Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599

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Renewable and Sustainable Energy Reviews

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Preparation of carbon molecular sieve from lignocellulosic biomass: A review

Abdul Rahman Mohamed a,*, Maedeh Mohammadi b,1, Ghasem Najafpour Darzi b,1
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Faculty of Chemical Engineering, Noushirvani University of Technology, Babol, Iran

A R T I C L E I N F O A B S T R A C T

Article history: A literature review on preparation of carbon molecular sieve (CMS) from lignocellulosic biomass is
Received 22 December 2009 presented. The effect of various operation parameters such as pyrolytic temperature, flow rate of the
Accepted 21 January 2010 carbonizing agent and time of pyrolysis on the carbonization of the lignocellulosic biomass as a carbon
precursor was reviewed. Various physical and chemical processes for the activation of the biomass-
Keywords: based char and their effects on textural properties of the activated char were discussed. Conversion of
Activated char activated chars to CMS as the final stage of the preparation process through different techniques of
Carbon molecular sieve
chemical vapor deposition (CVD) and controlled pyrolysis was assessed. Survey of literature revealed
Lignocellulosic biomass
that production of CMS with BET surface area of 1247 m2/g and micropore volume of 0.51 cm3/g, under
Selectivity
appropriate conditions has been reported. Also, maximum selectivity of 7.6 and 400 for separation of O2/
N2 and CO2/CH4 was devoted to palm shell and coconut shell-based CMS, respectively.
ß 2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1591
2. Experimental conditions for production of CMS from lignocellulosic biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1592
2.1. Carbonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1592
2.2. Char activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1593
2.2.1. Thermal activation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1593
2.2.2. Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1595
2.3. Preparation of carbon molecular sieve (CMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1596
2.3.1. Chemical vapor deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1596
2.3.2. Controlled pyrolysis of carbon precursor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1597
2.3.3. Characterization of CMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1597
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1598

1. Introduction
Separation and purification of gaseous mixtures is an important
unit in the chemical and petrochemical industries. Nowadays,
there is a growing demand for high purity products which boosts
the importance of gas separation processes. Gas adsorption as a
physical treatment technique is proved to be effective in processes
* Corresponding author. Tel.: +60 4 599 6410; fax: +60 4 594 1013.
E-mail addresses: chrahman@eng.usm.my (A.R. Mohamed),
Mohammadi_fanni@yahoo.com (M. Mohammadi), Najafpour@nit.ac.ir (G.N. Darzi).
1
Tel.: +98 911 3138305; fax: +98 111 3210975.
which involve the gas separation and purification [1,2]. Although
adsorption may be a costly method however, utilizing low cost
materials as adsorbent makes the adsorption process cost effective.
Lignocellulosic biomasses are attractive materials as precursors for
preparation of carbonaceous materials used in adsorption pro-
cesses [3,4].
Biomass is the only renewable source of carbon which can be
converted to solid, liquid and gaseous product through various
conversion processes. Currently, biomass provides about 14% of
the word’s energy consumption [5], but still large quantities of
biomass have no specific use. They are burned in open air or
dumped which generate pollutants including dust and acid rain
gases such as sulfur dioxide and nitrogen oxides. According to the

1364-0321/$ – see front matter ß 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2010.01.024
1592 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599

