Fuel Processing Technology 88 (2007) 599 – 605

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Production of carbon molecular sieves from palm shell based activated

carbon by pore sizes modification with benzene
for methane selective separation
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 15 May 2006; received in revised form 20 January 2007; accepted 25 January 2007

Abstract

Palm shell based activated carbon prepared by K2CO3 activation is used as precursor in the production of carbon molecular sieve by chemical
vapor deposition (CVD) method using benzene as depositing agent. The influences of deposition temperature, time, and flow rate of benzene on
pore development of carbon molecular sieve (CMS) and methane (CH4) adsorption capacity were investigated. The parameters that varied are the
deposition temperature range of 600 to 1000 °C, time from 5.0 to 60 min, and benzene flow rate from 3.0 to 15 mL/min. The results show that in
all cases, increasing the deposition temperature, time, and flow rate of benzene result in a decrease in adsorption capacity of N2, pore volume and
pore diameter of CMS. The BET surface area of CMS (approximately 1065 m2/g) and the adsorption capacity of CH4 were at a maximum value at
a deposition temperature of 800 °C, time of 20 min and benzene flow rate of 6 mL/min. The product has a good selectivity for separating CH4
from carbon dioxide (CO2), nitrogen (N2), and oxygen (O2).
© 2007 Elsevier B.V. All rights reserved.

Keywords: Carbon molecular sieve; Chemical vapor deposition; Activated carbon; Methane

1. Introduction activated carbon from palm shell as the precursor in the

The use of CMS in gas separation processes is known for
decades. Chemical process industry has become increasingly
interested in the development of low cost gas separation
processes and gas separation technology is quite closely
connected to CMS [1–3]. CMSs are a special class of activated
carbons which may exhibit several advantages such as excellent
and sharp selectivity for the adsorption of planar molecules,
higher hydrophobicity, higher resistance to both alkaline and
acid media, and thermal stability at high temperatures under
inert atmosphere [4,5]. They can be prepared from a variety of
precursors such as polymers, coconut shells, wood, bituminous
carbon and other ligninocellulosic materials [6–8]. Neverthe-
less, the usefulness and feasibility of using chemically produced
⁎ Corresponding author. Tel.: +60 379676897; fax: +60 379675371.
E-mail address: ashri@um.edu.my (W.M.A. Wan Daud).
0378-3820/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.01.009
preparation of CMS have yet to be explored.
An affective CMS is defined by two properties: selectivity
for the adsorption of one of the species in a gas mixture to be
separated, and adsorption capacity for this species [9].
Selectivity is provided by a narrow pore size distribution
around an appropriate pore size determined according to a
particular gas mixture, whereas capacity is related to a relatively
high micropore volume. CMS can be prepared through several
processes such as via controlled pyrolysis or activation of
carbonaceous materials and modification of the texture of
activated carbons through CVD of an organic substance [10].
The CVD method has attracted much interest as it allows
optimizing adsorption capacity and selectivity. Adsorption
capacity is developed during the production of the activated
carbon while selectivity is introduced by depositing carbon at
the entrances of pores. The hydrocarbon species often used as
depositing agent were methane, benzene, toluene, ethane, and
hexane [11–14]. Benzene is widely used since it does not
600 D. Adinata et al. / Fuel Processing Technology 88 (2007) 599–605
produce intermediate species in the cracking process, which
makes deposition easier to be controlled. However, the use of
benzene has its own drawbacks. It is such a highly toxic
substance.
In Malaysia, the research on palm shell for production of
carbon adsorbents has been encouraged by the large availability
of this solid waste. For example, in 1998, 3.38 million tons of
dry empty fruit bunches (EFB), together with 3.56, 2.41 and
1.43 million tons of mesocarp fibers, shell, and palm oil mill
effluent (POEM), were generated at the mills, respectively.
Consequently, this is an advantage to the industry if the excess
shells can be used to produce useful products such as carbon
adsorbents. Production of CMS from palm shell by carboniza-
tion for air separation and the effect of different carbonization
temperatures on the pore structures and adsorptive properties for
oxygen and nitrogen were investigated [15]. Although there are
many studies in literature relating to the preparation and
characterization of CMS from agricultural wastes as mentioned
before, however, the production of CMS, as an adsorbent, by
CVD method with benzene using chemically-activated carbon
from palm shell for carbonaceous precursors has not been
investigated. The aim of this work is to use benzene as CVD to
produce CMS using palm shell based activated carbon produced
through chemical activation—K2CO3 as precursor. The influ-
ences of deposition temperatures, times, and flow rates of
benzene on pore development of CMS and adsorption capacity
of CH4 were investigated.
