structural heterogeneity of porous materials
employed in industrial application [17].
3.4. FTIR analysis
The adsorption capacity of activated carbon depends upon poros-
ity as well as the chemical reactivity of functional groups at surface.
Knowledge of surface functional groups would give insight to the

Table 3
1800
Surface areas and pore volumes of activated carbons produced at different activation 1:1
temperatures and impregnation ratios.
1700
2:1
SBET Smicro Smeso Vtotal Vmicro Vmeso Dp
BET Surface Area (m 2 g -1)

(m2/g) (m2/g) (m2/g) (cm3/g) (cm3/g) (cm3/g) (nm) 1600 3:1

ZnCl2 impregnation ratio: 3:1 1500 4:1

Activation temperature (°C)
500 1321 989 332 1.077 0.712 0.365 1.92 1400
600 1482 1008 474 1.207 0.880 0.327 1.81
700 1704 1184 520 1.566 0.984 0.582 2.29 1300
800 1522 1083 439 1.351 0.926 0.425 2.02
900 1387 1004 383 1.189 0.801 0.388 2.27 1200

Activation temperature: 700 °C 1100

Impregnation ratio
1:1 1382 1058 324 1.112 0.854 0.258 1.98 1000 Experimental
2:1 1652 1093 559 1.435 0.970 0.465 2.13 Predicted
3:1 1704 1184 520 1.566 0.984 0.582 2.29 900
4:1 1539 1076 463 1.342 0.935 0.407 2.22 450 500 550 600 650 700 750 800 850 900 950
Activation Temperatures (°C)
SBET: BET surface area, Smicro: micropore surface area, Smeso: mesopore surface area,
Vtotal: total pore volume, Vmicro: micropore volume, Vmeso: mesopore volume, Dp: Fig. 2. Effect of activation temperature and impregnation ratio on the BET surface
average diameter. area of activated carbons.
808 D. Angin / Fuel 115 (2014) 804–811

(a) 800
500 °C (a) 800

600 °C 700
700 700 °C
800 °C

Volume Adsorbed (cm 3g -1)

Volume Adsorbed (cm3g -1)

600
600 900 °C

500
500
400
400
300
300 1:1
200 2:1
200 3:1
100 4:1
100
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1 0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Relative Pressure (P/P0 )
Relative Pressure (P/P0)

(b) 0,08
500 °C
600 °C
(b) 0,09
0,07
700 °C 0,08

0,06 800 °C
900 °C 0,07
Dvd (cm3/A°/g)

0,05 0,06
Dvd (cm 3/A°/g)

0,04 0,05

0,03 0,04

0,03 1:1
0,02 2:1
0,02 3:1
0,01
0,01 4:1
0
0 10 20 30 40 50 60 70 80 0
0 10 20 30 40 50 60 70 80
Pore width (A0 )
Porewidth (A0)
Fig. 3. Nitrogen adsorption–desorption isotherms (a), and pore size distributions
(b) for prepared activated carbons with variable temperature (impregnation Fig. 4. Nitrogen adsorption–desorption isotherms (a) and pore size distributions (b)
ratio = 3:1). for prepared activated carbons with variable impregnation ratio
(temperature = 700 °C).

