Bioresource Technology 98 (2007) 145–149

Preparation and characterization of activated carbon from palm shell

by chemical activation with K2CO3
Donni Adinata, Wan Mohd Ashri Wan Daud *, Mohd Kheireddine Aroua
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

Received 28 June 2005; received in revised form 30 October 2005; accepted 5 November 2005
Available online 27 December 2005

Abstract

Palm shell was used to prepare activated carbon using potassium carbonate (K2CO3) as activating agent. The influence of carboniza-
tion temperatures (600–1000 C) and impregnation ratios (0.5–2.0) of the prepared activated carbon on the pore development and yield
were investigated. Results showed that in all cases, increasing the carbonization temperature and impregnation ratio, the yield decreased,
while the adsorption of CO2 increased, progressively. Specific surface area of activated carbon was maximum about 1170 m2/g at 800 C
with activation duration of 2 h and at an impregnation ratio of 1.0.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Activated carbon; Palm shell; Chemical activation; Pore development

1. Introduction row micropore distribution. Although it is a frequently

Activated carbon is a well known as porous material,
with large specific surface area, which is useful in adsorp-
tion of both gases and solutes from aqueous solution.
Therefore, it has been widely used for separation of gases,
recovery of solvents, removal of organic pollutants from
drinking water and a catalyst support. As environmental
pollution is becoming a more serious problem, the need
for activated carbon is growing. It is a versatile adsorbent
because of its good adsorption properties. Various materi-
als are used to produce activated carbon and some of the
most commonly used are agriculture wastes such as coco-
nut shell (Kirubakaran et al., 1991), pistachio shell (Abe
et al., 1990), saw dust (Xiongzun et al., 1986), walnut shell
(Khan et al., 1985), tropical wood (Maniatis and Nurmala,
1992) and almond shell (Hayashi et al., 2000).
Chemical activation has been shown as a efficient
method to obtain carbons with high surface area and nar-
*
Corresponding author. Tel.: +60 379676897; fax: +60 379675371.
E-mail address: ashri@um.edu.my (W.M.A. Wan Daud).
used to prepare activated carbons, the general mechanism
of chemical activation is not well understood, and the
various interpretations found in literature underline the
process complexity. In general terms, chemical activation
by alkalis consists in solid–solid or solid–liquid reaction
involving the hydroxide reduction and carbon oxidation
to generate porosity. McKee (1983) studied the gasification
of graphite by alkali metal compounds and found that
K2CO3 was reduced by carbon in an inert atmosphere
(Hayashi et al., 2002b; Okada et al., 2003).
Other chemicals, which frequently used are ZnCl2,
H3PO4, ZnCl2, KOH and NaOH (Guo and Lua, 2003;
Lua and Yang, 2004; Raymundo-Pinero et al., 2005). How-
ever, alkali hydroxides such as KOH and NaOH are haz-
ardous, expensive and corrosive (Lillo-Rodenas et al.,
2004) and ZnCl2 is unfriendly the environment and create
waste disposal problem (Guo and Lua, 2002). Thus, a more
benign chemical is desired; K2CO3 is not a hazardous
chemical and not deleterious as it is frequently used for
food additives.
Palm shell (also known as endocarp) is a cheap and
abundant agricultural by-product in tropical countries like