2. Experimental
2.1. Materials and chemicals
2.1.1. Materials and raw material analysis
Palm shells were dried, crushed and sieved to a particle size fraction of
1–2 mm, which is the commonly used precursor size for preparation of
activated carbon.
An elemental analysis of the palm shell was carried out using a Perkin Elmer
CHNO/S Analyzer 2400 and the results are shown Table 1. As for the
ligninocellulosic contents, they were determined using Technical Association of
Pulp Paper Industry (TAPPI) analytical methods whereby methods T-13wd-74,
T-17wd-70 and T-9m-54 were followed for determining the content of lignin,
cellulose and halo cellulose, respectively. The results obtained are shown in
Table 2.
2.1.2. Chemicals
Potassium carbonate (K2CO3) with purity of 99.9% supplied by Fisher
Scientific was diluted with distilled water to prepare a saturated solution of
chemical activation agent (K2CO3). Benzene with purity of 99.99% supplied by
Fisher Scientific was used as a deposition agent in the CVD process. A
commercial grade carbon molecular sieve (CMS comm) was supplied from
Bergaur by Bergbau Forschung (Germany) and used for performance
comparison with the prepared CMS.
Table 1
Proximate and ultimate analyses of palm shell
Sample Proximate analysis (wt.%) Element analysis (wt.%)
Carbon Moisture Ash Volatile C H N S O
a
Palm shell 18.7 7.96 1.1 72.47 50.01 6.9 1.9 ND 41
a
ND: not detectable.
Table 2
Cellulose, halo cellulose and lignin contents of palm shell
Sample Cellulose (%) Halo cellulose (%) Lignin (%)
Palm shell 29.7 47.7 53.4
2.2. Experimental procedures
2.2.1. Preparation of activated carbon from palm shell (ACP)
Potassium carbonate (K2CO3) was diluted with distilled water to prepare a
saturated solution of K2CO3. Palm shells were mixed with saturated solution of
K2CO3. This mixture was then dried in an oven at 110 °C for 24 h to prepare the
impregnated sample. In this work for all the samples, the impregnation ratio was
1.0.
ðweight of K2 CO3 in solutionÞ
impregnation ratio ¼ : ð1Þ
ðweight of palm shellÞ
A typical carbonization run began by charging 100 g of the impregnated
sample in the reactor and heating it up to the carbonization temperature in a
flowing stream of nitrogen (N2) (15 L/min) [16]. The temperature of the reactor
was increased at the rate of 10 °C/min, until it reached the final carbonization
temperature of 800 °C and this temperature was maintained for 2.0 h. After that,
the sample was cooled down under N2 flow, and the sample was washed several
times with hot water, and finally with cold distilled water. Then the sample
known as activated carbon from palm shell (ACP) was dried at 110 °C and later
used for production of CMS.
2.2.2. Preparation of CMS
Approximately 10.0 g of ACP was loaded into the reactor and the reactor
was purged with N2 gas at the rate of 15 L/min for about 15 min to drive out all
air inside the reactor. The sample was heated up to the deposition temperature in
a flowing stream of N2 (2.0 L/min) at the rate of 10 °C/min, until it reached the
final deposition condition. After that, the furnace for preheating benzene and the
metering pump were switched on to inject the benzene vapor into the reactor.
After the deposition process, the sample was cooled down under nitrogen flow.
The deposition process was varied over the deposition temperature range of 600
to 1000 °C, times of 5.0 to 60 min, and flow rates of benzene from 3.0 to 15 mL/
min, respectively.
2.3. Characterization
Palm shell based CMS and commercial CMS were characterized using N2
adsorption at 77 K and the adsorption capacities of CH4, CO2, O2, and N2 are
measured at room temperature (30 °C) using a Micromeritics ASAP 2010
surface area analyzer. The sample was placed inside a tube and a glass bulb was
inserted inside the tube. The bulb was inserted by slanting the sample tube
almost to a horizontal position. Before an experiment began, the adsorbents were
degassed (10− 4 mm Hg) at 393 K. The surface area of the samples was measured
based on the Brunauer–Emmet–Teller (BET) method. The Dubinin–Radush-
kevich (DR) method was applied to calculate the micropore volume, and the
pore size distribution was investigated based on the Horvath–Kawazoe (HK)
method [17].
