High surface area activated carbon prepared from cassava peel

by chemical activation
Y. Sudaryanto, S.B. Hartono, W. Irawaty, H. Hindarso, S. Ismadji
*
Department of Chemical Engineering, Widya Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia
Received 15 January 2004; received in revised form 29 March 2005; accepted 4 April 2005
Available online 15 June 2005
Abstract
Cassava is one of the most important commodities in Indonesia, an agricultural country. Cassava is one of the primary foods in
our country and usually used for traditional food, cake, etc. Cassava peel is an agricultural waste from the food and starch process-
ing industries. In this study, this solid waste was used as the precursor for activated carbon preparation. The preparation process
consisted of potassium hydroxide impregnation at dierent impregnation ratio followed by carbonization at 450750 C for 13 h.
The results revealed that activation time gives no signicant eect on the pore structure of activated carbon produced, however, the
pore characteristic of carbon changes signicantly with impregnation ratio and carbonization temperature. The maximum surface
area and pore volume were obtained at impregnation ratio 5:2 and carbonization temperature 750 C.
2005 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Pore structure; Cassava peel; Activation
1. Introduction
Activated carbons are materials having complex por-
ous structures with associated energetic as well chemical
inhomogeneities. Their structural heterogeneity is a re-
sult of existence of micropores, mesopores and macro-
pores of dierent sizes and shapes. Activated carbon is
one of the most important adsorbents from an industrial
view of point. The main application of this adsorbent is
for separation and purication of gaseous and liquid
phase mixtures (Ismadji and Bhatia, 2001).
A challenge in activated carbon production is to pro-
duce very specic carbons with a given pore size distri-
bution from low cost materials at low temperature.
Activated carbons with high specic surface area and
pore volumes can be prepared from a variety of carbo-
naceous materials such as coal (Hsu and Teng, 2000;
Ganan et al., 2004; Qiang et al., 2005), coconut shell
(Qiao et al., 2002; Sekar et al., 2004), wood (Tancredi
et al., 2004; Diaz-Diez et al., 2004), agricultural wastes
(Guo et al., 2004; Youssef et al., 2005; Zhang et al.,
2004), or industrial wastes (Hayashi et al., 2005; Ko
et al., 2004). In industrial practice, coal and coconut
shell are two main sources for the production of
activated carbons.
There are two processes for preparation of activated
carbon: chemical activation and physical activation.
Chemical activation is known as a single step method
of preparation of activated carbon in the presence of
chemical agents. Physical activation involves carboniza-
tion of a carbonaceous materials followed by activation
of the resulting char in the presence of activating agents
such as CO
2
or steam. The chemical activation usually
takes place at a temperature lower than that used in
physical activation, therefore it can improve the pore
development in the carbon structure because the eect
0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.04.029
*
Corresponding author. Tel.: +62 31 3891264; fax: +62 31 3891267.
E-mail address: suryadi@mail.wima.ac.id (S. Ismadji).
Bioresource Technology 97 (2006) 734739
of chemicals. The carbon yields of chemical activation
are higher than physical one (Ahmadpour and Do,
1997).
Cassava is one of the most important commodities in
Indonesia, an agricultural country. Cassava is one of the
primary foods in our country and usually used for tradi-
tional food, cake, etc. The cassava production in Indo-