0960-8524/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.11.006
146 D. Adinata et al. / Bioresource Technology 98 (2007) 145–149
Malaysia and Indonesia. Palm shell has been successfully
converted into a well-developed activated carbon by ther-
mal activation (physical activation) and chemical activa-
tion using with carbon dioxide (CO2) and H2PO3 (Guo
and Lua, 2000, 2002). However, activated carbon prepared
from palm shell using K2CO3 activation for carbonaceous
precursors has not been thoroughly investigated. The aim
of this work was to use K2CO3 as activating agent and
study the influences of carbonization temperatures and
impregnation ratios on pore development and yield.
2. Methods
2.1. Material and chemical reagent
Palm shell obtained from Malaysia oil palm shell
(MOPS) were dried, crushed and sieved to a particle size
fraction of 1–2 mm. Potassium carbonate (K2CO3) (purity
99.9%; Fisher Scientific) was dissolved in distilled water to
prepare a saturated solution.
2.2. Raw material analysis
An elemental analysis was carried out using a Perkin
Elmer CHNO/S Analyzer 2400. Lignin, cellulose and halo-
cellulose were determined using TAPPI method (T-13wd-
74, T-17wd-70 and T-9m-54, respectively).
2.3. Characterization of activated carbon
The characterization of activated carbon samples was
carried out using CO2 adsorption at 273 K using a
Micromeritics ASAP 2010 surface area analyzer. The sam-
ple was placed inside the tube and the glass bulb was
inserted inside the tube and stopper. The bulb was inserted
by slanting the sample tube almost to a horizontal position
and the bulb was allowed to gradually down the sample
tube. Before the experiment began, the adsorbents were
degassed (104 mmHg) at 393 K. The surface areas of the
samples were measured based on Brunauer–Emmet–Teller
(BET) method and Dubinin–Radushkevich (DR) method
was applied to calculate the micropore volume. Pore size
distribution (PSD) was obtained from Horvath–Kawazoe
(HK) analysis and solid density of activated carbon was
measured by helium displacement with an ultrapycnometer
(AccuPyc 1330 pycnometer).
2.4. Preparation of activated carbon
Palm shells were mixed with saturated solution K2CO3
and kneaded. This mixture was then dried in an oven at
110 C for 24 h to prepare the impregnated sample. In this
work, 0.5, 0.75, 1.0, 1.5 and 2.0 impregnation ratios were
used. The impregnation ratio is given by
ðweight of K2 CO3 in solutionÞ
impregnation ratio ¼
ðweight of palm shellÞ
A typical carbonization run began by changing 100 g of
impregnated sample in the reactor and heated up to the
carbonization temperature in flowing stream of nitrogen
(15 l/min) (Wan Daud and Wan Ali, 2004). The tempera-
ture of reactor was increased at the rate of 10 C/min, until
it reached the final carbonization temperature. The carbon-
ization temperature was varied from 600 to 1000 C with
activation duration of 2 h. After carbonization, the sample
was cooled down under nitrogen (N2) flow and was washed
sequentially several times with hot water, and finally with
cold distilled water to remove residual chemicals. Then
the sample was dried at 110 C.
3. Results and discussion
3.1. Yield of activated carbon and chemical recovery
ratio of K2CO3
The proximate analyses of palm shell were as follows
(dry wt basis %): carbon 18.7, moisture 7.96, ash 1.1, vol-
atile 72.47, C 50.01, H 6.9, N 1.9, S 0, O 41, cellulose 29,
halocellulose 47.7 and lignin 53.4 more than 100%. The
yield of activated carbon decreased as the activation
temperature increased (Table 1). When chemical activation
with K2CO3 impregnation was used, increasing the carbon-
ization temperature decreased the yield progressively due
to be release of volatile products as a result of intensifying
dehydration and elimination reaction; it also indicated that
char of the palm shell was gasified by K2CO3. McKee
(1983) studied the gasification of graphite by alkali metal
and found that K2CO3 was reduced in an inert atmosphere
by carbon (Hayashi et al., 2002b; Okada et al., 2003).
The presence of K2CO3 in the interior of the precursor
restricted the formation of tar as well as other liquids such
as acetic acid and methanol by formation of cross-links, and
inhibited the shrinkage of the precursor particle by occupy-
ing certain substantial volumes (Guo and Lua, 2003). The
results showed that the chemical recovery ratio of K2CO3
with selected conditions above was 0.99, 0.96, 0.86, 0.65
and 0.25 for carbonization temperature of 600, 700, 800,
900 and 1000 C, respectively. This results supported previ-
ous findings that K2CO3 was reduced by carbon in inert
atmospheres, whereby char reacted with K2CO3 and then
the later was removed during gasification. Above 800 C,
carbon reduced the impregnated K2CO3 and was consumed
through the formation of CO. Thus, the specific surface
area and the pore volume increased (Hayashi et al., 2002b).
As shown in Table 1, the yield was strongly affected by
the impregnation ratio. Increasing the impregnation ratio
decreased yield and increased ‘‘burn-off’’ of palm shell
(Gomez-Serrano et al., 2005). Higher K2CO3 concentra-
tions consistently yielded products with a much larger
external surface area, as well as large micropore volumes
(Evans et al., 1999). The chemical recovery ratio of
K2CO3 was 0.15, 0.37, 0.86, 0.89, and 0.98 for the impreg-
nation ratio of 0.5, 0.75, 1.0, 1.5, and 2.0, respectively,
which showed high chemical recovery ratio of products
 D. Adinata et al. / Bioresource Technology 98 (2007) 145–149 147

