b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

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The comparison of two activation techniques to prepare

activated carbon from corn cob
Min Song*, Baosheng Jin, Rui Xiao, Li Yang, Yimin Wu, Zhaoping Zhong, Yaji Huang
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University,
Sipailou 2, Nanjing 210096, China

article info

abstract

Article history:

We report on the preparation of biomass-based activated carbons by the steam physical

Received 12 August 2011

activation and KOH chemical activation methods. In addition, we also investigate their

Received in revised form

adsorption performance. By adjusting the reaction parameters, different carbon materials

23 October 2012

are prepared from corn residues and characterized using instrumental analyses such as

Accepted 20 November 2012

scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared

Available online

(FTIR), and BrunauereEmmetteTeller (BET). It is found that the synthesized activated

carbons exhibit high surface area (1600 m2 g
1) and large pore volume (2.01 cm3 g
1).

Keywords:

Furthermore, the high methylene blue and iodine adsorption value and a considerable CO2

Biomass

uptake (exceeding 1.5 mmol g
1) are attained with the activated carbons, showing their

Activated carbon

potential usage for the CO2 adsorbent.

2012 Elsevier Ltd. All rights reserved.

Porous materials
Activation
CO2 adsorption

1.

Introduction

Carbon dioxide removal is environmentally significant for

minimization of its effect on global warming [1,2]. Among the
diverse technologies for such separation purposes, physical
adsorption by microporous materials is a very promising costefficient technology, thus a variety of microporous materials
such as zeolites, porous carbon, and nanotubes etc. have been
screened and examined for their selective adsorption behaviors and separation capacities [3e7].
Activated carbon (AC) has been widely used as a versatile
adsorbent for separation of gases, removal of organic pollutants, and so on, due to its large specific surface area, porous
structure and good adsorption properties. Nevertheless, its
high cost precludes its application in most cases. Recognizing
this economic drawback, many investigators have made
efforts in low-cost alternatives to activated carbon from

a range of carbonaceous and mineral precursors, such as fruit

stones, nut shells, fly ash, minerals and scrap tires [8e11].
Utilization of biomass from agricultural residues as a raw
material for production of activated carbons is steadily
increasing in countries with vastly available biomass byproducts [12].
Numerous studies have been devoted to preparation of
high surface area carbon adsorbents for gas adsorption
and separation. There are basically two methods for
manufacturing activated carbons, i.e. physical and chemical
activation [13]. Physical activation involves carbonization of
the raw material below 1073 K in an inert atmosphere followed by mild oxidation of the raw material with activating
agent such as steam, air and CO2 at higher temperatures
(800e1000  C). The most widely used activating gas is steam.
Because the activated carbon produced with steam has larger
adsorptive capacity and wider pore size distribution than that

* Corresponding author. Tel.: 86 25 83794744; fax: 86 25 83795508.

E-mail address: sm@seu.edu.cn (M. Song).
0961-9534/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2012.11.007

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b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

produced with CO2 [14]. Chemical activation involves

impregnation of the raw material with dehydrating chemical
agents including phosphoric acid, sulfuric acid, potassium
hydroxide and zinc chloride in an inert atmosphere [15,16].
The common feature of these impregnation lead to increase of
carbonization ability, and therefore development of a desired
pore structure.
In this work, first, we focus on the utilization of corn residues as raw materials for the preparation of activated carbons
applying simple two-step process of pyrolysis. Second, we
illustrate the relationship between the different preparation
condition of activated carbons and the properties of the
biomass-derived carbons. In addition, we research the
detailed characterization of microporous carbons and investigate the carbon dioxide adsorption performance of such
inexpensive carbonaceous materials.

2.

Material and methods

2.1.

Raw materials

Corn cobs are used as raw materials for preparation of activated carbons. The average proximate and ultimate analyses
of the initial materials are shown in Table 1. The corns are
harvested in Kongchang village, Duotian town, Xinghua City,
Taizhou City, which is located in the middle of Jiangsu prov0
00
idence, China. The geographical coordinate is 32 01 57 N and
0
00

119 38 25 E. The site is characterized by warm, rainy climate.
The cultivar for corn is DJ602. Mean number of growing degree
days for this region is about 120. The corn cobs are collected
from local farmers (household). The used corn cob samples
are taken from the middle part of corn cob. The newly harvested corn cobs are dried under the sun on the ground floor in
order to reduce the moisture content. And then the sufficiently dried cobs, which are sealed in the plastic bag, are sent
to laboratory and stored in desiccators. The corn cob samples
are dried in 110  C for 24 h, mill-grinded and sieved at 250 mm
mesh. The whole samples could pass through 250 mm mesh
and used as substrate in the following the experiment.

2.2.