growing trend towards the use of biomass-based energy and
material in developed countries, it is important to utilize such
potential wastes to produce energy or valuable commercial
products. One of the promising technologies which utilize the
wastes or plant matter involves the production of CMS from
biomass-based materials.
The basic structure of all lignocellulosic biomass comprises of
three main natural polymers of cellulose (C6H10O5)x, hemicellu-
loses (C5H8O4)m and lignin [C9H10O3(OCH3)0.9–1.7]n [6]. Lignin is
a mononuclear aromatic polymer found in the cell wall of certain
biomass, especially wood species, whose function is to cement
cellulose fiber in plants [5,7]. It is the most abundant renewable
carbon resource on earth after cellulose, with worldwide
production of 40–50 million tons per year [8]. Lignin is the
most non-commercialized waste product which is proved to
have considerable potential in the field of adsorption and
preparation of activated carbon [3,7,9]. In fact, lignin is rich in
carbon and its molecular structure is similar to bituminous coal
which makes it a suitable precursor for activated carbon
production [7]. Lignin which consists about 27% of the biomass
content has low adsorption capacity in its natural form. But, its
performance can be highly improved under appropriate condi-
tions [3,6].
Generally, thermo-chemical processes such as pyrolysis are
applied to generate char, oil or gaseous product from biomass.
During thermal treatment, moisture and volatile compounds are
removed from the biomass and solid chars are generated whose
properties are different from the origin of the biomass materials
[10]. Such processes lead to materials with high porosity, large
surface area and high pore volumes. Therefore, the generated char
is an attractive and potential by-product for the preparation of
activated carbon and carbon molecular sieve (CMS) [3,10]. CMS is
an amorphous structure, carbonaceous material which is charac-
terized by a very narrow micropore size distribution to discrimi-
nate molecules on the basis of their size and shape. It has practical
use in the field of catalysis, membrane and separation of gaseous
mixtures via pressure swing adsorption (PSA). The biomass-based
CMSs have been extensively used for separation of nitrogen and
oxygen from air stream [11–16], carbon dioxide and methane
[11,14,17–20], propane and propylene [21] and benzene and
cyclohexane [22] from their mixtures.
Any carbonaceous material with low inorganic compounds can
be used as a raw material for CMS preparation. But, use of
lignocellulosic biomass as a cheap and abundant carbon source for
generation of CMS will enhance the economical feasibility of the
adsorption process. A survey of literature indicated that various
lignocellulosic biomass have been used as the substrate for CMS
production such as eucalyptus wood [18] spruce, oak and beech
wood [23] some other resinous woods [21,24], peach stone [19,25],
apricot stone [26], walnut shell [27,28], macadamia nut shell [13],
coconut shell [29,30] and palm shell [11,15,17,31,32].
The purpose of current paper is to present a detailed review on
preparation of CMS from lignocellulosic biomass. Various experi-
mental methods for preparation of biomass-based CMS are
reviewed. The effect of several process parameters on textural
characterization of the generated CMS such as BET surface area and
pore volume is discussed and the obtained results from the
literature are reported.
2. Experimental conditions for production of CMS from
lignocellulosic biomass
Basically, preparation of the CMS from lignocellulosic material
involves three steps of carbonization of the lignocellulosic
biomass, activation of the chars and pore modification of the
activated carbons to obtain CMS.
2.1. Carbonization
Pyrolytic conversion of lignocellulosic biomass generates three
phases of char, oils (tar) and gases [33]. The distribution of the
phases is a function of process parameters, especially heating rate
[34,35]. Slow heating promotes solid conversion rate while flash
pyrolysis is implemented for high liquid rates. When charcoal is
the desired end product, the pyrolytic conversion is conducted by
slow heating which is known as carbonization [35]. Char is the
carbonaceous residue of the carbonization process after removing
non-carbon elements such as hydrogen and oxygen from the
starting material [36]. It has a rudimentary porous structure which
can be used for activated carbon and CMS production. Char has a
high fixed carbon content which makes it a suitable precursor for
such purposes [34]. Table 1 presents the proximate and ultimate
analysis of various lignocellulosic biomasses.
Pyrolytic temperature, heating rate, nitrogen flow rate which
is used as the carbonizing agent and time of pyrolysis are the
main operation parameters involved in carbonization process.
Also, the lignocellulosic composition of the biomass has a
significant effect on micropore structure of the end product
[9]. Researchers confirmed that lignin is the main source of char,
whereas cellulose and hemicelluloses are the volatile fractions of
biomass [45]. Lignin decomposition starts at low temperatures
(160–170 8C) and this process continues at low rate until elevated
temperature of 900 8C. The second component which starts to
decompose is hemicellulose, followed by cellulose. The decom-
position of these two polymers takes place in a narrow
temperature range of about 200–400 8C. In this temperature
interval the main decomposition of the biomass occurs [37].
Therefore, the composition of the lignocellulosic biomass is an
important parameter in char formation and the higher lignin
content results in higher char yield [7,35]. The lignocellulosic
composition of the biomasses and their high heating value (HHV)
are tabulated in Table 2.