Table 1
The pore characteristics and properties of activated carbons prepared from palm shell at different carbonization temperature and impregnation ratio
Activation conditionsa Yield (%) Variation (%) Solid density (g/cm3) Variation (%) BET (m2/g) Variation (%)
600–2–1 26.34 1.6 1.7659 0.4 319 1.3
700–2–1 22.24 1.4 2.0872 0.5 425 0.9
800–2–1 18.86 1.1 2.3567 0.1 1170 1.4
900–2–1 16.79 1.0 2.5341 1.6 544 1.9
1000–2–1 12.82 1.9 2.7341 1.1 339 1.0
800–2–0.5 27.84 2.2 2.7159 1.0 248 2.0
800–2–0.75 25.24 0.7 2.4561 1.2 476 1.3
800–2–1.5 14.79 1.8 1.9322 1.1 540 0.8
800–2–2.0 11.85 0.6 1.7113 0.5 332 1.1
a
Note: a–b–c denote carbonization temperature (C)–during activation (h)–impregnation ratio of K2CO3.

subjected to high impregnation ratio. Hot water washing
was, thus, very effective in reducing K2CO3, which has been
found to be related to formation of atomic K. Thus, atomic
K may intercalate and expand the inter layers of adjacent
hexagonal network planes consisting of C atoms, enhanc-
ing pore formation though hexagonal planes that are not
well developed as in graphite. K2CO3 was not detected
on the surface, indicating that the washing of this sample
was effective to remove K from the surface on the products
(Okada et al., 2003).
3.2. Pore development and characteristic of
activated carbon
The results showed that the specific surface areas
increased with the increase in carbonization temperature
from 600 to 800 C and decreased slightly at 800–
1000 C. The maximum specific area obtained was
1170 m2/g. Therefore, it was deduced that K2CO3 was
effective as activation reagent below 800 C. This progres-
sive carbonization temperature increased the C–K2CO3
reaction rate, resulting in increasing carbon ‘‘burn-off’’.
Concurrently, the volatiles from the samples continued
to evolve with increasing carbonization temperature. The
develotilization process further developed the rudimentary
pore structure in the char, whereas the C–K2CO3 reaction
enhanced the existing pores and created new porosities
(Hayashi et al., 2002a).
The surface area of activated carbon increases with
increasing impregnation ratio from 0.5 to 1.0 and
decreased slightly for ratios larger than 1. However, mes-
oporous surface area increased continually. The micropore
surface areas were obtained by subtracting mesopore
surface area from the corresponding BET surface area.
Under the same condition when the impregnation ratio
was 0.5, 0.75, 1.0, 1.5, and 2.0, the corresponding specific
surface area of activated carbon was 248, 476, 1170, 540,
and 332 m2/g, respectively. There was a pronounced
decrease in micropore surface area when the ratio was
higher than 1 due to enlargement of micropores to meso-
pores. These results suggested that to obtain the optimal
value of surface area, the impregnation ratio should be
around 1.0.
Adsorption capacity of activated carbon largely depends
on the amount of micropores that are present in the acti-
vated carbon. Hence, its measurement can be directly
related to quantity of micropore volume in the sample.
The micropore volume was estimated from the adsorption
of carbon dioxide at 273 K. The results showed that micro-
pore volume of activated carbon prepared with selected
conditions above was 0.23, 0.50, 0.57, 0.48, and 0.15 cm3/
g for the carbonization temperature of 600, 700, 800, 900,
and 1000 C with activation duration of 2 h at an impreg-
nation ratio of 1.0, respectively. The micropore volume
increased with carbonization temperature from 600 to
800 C and then between 800 and 1000 C, the micropore
volume of activated carbon slightly decreased, because of
enlargement surface of the micropores to mesopores. When
impregnation ratio was 0.5, 0.75, 1.0, 1.5, and 2.0, micro-
pore volume of activated carbon was 0.13, 0.28, 0.57,
0.43, and 0.21 cm3/g, respectively. It showed that increas-
ing the impregnation ratio from 0.5 to 1.0 progressively
increased both the micropore volume. There was a pro-
nounced decreased in micropore volume when the ratio
was higher than 1.0 because rapid increase in mesopore
volume increased and the total pore volume (micropore
volume and mesopore volume) increased with increasing
impregnation ratio.
The results obtained showed that increasing the impreg-
nation ratio decreased the density of activated carbon
(Table 1). Higher impregnation ratio also tends to produce
lower yield and density of activated carbon. When higher
impregnation ratio was used, the weight losses were due
to the increasing release of volatile products as result of
intensifying dehydration and elimination reactions (Evans
et al., 1999). By increasing the carbonization temperature
the solid density increased progressively due to the release
of low-molecular weight products (water, furan derivates
and laevoglucose) due to of dehydration and elimination
reactions (Guo and Lua, 2002; Lua and Yang, 2004).
3.3. CO2 adsorption isotherm and pore size distribution of
activated carbon
Figs. 1 and 2 show the CO2 adsorption isotherms on
the prepared activated carbons at different carbonization
148 D. Adinata et al. / Bioresource Technology 98 (2007) 145–149