adsorptioncapabilityofthe producedactivatedcarbon.Fourier trans-
form infrared spectra (FTIR) were collected for the qualitative
characterization of surface functional groups of activated carbon by
chemical methods. FTIR analyses results of sour cherry stones and
activated carbons obtained at different activation temperatures and
impregnation ratios are given in Fig. 5. The peaks for samples were
determined particularly between 700 and 3000 cm1 wavenumber.
The FTIR analyses indicated that the functional groups of activated
carbons obtained at different conditions were similar and the aro-
matic and aliphatic groups were predominant. In Fig. 5a, while the
bands about 1985–2462 cm1 which were generally attributed to
symmetric or asymmetric stretching of aliphatic band in –CH, –CH2
or –CH3 were observed as much stronger at produced activated car-
bons, they were not seen in the FTIR spectrum of the sour cherry
stones. As the activation temperature increased, the contents of ali-
phatic structures increased. These functional groups were formed,
possibly due to the extraction of H element and OH groups from the
aromatic rings during the impregnation and heat treatment stages
as a result of the dehydration effect of ZnCl2. The bands about 1020–
1230 cm1 show the C–O–C stretching (alcohols, ethers or phenols)
and O–H deformation vibrations [23]. These bands decreased with
increasing temperature at activation process as compared to the
raw material. These results indicated that the carbonyl groups and
substitution in aromatic rings were affected by thermal effect [24].
Also, the FTIR analyses indicated that the surface functional groups
of activated carbons obtained at different impregnation ratios were
very similar and the aliphatic groups were predominant (Fig. 5b).
3.5. Scanning electron microscopy
Scanning electron microscopy (SEM) technique was used to
investigate the surface physical morphology of activated carbons.
Fig. 6 illustrates the SEM photographs of sour cherry stones and acti-
vated carbons produced at different activation temperatures. The
significant differences were observed between the surface topogra-
phies of sour cherry stones and activated carbons. SEM image of
sour cherry stones showed the absence of micropores, as supported
by the BET results. Depending on the activation temperatures, the
external surfaces of the activated carbons have the pores which
were at different sizes and different shapes. SEM images of activated
carbons were analyzed and the pore size was observed to grow with
increasing activation temperature from 500 to 700 °C. Due to this
well-developed pores, the activated carbons possessed high BET
surface area and adsorptive capacity. But, at higher activation tem-
peratures of 800 °C and 900 °C, the activated carbons had lower BET
surface areas owing to the shrinkage of carbons at post-softening
and swelling temperatures, resulting in narrowing or closing pores.
Besides, activated carbons exhibit an even, highly porous and well
pronounced array of porous structures, indicating good possibility
 D. Angin / Fuel 115 (2014) 804–811 809

(a) Aliphatics
(– CH, –CH 2 or –CH3)
(b) Aliphatics
(–CH, –CH2 or –CH3)
900 °C
Alcohols, Phenols, 4:1
Ethers, etc.
800 °C
1029.99
3:1
700 °C

Transmittance, (%)
Transmittance, (%)
2:1
600 °C

500 °C
1:1

Raw material 1020.34

2364.73
1992.47
1988.61
2854.65 2331.94

1734.01
1230.58

1029.99

4000 3000 2000 1500 1000 500 4000 3000 2000 1500 1000 500
Wavenumber, (cm ) -1
Wavenumber, (cm-1)

Fig. 5. FTIR spectra of sour cherry stones and activated carbons obtained at different activation temperatures (a), and impregnation ratio (b).

Sour cherry stones 500 °C

600 °C 700 °C

800 °C 900 °C

Fig. 6. Scanning electron microscopy of sour cherry stones and activated carbons obtained at different activation temperatures (impregnation ratio = 3:1).
810 D. Angin / Fuel 115 (2014) 804–811

Table 4
Experimental data for modeling.

Run Input data Output data

Activation temperature Impregnation BET surface Yield (%) Y2
(°C) X1 ratio X2 area (m2 g1) Y1
1 500 1:1 972.8 28.41 ± 0.45
2 500 2:1 1140 25.68 ± 0.63
3 500 3:1 1321 20.93 ± 0.12
4 500 4:1 1199 18.28 ± 0.38
5 600 1:1 1184 23.89 ± 0.16
6 600 2:1 1447 22.45 ± 0.51
7 600 3:1 1482 17.54 ± 0.43
8 600 4:1 1439 11.93 ± 0.57
9 700 1:1 1382 21.54 ± 0.20
10 700 2:1 1652 18.46 ± 0.55
11 700 3:1 1704 16.22 ± 0.22
12 700 4:1 1539 10.19 ± 0.29
13 800 1:1 1300 19.51 ± 0.57
14 800 2:1 1495 16.46 ± 0.44
15 800 3:1 1522 10.67 ± 0.45
16 800 4:1 1319 8.33 ± 0.39
17 900 1:1 1192 17.17 ± 0.55
18 900 2:1 1276 12.67 ± 0.19
19 900 3:1 1387 9.54 ± 0.29
20 900 4:1 1263 6.17 ± 0.27

Table 5
The fitted model equations for the BET surface area (Y1) and yield (Y2) of activated carbon.