Preparation of the activated carbons

Activated carbon samples are prepared by carbonization and

activation of corn cob. Detailed procedures are described as
follows. 10 g of corn cob materials are loaded in quartz pipe
after pretreatment, and then are carbonated at different
temperature for different carbonization time under nitrogen
atmosphere. The samples are cooled. After that, the materials are activated with steam in the quartz pipe reactor by
heating the reactor from room temperature to different

activation temperature. The steam is generated by the electrical heating equipment, and is introduced into the quartz
pipe with the flow of N2. The quartz pipe is maintained for
certain activation time. The products are cooled to room
temperature and then washed with deion water until the pH
6 to pH 7, dried. The two-step process is also used for the
KOH chemical activation. The carbonation method is the
same as the above description. And then, the carbonized
materials are put into the saturated KOH solution. After that,
the samples are activated at different temperature for
certain activation time and then allowed to cool to room
temperature.

2.3.

Characterization of the activated carbons

The morphologies of the samples are obtained with a scanning electron microscopy (SEM) (Hitachi, S-3000N), using an
accelerating voltage of 20 kV. The composition and structure
are analyzed using powder X-ray diffraction (XRD, Rigaku D/
max-2500 diffractometer with Cu Ka radiation), and Fourier
transform infrared spectroscopy (FTIR) (Bruker Tensor 27
spectrometer in the range of (500e4000) cm
1 on sample
pellets made with KBr). BrunauereEmmetteTeller (BET)
surface areas and pore volumes are measured on a Micromeritics ASAP 2020 sorptometer using nitrogen adsorption at
77 K.

2.4.

CO2 isotherm measurements

Low-pressure CO2 adsorption isotherms at 77 K or 298 K are

measured with a standard static volumetric technique
(Micromeritics ASAP 2020). Approximately 200 mg of sample is
used for each measurement. To obtain the highest gas
adsorption capacity, samples are degassed in vacuum at
150  C for at least 12 h prior to measurements to remove any
residual guest molecules.

2.5.

The methylene blue (MB) and iodine value

The methylene blue (MB) capacity and iodine value are

determined by China National Standards (GB/T12496.8-1999
and GB/T12496.10-1999) to examine the adsorption capability
of the prepared activated carbons.

3.

Results and discussion

3.1.

Orthogonal experiment

In order to optimize the reaction conditions, we mainly

investigate the effect of carbonization temperature/time,
activation temperature/time, and steam flow on the

Table 1 e The proximate and ultimate analysis of the corn cob materials.
Proximate analysis
Vdaf
0.7522

Ultimate analysis

FCad

Ad

Mad

Cad

Had

Nad

Oad

Sad

Pad

0.1895

0.0583

0.0493

0.4653

0.0591

0.0094

0.3672

0.0014

0.0294

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b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

characterization of the prepared activated carbons through

orthogonal experiments designing. Taking activated carbons
prepared by the steam physical activation and KOH chemical
activation as model, orthogonal experiments with 4 factors of
3 levels are designed. A series of activated carbons preparation
experiments are carried out with different reaction
conditions.
The methylene blue and iodine value at every level of
every factor are shown in Tables S1 and S2. Table 2 lists the
optimum reaction conditions for the preparation of activated carbon. The range analysis is aimed to clarify the
significance levels of different influencing factors on the
iodine and methylene blue adsorption characterization of
the prepared activated carbons. Based on the result of range
analysis, the most significant factor could be disclosed.
Tables S1 and S2 summarize the statistics analysis of the
effect of different factors on the iodine and methylene blue
value of prepared activated carbons. The K value is the sum
of each level of a factor. In the meanwhile, the k is the
average of K values, and the range value (R) for each factor is
the difference between the maximal and minimal value of
the three levels. Based on the results of range analysis, the
significance sequence of all the investigated influencing
factors is lined. For the methylene blue value, the order of
significance levels is shown as follows: activation temperature, carbonization temperature, steam flow and activation
time. In the meanwhile, for iodine value, the order is: activation temperature, steam flow, activation time, and
carbonization temperature. Based on the factors, the
optimum conditions for the steam physical activation and
KOH chemical activation are shown in Table 2. Under the
optimum conditions, the methylene blue and iodine value of
activated carbon prepared by the steam physical activation
are 187.67 cm3 g
1 and 665.23 mg g
1 respectively. For the
KOH chemical activation, those are 717.22 cm3 g
1 and
1262.25 mg g
1 respectively. The KOH chemical activation
exhibit the better adsorption capability than the steam
physical activation method.

3.2.

Characterization results

Fig. 1 shows the SEM images of the prepared carbon materials

by the physical and chemical activation methods. The
samples activated by steam (samples a, and b) exhibit smooth
surfaces with many irregularly small cavities over the surface.