3. Results and discussion
3.1. Adsorption isotherm of N2
One of the methods for estimating the type of pores present
in a solid is by analyzing its isotherm curve. Fig. 1 shows the
adsorption isotherm of N2 on the CMS prepared at different
deposition temperatures, times, and flow rates of benzene. The
amount of N2 adsorbed at approximately P/Po = 1.0 decreases
 D. Adinata et al. / Fuel Processing Technology 88 (2007) 599–605
Fig. 1. The adsorption isotherm of N2 on the CMS prepared at different
deposition temperatures, times, and flow rates of benzene.
with increasing deposition temperature, deposition time, and
benzene flow rate. In all cases, Type I isotherms were obtained
which indicate the presence of micropores. The increases in
deposition temperature, time, and flow rate of benzene have
reduced the pores mouth opening due to the depositing carbon
and then consequently decreased the volume of micropore, pore
volume and diameter causing the reduction of N2 adsorption
isotherm. The N2 adsorption isotherm on CMS prepared at
deposition temperature of 800 °C, time of 20 min, and benzene
flow rate of 6 mL/min was approximately similar to that
obtained on the commercial CMS.
3.2. Influence of deposition temperature on BET surface area of
CMS
The adsorption capacity of CMS is related to its internal
surface area and pore volume. Generally, the larger the BET
surface area of CMS, the higher its adsorptive performance will
be. The influence of deposition temperature on the BET surface
area of CMS at deposition time of 20 min and benzene flow rate
of 6 mL/min is shown in Fig. 2. The BET surface area increases
with an increasing deposition temperature from 600 to 800 °C
and decreases slightly for deposition temperature higher than
800 °C. However, the surface area of micropore increases
continually due to the surface areas of macropore and mesopore
being converted to surface areas of micropore. There is a
601
pronounced decrease in micropore surface area when the
deposition temperature is higher than 800 °C. This is because
many pore mouths of CMS are covered by the depositing
carbon. These results suggest that in order to obtain an optimal
value for the surface area, the deposition temperature should be
around 800 °C and the optimal value for the BET surface area of
CMS obtained in this condition is higher than the BET surface
areas of commercial CMS and ACP, which are 551 and 461 m2/
g, respectively.
3.3. Influence of deposition time on BET surface area of CMS
The influence of deposition time on the BET surface area of
CMS produced is very significant as seen in Fig. 3. The BET
surface area increases with the deposition time to reach a
maximum for a deposition time of 20 min, then decreases as the
deposition time exceeds 20 min. The maximum BET surface
area obtained is 1065 m2/g, which is significantly higher as
compared to the BET surface area of the ACP source (461 m2/
g). At deposition times of 5 to 20 min, the mesopore and
macropore of ACP were converted to micropore and conse-
quently increased the BET surface area. Prolongation of the
cracking time for more than 20 min led in fact to a reduction in
the value of the BET surface area due to excessive coke
formation, an increase in the amount of benzene deposition, and
probably to excessive filling of pores [18]. These results suggest
that to obtain the optimal value of the BET surface area, the
deposition time should be around 20 min.
3.4. Influence of benzene flow rate on BET surface area of
CMS
One of the factors that influence the BET surface area of
CMS is depositing agent flow rate. The influence of benzene
flow rate on the BET surface area of CMS at deposition
temperature of 800 °C and deposition time of 20 min is shown
in Fig. 4. The BET surface area of CMS increases initially with
the flow rate to reach a maximum at 6 mL/min and then
decreases with the flow rate. When the flow rate increased from
3 to 6 mL/min, some of mesopores and macropores of ACP
Fig. 2. The influence of deposition temperature on the BET surface area of CMS
at deposition time of 20 min and benzene flow rate of 6 mL/min.
602 D. Adinata et al. / Fuel Processing Technology 88 (2007) 599–605
Fig. 3. The influence of deposition time on the BET surface area of CMS
produced at deposition time of 20 min and benzene flow rate of 6 mL/min.
were converted to micropore and consequently increased the
BET surface area value of CMS. The reduction in the BET
surface area of CMS at a flow rate greater than 6 mL/min could
be due to the phenomena of the blocking effect of benzene, or
excessive filling of pores. These results indicate that to obtain
the optimal value of the BET surface area of CMS, the flow rate
of benzene should be around 6 mL/min.
3.5. Influence of deposition temperature on micropore volume
of CMS
The adsorption capacity of CMS largely depends on the
amount of micropores that are present in the CMS. The
influence of deposition temperature on micropore volume of
CMS at deposition time of 20 min and benzene flow rate of
6 mL/min is shown in Fig. 5. The results indicate that the
micropore volume increases with an increase in the deposition
temperature of up to 800 °C. However, it reduces slightly at the
deposition temperature of above 800 °C. Since the cracking
process of the benzene ring is a function of temperature, at low
temperature the vapor is adsorbed into the interior part of the
particle before cracking occurs at the pore wall. This process
reduces both the pore diameter and the adsorption capacity. At
Fig. 4. The influence of benzene flow rate on the BET surface area of CMS at
deposition temperature of 800 °C and deposition time of 20 min.