nesia is very huge and only small amounts are utilized
by traditional food industries, and the rest are used as
the raw material for cassava starch industries. Cassava
starch making operation produces a large amount of
solid wastes (cassava peel), and direct discharge of this
solid wastes will cause the environmental problems.
Although there are many studies in the literature relat-
ing to the preparation and characterization of activated
carbon from agricultural wastes as mentioned before,
there is no information for the preparation of the acti-
vated carbon using Indonesian cassava peel as the precur-
sor with KOHas chemical activating agent. In the present
study, we obtained cassava peel from cassava starch
industry located near Surabaya. The main objective in
this work is to study the eect of dierent preparation
variables on the pore characteristic of activated products.
2. Experimental
2.1. Materials
The proximate and ultimate analysis of the cassava
peel used in this study, are given in Table 1. The con-
tents of C, H, N, O and S elements in the ultimate anal-
ysis were determined by an elemental analyzer (Heraeus,
CHN-O-RAPID). The analytical results shown in Table
1 reveal that cassava peel has high carbon and low ash
content indicating that this precursor is suitable for
the preparation of activated carbon. Prior to the use,
the cassava peel was repeatedly washed with distilled
water in order to remove dust and other inorganic impu-
rities, then oven-dried for 24 h at 120 C to reduce the
moisture content.
2.2. Activated carbon preparation
Chemical activation of cassava peel was performed
using KOH. Dierent carbonization time, temperatures,
and impregnation ratios were studied in order to estab-
lish the optimal conditions for producing high surface
area activated carbons from cassava peel. Chemical acti-
vation was performed with method as follow: 10 g of
dried cassava peel was mixed with KOH solution with
dierent impregnation ratio for about 3 h at 50 C.
The concentration of KOH solution was adjusted to
give a mass ratio of chemical activating agent to cassava
peel range from 1:2 to 5:2 (mass basis). The resulting
homogeneous slurry was dried at 110 C for at least
24 h. The resulting sample was place in horizontal tubu-
lar furnace and then carbonized at desired temperatures
(450 C, 550 C, 650 C, and 750 C). The carbonization
and activation was performed under nitrogen ow of
150 cm
3
/min. The carbonization and activation process
was initiated by heating the sample at heating rate of
10 C/min from room temperature (around 30 C) until
the desired temperature was reached. Samples were
held at desired temperature for dierent carbonization
times of 1, 2, or 3 h before cooling down under nitrogen
ow. The activated carbon products were washed
sequentially with a 0.5 N HCl solution. Subsequently,
the samples were repeatedly washed with hot dis-
tilled water until the pH of solution reach 6.5 and
nally washed with cold distilled water. After that, the
samples were dried at 110 C for 24 h and stored in
desiccator.
2.3. Pore structure characterization
The pore structure characteristics of the resulting
carbons were determined by nitrogen adsorption at
196 C using an automatic Micromeritics ASAP-2010
volumetric sorption analyzer. Prior to gas adsorption
measurements, the carbon was degassed at 300 C in a
vacuum condition for a period of at least 24 h. Nitrogen
adsorption isotherms were measured over a relative
pressure (P/P
0
) range from approximately 10
5
to 0.995.
The BET surface area, micropore volume and micropore
surface area of the activated carbons were determined
by application of the BrunauerEmmettTeller (BET)