When activating with KOH, the resulting sample c and

d contain open holes. Hence, the activated carbon prepared by
the KOH activation method is expected to have large BET and
micropore surface areas.
FTIR, XRD, and BET are further carried out to analyze the
composition and structure of the samples. As shown in the
FTIR spectrum (Fig. 2(a, b)), the strongest peak at 3489 cm
1
reflects the hydroxyl stretching vibration. The 1642 cm
1 band
in the IR spectrum can be assigned to carbonyl groups such as
quinones, which are highly conjugated with the polyaromatic
matrix [17,18]. Furthermore, the spectrum of the activated
carbon sample has several other bands, which are assigned to
C]C (1570 cm
1), CeO (1065 and 1010 cm
1), and CeH or OeH
(776, 607 cm
1). Therefore, the prepared materials are mainly
composed of amorphous carbons with different oxygen containing surface groups. These carbon-oxygen surface groups
may exercise a profound effect on the surface properties of
activated carbons and thus influence their adsorption
characteristics.
The structural parameters and features of the carbon
materials prepared by steam physical and KOH chemical
activation method are obtained from the XRD analysis. The
XRD curves of carbon materials are shown in Fig. 2(c, d). For
the activated carbon prepared by steam physical activation,
the diffraction profiles exhibit two broad peaks at approximately 2q 24 and 2q 42 after activating with steam which
are assigned to the reflection from (002) and (100) planes,
respectively. XRD pattern reveals the amorphous state of the
obtained samples. Accordingly, no pronounced graphitization
occurs under the present carbonization/activation condition.
As comparison, the positions of the two peaks shift slight after
activating with KOH. The peak representing (002) slightly
sharpens and the intensity of the peak representing (100)
increases. This indicates that carbon tends to crystallize,
although it is a non-graphitized structure.
The most important property of the activated carbon is its
adsorptive capacity that is related to the specific pore surface
area. Generally, the higher pore surface area of the activated
carbon, the larger is its adsorptive capacity. The reaction
parameters remarkably influence the BET surface area of the
obtained carbons. The pore structures of biomass-based
carbons can be tuned to some extent by adjusting the
carbonization and activation parameters. Table 3 summarizes
the BET surface area and pore structures properties of the
synthesized carbons with different parameters. The products

Table 2 e The adsorption capability comparison with different activation methods.

b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

253

Fig. 1 e The SEM images of the activate carbons prepared by the steam physical (a, b) and KOH chemical activation method
(c, d) under the optimum conditions.

prepared by the steam physical activation with different

reaction parameters are designated as AC-1, AC-2, AC-3, AC-4,
and AC-5. Among them, in the steam flow of 10 cm3 h
1, the
detailed reaction parameters are shown in Table 3. As
a comparison, sample AC-6 is prepared by chemical activation
with KOH. In detail, the corn cob is carbonated at 400  C for 1 h,
and then is impregnated with KOH aqueous solution (the
mass ratio of precursor/KOH is 1:3). After that the above
product is activated at 800  C for 2 h under argon flow. At last,
the resulting solid is thoroughly washed with water and
finally dried under vacuum. Based on the results, as for the
physical activation, the BET surface area of AC-3 is 980 m2 g
1,
is slightly higher than the reported value [19]. And the pore
volume of 0.52 cm3 g
1 is also slightly higher than the reported
value. When the carbons are activated with the KOH, the
obvious increase in the surface area and pore volume can be
observed, which is shown in Table 3. The amount of KOH
plays a decisive role for the formation of pores. Under the high
temperature, metallic potassium is produced and they intercalated to the carbon matrix, which are responsible for further
carbon gasification and release of gaseous products such as
CO2, CO and H2 [20]. The detail reactions may take place as
follows during the activation processes under high temperature [21].
2KOH/K2 O H2 O
C H2 O/H2 CO
CO H2 O/H2 CO2
K2 O CO2 /K2 CO3
K2 O H2 /2K H2 O
K2 O C/2K CO

The nitrogen sorption isotherms (Fig. 2(e)) of the carbon

materials derived from biomass are of typical type I in the
IUPAC classification. A large amount of nitrogen can be
adsorbed by all samples. Very high adsorption of N2 occurs
in a relative low-pressure range, and the adsorption
capacity increases as the enhancement of the pressure.
Hysteresis is detected between adsorption and desorption
isotherms, indicating the presence of a little proportion of
mesopores and macropores. Therefore, the high BET
surface areas of the activated carbons render them to be
suitable as effective adsorbents for the removal of air
pollutants.

3.3.

Adsorption performance studies

3.3.1.