Fig. 5. The influence of deposition temperature on micropore volume of CMS at
deposition time of 20 min and benzene flow rate of 6 mL/min.
higher than 800 °C, the cracking process takes place before the
molecules are adsorbed into the interior part of the particle, thus
depositing onto the external part of the particle. Here, it seems
that 800 °C is approximately an optimal temperature, whereby
the cracking process takes place just at the mouth of the pore
thus reducing the pore mouth diameter without decreasing the
adsorption capacity. At a deposition temperature of 800 °C,
these results indicated that the micropore volume of prepared
CMS was higher than the micropore volumes of commercial
CMS and ACP, which are 0.092 and 0.088 cm3/g, respectively.
3.6. Influence of deposition time on micropore volume of CMS
Fig. 6 shows the influence of deposition time on micropore
volume of the CMS at deposition temperature of 800 °C and
benzene flow rate of 6 mL/min. The micropore volume
increases with increasing deposition times from 0 to 20 min,
however it decreases slightly at deposition times of 20 to
60 min, due to pore closing as a result of the deposition process.
During CVD processing, the pyrolyzed carbon is deposited on
the pore surface. One possible mechanism on how the
micropore volume could be increased or reduced during the
Fig. 6. The influence of deposition time on micropore volume of the CMS at
deposition temperature of 800 °C and benzene flow rate of 6 mL/min.
 D. Adinata et al. / Fuel Processing Technology 88 (2007) 599–605
Fig. 7. The influence of benzene flow rate on micropore volume of the CMS at
deposition temperature of 800 °C and deposition time of 20 min.
CVD process is that the hydrocarbon molecules (benzene) in
vapor phase are firstly adsorbed onto the pore surface (micro-,
meso-, and macropore surface) and then pyrolyzed into carbon.
As a result, some of the meso- and macropores are converted to
micropore. When they are exposed to the benzene vapor for a
long period, some of the pores became constricted or even
blocked by the pyrolyzed carbon. The micropore volume of the
prepared CMS obtained in this work was found higher than the
micropore volume of commercial CMS and ACP at a time
deposition of 20 min.
3.7. Influence of benzene flow rate on micropore volume of
CMS
The influence of the benzene flow rate on the micropore
volume of the CMS at deposition temperature of 800 °C and
deposition time of 20 min is shown in Fig. 7. The micropore
Fig. 8. The pore size distribution of CMS produced at different deposition
temperatures, times, and flow rates of benzene.
603
Fig. 9. Adsorption capacity of CH4 onto the prepared CMSs at different
deposition temperatures, times, and flow rates of benzene and the adsorption
capacities of carbon dioxide (CO2), nitrogen (N2), and oxygen (O2) onto the
prepared CMS at deposition temperature range of 800 °C, time of 20 min and
benzene flow rate of 6 mL/min.
volume increases with increasing benzene flow rates from 0 to
6 mL/min and reduces the value of the micropore volume at
benzene flow rates from 6 to 15 mL/min. At benzene flow rates
from 3 to 6 mL/min, mesopore volume and macropore volume
of ACP were converted to micropore volume so that micropore
volumes of CMS increase. At a higher benzene flow rate, the
amount of CVD increased so that the micropore volume of
CMS is reduced. Many micropores of the surface area were
coated and blocked by coke deposition. At this stage, the
deposition process controls the overall rate of reaction, thus the
deposition also occurs at the outer surface of the particle thus
blocking the accessibility of some micropores. At low benzene
flow rate, the process could be due to diffusion control and as a
result more mesopores are converted to micropores.
3.8. Pore size distribution of CMS
The structural homogeneity of a porous material from CMS
is generally characterized in terms of the pore size distribution.
The pore size distribution of CMS produced at different
deposition temperatures, times, and flow rates of benzene is
given in Fig. 8. From the measurement of the pore size
distribution of CMS using the Horvath–Kawazoe (HK) method,
it was confirmed that the deposition temperature, time, and flow
rate of benzene have significant effects on the pore development
of CMS. At high deposition temperature, long deposition time,
and high flow rate of benzene, the pore diameter and pore
volume values of the samples will be smaller than the ACP
source. This also implies that carbon deposition occurred in the
channels of activated carbon source and the pores are filled by
coke deposition. When deposition temperature, time and flow
rate of benzene are 800 °C, 20 min, and 6 mL/min the pore size
604 D. Adinata et al. / Fuel Processing Technology 88 (2007) 599–605
Table 3
Comparison of CO2/CH4 and O2/N2 selectivity on selected CMS with
commercial CMS
Sample k(CO2)/k(CH4) k(O2)/k(N2)
CMS (800-20-6) a
0.92 0.73
CMS comm. 0.93 0.72
a
Note: 800-20-6 represents.
and pore volume of prepared CMS were relatively similar to
those of commercial CMS.