and DubininAsthakov (DA) analysis software avail-
able with the instrument, respectively. The BET surface
area was determined by means of the standard BET
equation applied in the relative pressure range from
0.06 to 0.3. The pore size distribution of carbons were
determined from argon adsorption isotherm data using
the Micromeritics density functional theory (DFT) soft-
ware, with medium regularization. The argon adsorp-
tion experiments were carried out at 186 C using an
automatic Micromeritics ASAP-2010 volumetric sorp-
tion analyzer. Here, the argon adsorption with DFT
Table 1
Proximate and ultimate analysis of cassava peel
Analysis wt% Variation (%)
Proximate
Moisture 11.4 1.2
Volatile matter 59.4 0.8
Fixed carbon 28.9 0.9
Ash 0.3 1.0
Ultimate
Carbon 59.31 1.1
Nitrogen 2.06 1.1
Hydrogen 9.78 1.1
Oxygen 28.74 1.1
Sulphur 0.11 1.1
Y. Sudaryanto et al. / Bioresource Technology 97 (2006) 734739 735
analysis of the data is used to provide independent pore
size distribution. We used the argon adsorption data
instead of the nitrogen isotherm because when this
method (DFT) applied to nitrogen isotherm suer from
the drawback that interactions of surface chemical
heterogeneities with quadrupolar nitrogen can aect
the pore size distribution determined.
3. Results and discussion
A series of activated carbons were prepared from cas-
sava peel as precursor with chemical activation using
KOH as activating agent. The eects of dierent prepa-
ration variables on the pore characteristic and surface
chemistry (surface acidity) of activated products were
also studied. Details are discussed as follow.
3.1. Yield of activated carbon
Carbonization temperature plays an important role
on the yield of activated carbon. Fig. 1 depicts the eect
of carbonization temperature on the yield of activated
carbon at dierent carbonization time (impregnation
ratio 1:1). As seen in the gure, carbonization time does
not have much eect on the yield of activated carbon
while the carbonization temperature has signicant ef-
fect. At carbonization temperature range 450550 C,
the rate of weight loss is high primarily due to the initial
large amount of volatiles that can be easily released with
increasing temperature as well as the loss of moisture to
a lesser extent. The yield of the activated carbon at car-
bonization temperatures more than 650 C are less than
xed carbon in initial precursor (see Table 1). Since the
potassium hydroxide is a strong base, it catalyzes the
oxidation reactions.
3.2. Eect of carbonization time on the pore
characteristic
As mentioned before that the carbonization time has
no signicant eect on the yield of activated carbon.
Table 2 summarizes the eect of carbonization time on
the pore characteristic of chemically activated carbons
under conditions of carbonization temperature 650 C
and impregnation ratio 1:1. This table clearly shows that
carbonization time does not have much eect on the
pore characteristic of activated carbon products. In gen-
eral, the BET surface area and total pore volume, V
T
, re-
main constant.
3.3. Eect of temperature on the pore structure
Since the carbonization time does not have any signif-
icant eect on the activated carbon properties, we dis-
cuss the eect of temperature on the pore structure
and surface chemistry only at carbonization time 1 h.
Pore evolution of the activated carbon with varying car-
bonization temperature is shown in Fig. 2. Details of
pore characteristics of activated carbon at dierent car-
bonization temperatures are given in Table 3. Fig. 3
shows the nitrogen adsorption isotherms at 196 C of
activated carbons derived from cassava peel.
Temperature, C
o
400 450 500 550 600 650 700 750 800
Y
i
e
l
d
,