CO2 adsorption isotherm

Fig. 3(a) shows CO2 adsorption isotherm of the activated

carbon materials at 298 K. As for the chemical activation, the
isotherm of AC-6 shows the highest CO2 adsorption capacity
(1.5 mmol g
1) at 298 K with the pressure of 100 kPa. For the
physical activation, the CO2 adsorption capacity varies with
the different carbonization and activation parameters. Among
them, the AC-3, which exhibits the higher BET surface area,
shows the higher CO2 adsorption capacity (1.4 mmol g
1) at
298 K with the pressure of 100 kPa. The amounts of CO2
adsorbed onto activated carbon increase progressively as the
enhancement of the BET surface area. Actually, a linearly
proportional relationship between the adsorptive capacity
and the BET surface area is suggested, which is shown in
Fig. 3(b).

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b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

Fig. 2 e The FTIR spectra (a, b) and XRD spectra (c, d) of the activate carbons prepared by the steam physical (a, c) and KOH
chemical activation method (b, d) under the optimum conditions. (e): The nitrogen adsorption isotherm of the activated
carbon prepared by the steam physical activation method.

3.3.2.

The methylene blue (MB) and iodine number

The iodine number (mg of iodine adsorbed/g of carbon) and

methylene blue number (mg of methylene blue adsorbed/g
of carbon) are considered as a measure of adsorption
capability of activated carbon. Normally, qiodine denotes the
amount of micropore and qmb denotes the amount of mesopore of activated carbon. As for the physical activation, the
high adsorption capacities for methylene blue and iodine of
porous carbons could be obtained with the enhancement of

high surface area. Under the optimal preparation condition,

the activated carbon samples show the values of qiodine
(665 mg g
1) and qmb (281 mg g
1). Particularly by the twostage method, in which the corn cob is carbonized at the
first stage and activated with KOH at the subsequent stage,
the higher values of qiodine (1262 mg g
1) and qmb
(1076 mg g
1) can be obtained. Therefore, the chemical
activation exhibit the better adsorption capability than the
physical activation with different preparation condition (as

Table 3 e The texture properties of the different activated carbons.

Sample

AC-1
AC-2
AC-3
AC-4
AC-5
AC-6

Carbonation
temperature
( C)

Carbonation
time (min)

Activation
temperature
( C)

Activation
time (min)

400
450
400
500
600
400

60
60
60
90
90
60

700
800
800
850
900
800

60
90
120
90
120
120

Alkali/
carbon
ratio

Pore
diameter
(nm)

BET surface
area (m2 g
1)

Pore volume
(cm3 g
1)

3:1

2.18
2.16
2.09
2.12
2.14
2.01

759
810
980
932
855
1600

0.41
0.45
0.52
0.49
0.46
0.62

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b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

Fig. 3 e (a): The CO2 adsorption isotherms of the activate carbons prepared by the steam physical and KOH chemical
activation method with different reaction parameters. (b): Amounts of CO2 gases adsorbed versus BET surface area of the
activated carbons prepared by the steam physical activation method with different reaction parameters. (c): The iodine and
methylene blue value comparison between the steam physical and KOH chemical activation method under the optimum
reaction parameters.

Table 4 e The comparison between the prepared and commercial activated carbon.
Project

Main index
GB/T13803-1999

Methylene blue number (cm3 g
1)

Iodine number (mg g
1)
Moisture
Ash

First-grade
product

Second-grade
product

90
1000
0.10
0.05

70
900
0.10
0.05

shown in Fig. 3(c)), which is consistent with the results of

CO2 adsorption value. The iodine and the methylene blue
value of the activated carbon prepared under the optimum
condition are higher than that of the first-grade product
specified in the National Standard. The capability comparison between the corn cob based activated carbon and the
National Standard is shown in Table 4. From the results, we
can observe that the characteristics of the prepared activated carbon are found comparable to the commercial
activated carbon.

4.

Steam activation
method

KOH activation
method

187.67
665.23
0.057
0.029

717.22
1262.25
0.083
0.13

Conclusions

A series of corn cob based activated carbons are prepared by

KOH chemical and steam physical activation methods with
the different carbonization and activation parameters. The
optimum conditions are obtained respectively. The characterization results reveal that chemical activation is better than
the steam activation with respect to the porosity development, the BET surface area and total pore volume. Therefore,

256

b i o m a s s a n d b i o e n e r g y 4 8 ( 2 0 1 3 ) 2 5 0 e2 5 6

the as-obtained carbon products by chemical activation

method exhibit the high values of qiodine (1262 mg g
1) and qmb
(1076 mg g
1) and considerable CO2 uptake capacities
(1.5 mmol g
1).

Acknowledgments
The authors are grateful for the financial support of the
National Hi-tech Research and Development Program of
China (973) (2010CB732206 and 2011CB201505), the National
Natural Science Foundation of China (20907008) and Specialized Research Fund for the Doctoral Program of Higher
Education (20090092120010). Dr. Song specially thanks the
support of the Foundation for Southeast University excellent
young teacher.

Appendix A. Supplementary data

Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.biombioe.2012.11.007.

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