Regression model Equation R2 RMSE

Linear Y1 = 1046.7 + 0.2636X1 + 51.812X2 0.1539 175.199
Y2 = 46.5455  0.0291X1  3.7536X2 0.9751 1.0193
Pure quadratic Y 1 ¼ 2921:2 þ 10:8646X 1 þ 460:862X 2  0:0076X 21  81:81X 22 0.8916 66.7651
Y 2 ¼ 57:0794  0:0643X 1  2:4536X 2 þ 2:5179X 21  0:26X 22 0.9818 0.9224
Interaction Y1 = 733.98 + 0.7104X1 + 176.916X2  0.1787X1X2 0.1798 177.806
Y2 = 46.4545  0.029X1  3.7172X2  5.2  105X1X2 0.9751 1.0507
Full quadratic Y 1 ¼ 3234 þ 11:3114X 1 þ 585:966X 2  0:1787X 1 X 2  0:0076X 21  81:81X 22 0.9175 60.293
Y 2 ¼ 56:9884  0:0642X 1  2:4172X 2  5:2  105 X 1 X 2 þ 2:5179  105 X 21  0:26X 22 0.9819 0.9547

for the dyes to be trapped and adsorbed [25]. It can be seen from the
SEM images that the external surface of the activated carbons were
full of cavities. It seems that the cavities on the surface of the car-
bons resulted from the evaporation of ZnCl2 during carbonization,
leaving the space previously occupied by the ZnCl2 [26]. Therefore,
the ZnCl2 is an effective activating agent to obtain activated carbon
having high-surface area.
respectively. These values indicated 91.75% and 98.19% of the total
variation, which could be explained by the model equation ob-
tained from full quadratic model for the BET surface area and the
yield, respectively. Furthermore, it was showed that the predicted
value for the yield of activated carbon (Y2) would be more accurate
and closer to its actual value, compared to BET surface area (Y1).

3.6. Development of regression model equations
In this section of the study, regression analyses were performed
on the data obtained from experiments (Table 4) and experimental
data were fitted first-order and second-order polynomial models.
The regression equations obtained for the BET surface area (Y1)
and yield (Y2) of activated carbons are presented in Table 5. In
addition, experimental and predicted values were compared in 1
for the yields and in 2 for the BET surface areas of activated
carbons.
The quality of the developed model was evaluated based on the
correlation coefficient value. As indicated in Table 5, the fits of the
regression models were evaluated by the determination of coeffi-
cients (R2) and Root Mean Squared Error (RMSE) and full quadratic
model which is a second order response model showed a good cor-
relation with the experimental data. The coefficient of determina-
tion of full quadratic model for the BET surface area and the yield of
activated carbons were determined as 0.9175 and 0.9819,
4. Conclusion
High surface area activated carbons were prepared from sour
cherry stones by chemical activation with zinc chloride. The exper-
imental results showed that activation temperature and impregna-
tion ratio were highly effective on the porosity, surface area and
pore volume of activated carbons. In addition, the experimental val-
ues obtained for the BET surface areas and carbon yields were found
to agree satisfactorily with the values predicted by the regression
models. The produced activated carbons had high carbon content
(67.16–83.36 wt.%) and contained predominantly aliphatic com-
pounds. BET surface area of activated carbon increased to
1704 m2 g1 as compared with raw material (41.54 m2 g1). Simi-
larly, it’s total pore volume raised from 0.0975 cm3 g1 to
1.566 cm3 g1. Depending on the activation temperature, the exter-
nal surfaces of the activated carbons had the pores which were dif-
ferent sizes and shapes. The production of activated carbons with
high surface area from sour cherry stones, a waste of fruit juice
industries, is indeed of importance from the view point of economic
 D. Angin / Fuel 115 (2014) 804–811
and environmental aspects. Also, activated carbon obtained at opti-
mum conditions (700 °C activation temperature and 3:1 impregna-
tion ratio) can be effectively used as adsorbents for various
environmental applications such as removing hazardous com-
pounds from industrial waste gases and wastewater.
Acknowledgement
I would like to present my gratitude to instructor Halil Ibrahim
Balkul for proofreading of the current manuscript on behalf of
‘‘post-eding office of Sakarya University for academic publica-
tions’’. The author would also like to thank Dr. Serpil Ozturk for
editing of manuscript and ASYA Fruit Juice and Food Ind. Inc.
(Isparta, Turkey) for providing sour cherry stones.
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