%
20
25
30
35
40
Carbonization time = 1 h
Carbonization time = 2 h
Carbonization time = 3 h
Fig. 1. Eect of carbonization temperature on the yield of activated
carbon (impregnation ratio 1:1).
Table 2
Eect of carbonization time on the pore characteristic of chemically
activated carbons under conditions of: carbonization temperature
650 C, impregnation ratio 1:1
Carbonization
time (h)
Pore characteristic
BET
(m
2
/g)
Variation
(%)
V
T
(cm
3
/g)
Variation
(%)
1.0 1154 0.6 0.519 0.6
2.0 1108 0.9 0.517 0.9
3.0 1183 0.5 0.520 0.5
Carbonization temperature, C
o
400 450 500 550 600 650 700 750 800
P
o
r
e

v
o
l
u
m
e
,

c
m
3
/
g
0.35
0.40
0.45
0.50
0.55
0.60
Micropore volume
Total pore volume
Fig. 2. Pore evolution during carbonization.
736 Y. Sudaryanto et al. / Bioresource Technology 97 (2006) 734739
The eect of carbonization temperature in the pore
development is very signicant as seen in Fig. 2. Increas-
ing the carbonization temperature from 450 C to
750 C increases the evolution of volatile matters from
the precursor, leading to increase of the pore develop-
ment, and creates new pores. At temperature higher
than 400 C, the reaction between potassium hydroxide
and carbon occurs (Ganan et al., 2004) according the
following reaction
6KOH+C$2K+3H
2
+2K
2
CO
3
1
The presence of metallic potassium will intercalate to
the carbon matrix. This phenomenon results in widening
of the spaces between carbon atomic layers and increas-
ing the total pore volume, V
T
(Ahmadpour and Do,
1997). However, the micropore volume, V
P
, increase
until the carbonization temperature reach 650 C and
at higher temperature, the micropore volume decreases.
At temperature higher than 650 C, the surface metal
complex is responsible for further carbon gasication,
leading to widening of micropore to mesopore (Ganan
et al., 2004).
The adsorption isotherm of activated carbons pro-
duced from cassava peel at carbonization temperature
450650 C belong to a mixture of Type I and Type
IV isotherms (see Fig. 3). According to IUPAC classi-
cation, the Type I isotherm is associated with micropo-
rous structures and Type IV isotherm indicates mixture
of microporous and mesoporous material. The plateau
of this isotherm commences at high relative pressures
(P/P
0
) and toward the end of isotherm, steep gradient
is seen as the result of a limited uptake of nitrogen, indi-
cating capillary condensation in the mesopores. This
characteristic indicates the development of micro and
mesoporous structure on this char during carbonization
process. The adsorption isotherm of carbon as seen in
Fig. 3 clearly shows the largely microporous nature of
the activated carbon produced from cassava peel at car-
bonization temperature 450650 C, with some meso-
pores leading to gradual increase in adsorption after
the initial lling of the micropores, followed by more
rapid increase near saturation. At carbonization temper-
ature 750 C, the activated carbon has more mesoporous
structures as indicated by adsorption isotherm of nitro-
gen at 196 C. At 750 C the development of meso-
pores are more pronounced and thermal degradation
of the pore wall occurs causing the widening of
micropores.
The structural heterogeneity of porous material is
generally characterized in terms of the pore size distribu-
tion (Ismadji and Bhatia, 2001). This pore size distribu-
tion represent 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 heter-
ogeneity of porous materials used in industrial applica-
tion. As mentioned before, here, the argon adsorption
with DFT analysis of the data is used to provide inde-
pendent pore size distribution. We used the argon
adsorption data instead of the nitrogen isotherm be-
cause when this method (DFT) applied to nitrogen
isotherm suer from the drawback that interactions of
surface chemical heterogeneities with quadrupolar nitro-
gen can aect the pore size distribution determined. The
pore size distributions of activated carbon derived from
cassava peel at various carbonization temperatures are
shown in Fig. 4. These gures conrm that the activated
carbons produced at carbonization temperatures 450
650 C contain micro and mesoporous structure while
at 750 C has signicant mesoporous nature.
3.4. Eect of chemical ratio
The impregnation ratio has been found to be one of
the important parameter in preparation of activated car-
bon using chemical activation (Ahmadpour and Do,
1997). In order to study the eect of impregnation ratio
on the pore characteristic of the activated carbons, here
Table 3
Pore characteristics of activated carbon at dierent carbonization
temperatures (impregnation ratio 1:1)
Carbonization
temperature
(C)
Pore structure
BET
(m
2
/g)
V
P
(cm
3
/g)
V
T
(cm
3
/g)
Micropore
surface
area (m
2
/g)
Variation
(%)
450 972 0.383 0.421 857 0.3
550 1074 0.394 0.435 908 0.2
650 1154 0.462 0.519 938 0.6
750 1378 0.393 0.583 881 0.5
Relative pressure, p/p
o
0.0 0.2 0.4 0.6 0.8 1.0
V
o
l
u
m
e