180 12
Volume Adsorbed (cm3/g) STP

Average variation of each line is < 0.2% Average variation of each line is < 0.2%
160
140 10

Pore Volume (cm3/g-nm)

120
100 8
80
60 6
40
20 4
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
2
Relative Pressure (P/P0)

Fig. 1. CO2 adsorption isotherm on the prepared activated carbon at 0

0.4 0.5 0.6 0.7 0.8 0.9 1
different carbonization temperatures: (m) 600 C, (j) 700 C, (d) 800 C,
Pore Diameter (nm)
(·) 900 C, (s) 1000 C.
Fig. 3. The influence of carbonization temperatures on the pore size
distribution of activated carbon: (·) 600 C (h) 700 C (d) 800 C, (D)
120 900 C, (s) 1000 C.
Average variation of each line is < 0.2%
Volume Adsorbed (cm3/g) STP

100

80 12 Average variation of each line is < 0.2%

PoreVolume (cm3/g-nm) 10
60
8
40
6

20 4

0 2
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Relative Pressure (P/P0) 0
0.4 0.5 0.6 0.7 0.8 0.9 1
Fig. 2. Adsorption isotherm of CO2 on the prepared activated carbons at Pore Diameter (nm)
different impregnation ratios: (j) 0.5, (m) 0.75, (d) 1, (+) 1.5, (s) 2. Fig. 4. The influence of impregnation ratios on the pore size distribution
of activated carbon: (s) 0.5, (·) 0.75, (d) 1, (j) 1.5, (D) 2.

temperatures and impregnation ratios. The amount of CO2

adsorbed at P/P0 = 0.03 increased for activated carbons increased the total pore volume of activated carbon (Isma-
prepared at relatively higher carbonization temperature dji and Bhatia, 2000, 2001).
and impregnation ratio. The isotherm curves are of Type
I isotherms, which generally exhibit the presence of micro- 4. Conclusions
pores. Further increase in carbonization temperature and
impregnation ratio through activation process widened The activated carbon prepared by chemical activation
the pores as well as increased the volume of micro pore with K2CO3 attained a maximum value of 1170 m2/g at a
and total of pore volume. carbonization temperature of 800 C with activation
The structural heterogeneity of porous material is gener- duration of 2 h and at an impregnation ratio of 1.0. The
ally characterized in term of the pore size distribution. The increase in the carbonization temperature and impregna-
pore size distribution is closely related to both kinetic and tion ratio decreased yield and increased the product
equilibrium properties of porous materials used in indus- adsorption capacity of CO2. From the results of yield of
trial application. The pore size distribution of activated activated carbon and reagent recovery ratio, it was con-
carbon produced from palm shell at different carbonization cluded that the carbon involved in the palm shell char
temperatures and impregnation ratios are given in Figs. 3 was removed as CO by reduction of K2CO3 above
and 4. From these figures, it was obvious that the carbon- 800 C. It was also found that for 2 h activation, the
ization temperature and impregnation ratio had significant mesopore volume increased with the increase in impregna-
effect on the pore structure of activated carbon produced. tion ratio and carbonization temperature.
At low temperature and impregnation ratio, the pore struc-
ture of mainly consisted of micropore; however, with the Acknowledgement
increase of carbonization temperature and impregnation
ratio, the creation of micropore structure and widening Financial support for this work was provided by IRPA
of micropores to mesopores also increased and also Grant (08-02-03-0233-EA233), University Malaya.
 D. Adinata et al. / Bioresource Technology 98 (2007) 145–149
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