3.9. Adsorption capacity
The adsorption capacity of CMS strongly depends on the
amount of micropores present in it. Some of the factors that
enhance the adsorption capacity and control of pore diameter
and micropore volume of the CMS are the deposition
temperature, time, and flow rate of benzene. Fig. 9 shows the
adsorption capacity of CH4 onto the prepared CMSs at different
deposition temperatures, times, and flow rates of benzene.
Adsorption capacity of CH4 increases in accordance to the
deposition temperature of 600 to 800 °C, time from 5 to 20 min,
and the flow rate of 6 to 15 mL/min and reduces slightly at the
deposition temperatures of 800 to 1000 °C, times of 20 to
60 min, and flow rates of 6 to 15 mL/min. At deposition
temperature of 800 °C, time of 20 min and flow rate of 6 mL/
min, the adsorption capacity of CH4 was at the maximum value
due to the largest micropore volume and BET surface area
created. At these conditions some macropores and mesopores of
ACP are converted to micropores through the benzene cracking
process [19]. At higher deposition temperature, longer time, and
higher flow rate than 800 °C, 20 min, and 6 mL/min, the
micropore volume decreases because some pores were blocked
by coke deposition thus decreasing the overall adsorption
capacity of CH4. These results indicated that to obtain a high
value of the adsorption capacity of CH4, the deposition
temperature, time, and flow rate of benzene should be around
800 °C, 20 min, and 6 mL/min.
The adsorption capacities of carbon dioxide (CO2), nitrogen
(N2), and oxygen (O2) onto the prepared CMS at deposition
temperature of 800 °C, time of 20 min and flow rate of benzene
from 6 mL/min are also shown Fig. 9. These parameters were
chosen because they were an optimal condition for the
production of CMS in terms of micropore volume than other
samples. These results indicated that CMS can be useful for
CH4 separation from gas mixtures [20]. However, CH4
adsorption capacity is smaller than CO2, N2, and O2 and the
adsorption capacity of CO2 is the highest and this could be due
to the molecular diameter of CO2 which is the smallest
compared to O2, N2, and CH4. The molecular diameters of CO2,
O2, N2, and CH4 are 0.33, 0.346, 0.364, and 0.38 nm,
respectively [21].
The overall efficiency of the separation process is not only
defined by the adsorption capacity for different species but also
by absolute adsorption rate constants of the species to be
separated [22]. Absolute adsorption rates for the samples under
study have been determined by fitting experimental curves to
the linear driving force mass transfer kinetic model (LDF) [23]
described by the following equation:
Mt =Me ¼ 1−expð−ktÞ ð2Þ
where Mt is the mass uptake at time t, Me is the mass uptake
at equilibrium and k can be determined from the gradient of
the graphs of ln(1 − Mt / Me) vs. time. The selectivity for each
gas couple was calculated as the ratio of the corresponding
rate constants (k(CO2)/k(CH4) for the gas couple CO2/CH4
and k(O2)/k(N2) for O2/N2). Comparison of CO2/CH4 and O2/
N2 selectivity on selected CMS with commercial CMS is
shown in Table 3. The result shows that selectivities of CO2/
CH4 and O2/N2 for both selected CMSs are about the same.
4. Conclusions
Based on the experimental investigations, the following
conclusions can be drawn. The specific surface area of CMS
from chemically-activated carbon palm shell by CVD method
was at a maximum value (about 1065 m2/g) at a deposition
temperature of 800 °C, time of 20 min, and benzene flow rate of
6 mL/min. By increasing the deposition temperature, time, and
flow rate of benzene, the adsorption isotherm of N2, pore
volume and pore diameter of CMS decrease and benzene is a
good depositing agent. The deposition temperature, time and
flow rate of benzene have been shown to strongly affect the
adsorption capacity of CH4. By the increasing the deposition
temperature, time and flow rate of benzene, adsorption isotherm
of N2, pore volume and pore diameter of CMS progressively
decrease. The CMS produced has a good selectivity for
separating CH4 from CO2 and O2 from N2.
Acknowledgments
Financial support for this work was provided by IRPA
Grant (08-02-03-1003), Ministry of Science, Technology and
Innovation (MOSTI) of Malaysia and the University of
Malaya.
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