a
d
s
o
r
b
e
d
,

c
m
3
/
g

S
T
P
0
100
200
300
400
500
600
Carbonization temperature 450 C
Carbonization temperature 550 C
Carbonization temperature 650 C
Carbonization temperature 750 C
Fig. 3. Nitrogen adsorption isotherm on activated carbons prepared
from cassava peel.
Y. Sudaryanto et al. / Bioresource Technology 97 (2006) 734739 737
we used carbonization time 1 h and carbonization tem-
perature 750 C. The pore characteristic of activated
carbons produced at various impregnation ratios are
given in Table 4. The yield of activated carbon decrease
with increase of impregnation ratio as seen in Fig. 5.
Potassium hydroxide promotes the oxidation process,
with high KOH ratio the gasication of surface carbon
atoms is the predominant reaction leading to increase
in the weight loss of carbon.
Table 4 indicates that the BET surface area and pore
volume (both total and micropore volumes) are both
increasing continuously with impregnation ratio. The
pores were created due to the evolution of gaseous car-
bonization products and catalytic oxidation of carbon
surface by potassium metallic salt. The catalytic oxida-
tion causes the widening of some micropores to meso-
pores as mentioned before. From Table 4, it also can
be noted that the micropore volume of the activated
carbon products are also increase with increasing
impregnation ratio. At high ratio of KOH, the micro-
porosity development is mostly due to the intercalation
of potassium metal in the carbon structure.
The pore size distribution of activated carbons pro-
duced from cassava peel at various impregnation ratios
at carbonization temperature 750 C are given in Fig. 6.
These pore size distributions are determined using DFT
software package with medium regularization. From
this gure, it is obvious that the impregnation ratio gives
Pore size,
3 6 20 30 60 200 300 600 10 100
P
o
r
e

s
i
z
e

d
i
s
t
r
i
b
u
t
i
o
n
,

c
m
3
/
g
.

0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
Carbonization temperature, 450
o
C
Carbonization temperature, 550
o
C
Carbonization temperature, 650
o
C
Carbonization temperature, 750
o
C
Fig. 4. Pore size distribution of activated carbons prepared from
cassava peel.
Table 4
Pore characteristics of activated carbon at dierent impregnation ratio
(carbonization temperature 750 C)
Impregnation
ratio
Pore structure
BET
(m
2
/g)
V
P
(cm
3
/g)
V
T
(cm
3
/g)
Micropore
surface
area (m
2
/g)
Variation
(%)
1:2 1027 0.390 0.434 850 0.8
1:1 1378 0.393 0.583 881 0.5
3:2 1491 0.432 0.612 1023 0.7
2:1 1562 0.487 0.668 1074 0.5
5:2 1605 0.513 0.691 1100 0.3
Impregnation ratio
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Y
i
e
l
d
,

%
20
22
24
26
28
30
Fig. 5. Eect of impregnation ratio on the yield of activated carbon.
Relative pressure, p/p
o
0.0 0.2 0.4 0.6 0.8 1.0
V
o
l
u
m
e

a
d
s
o
r
b
e
d
,

c
m
3
/
g

S
T
P

0
200
400
600
800
1000
Impregnation ratio 1:2
Impregnation ratio 1:1
Impregnation ratio 3:2
Impregnation ratio 4:2
Impregnation ratio 5:2
Fig. 7. Nitrogen adsorption isotherm on activated carbons prepared
from cassava peel under dierent impregnation ratio.
Pore size,
5 20 50 200 500 2000 10 100 1000
p
o
r
e

s
i
z
e

d
i
s
t
r
i
b
u
t
i
o
n
,

c
m
3
/
g
.

0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
Impregnation ratio 1:2
Impregnation ratio 1:1
Impregnation ratio 3:2
Impregnation ratio 2:1
Impregnation ratio 5:2
Fig. 6. Eect of impregnation ratio on the pore size distribution of
activated carbon.
738 Y. Sudaryanto et al. / Bioresource Technology 97 (2006) 734739
signicant eect on the pore structure of activated
carbon produced. At low impregnation ratio (50%),
the pore structure of activated carbon produced mainly
consists of micropore, however with the increase of
impregnation ratio, the creation of micropore structure
and widening of micropores to mesopores also increase.
The adsorption isotherms of activated carbons produced
under dierent impregnation ratio are shown in Fig. 7.
Here, as mentioned before, potassium metallic acts as
the catalyst for oxidation reaction, therefore more
carbon atom in surface is oxidized leading to widening
of the pore structures.
4. Conclusion
High surface area activated carbons were prepared
from Indonesian cassava peel with chemical activation.
As the activating agent, potassium hydroxide was used.
From this study it was found that cassava peel is a good
precursor for activated carbon preparation. Carboniza-
tion temperature and impregnation ratio give signicant
eect in the pore characteristic of activated carbons
produced.
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