Table 1
Ultimate and proximate analysis of lignocellulosic biomass.

Biomass type Ultimate analysis (db, % w/w) Proximate analysis (db, % w/w) Reference

C H O N S Ash Volatile Fixed carbon

Palm shell 50.01 6.9 41 1.9 0.0 1.19 78.49 20.32 [31]
Coconut shell 53.9 6.1 39.72 0.26 0.02 0.7 74.9 24.4 [37]
Walnut shell 45.1 6.0 48.6 0.3 0.0 1.46 80.67 17.87 [34,38]
Macadamia shell 53.0 6.0 40.65 0.32 0.03 0.44 79.66 19.9 [35]
Eucalyptus wood 47.1 5.9 46.6 0.1 0.0 0.3 85.7 14.0 [39,40]
Spruce wood 50.19 6.1 43.54 0.16 0.01 0.25 86.97 12.78 [41,42]
Oak wood 51.8 6.6 41.3 0.3 0.0 0.63 86.92 12.45 [43]
Beech wood 49.59 6.06 44.08 0.26 0.01 0.39 88.15 11.46 [41]
Apricot stone 52.38 6.57 38.78 1.07 0.15 1.02 80.40 18.58 [44]
Peach stone 51.35 6.01 40.32 0.58 0.14 1.61 79.04 19.35 [44]
 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599 1593

Table 2 is performed by chemical treatment of the starting material with a

Lignocellulosic composition of biomass.
dehydrating agent followed by heat treatment of the impregnated
Biomass type Cellulose Hemicellulose Lignin HHV Reference material in an inert atmosphere [65–68]. Table 4 presents various
(MJ/kg) activation conditions of the lignocellulosic chars.
Palm shell 29.7 16.9 53.4 17.43 [46]
Coconut shell 48.9 19.8 30.1 20.52 [37] 2.2.1. Thermal activation
Walnut shell 25.6 22.1 52.3 21.6 [47] In process of carbonization, a carbon skeleton with a
Eucalyptus wood 57.3 16.8 25.9 20.3 [48,49]
rudimentary porous structure is formed which is known as char.
Spruce wood 50.8 21.2 27.5 20.1 [47]
Oak wood 53.2 24.7 24.6 19.8 [50] The pores of the produced char can be blocked by the tar formed in
Beech wood 45.8 31.8 21.9 19.2 [47] thermal process and result in a low adsorption capacity. Therefore,
Apricot stone 39.75 34.5 25.75 22.08 [44,51] physical or thermal activation after the carbonization process is
Peach stonea 26.6 24.3 47.7 20.66 [44,52]
required to remove the blockage caused by tar. This activation
a
Ash = 1.45. process develops the porosity of the char and makes it suitable for
adsorption purposes [83]. Thermal activation is performed by an
Reed and Williams [53] studied five biomass samples that their oxidizing agent such as CO2, steam, O2 or a mixture of them at
cellulose, hemicellulose and lignin contents were significantly elevated temperatures. The reactions that may occur under such
different. They observed that the thermal decomposition temper- condition to extract carbon atoms from the char structure are
ature in nitrogen was in the range of 325–400, 250–350 and 200– summarized as follows [2,83]:
720 8C for cellulose, hemicellulose and lignin, respectively. They C þ H2 O ! CO þ H2 ; DH ¼ þ117 kJ=mol
also concluded that the sample with highest lignin content
produced the highest yield of char and consequently highest C þ 2H2 O ! CO2 þ 2H2 ; DH ¼ þ75 kJ=mol
amount of activated carbon. In another investigation conducted by
Daud and Ali [46], activation rate of palm shell and coconut shell C þ CO2 ! 2CO; DH ¼ þ159 kJ=mol
were compared. It was observed that the activation rate of the
coconut shell-based char was significantly higher than that of palm All of these reactions are endothermic; therefore external energy is
shell which was due to the higher lignin content of the palm shell. required to supply the high activation temperature which is almost
In another study performed by Daud et al. [54], the effect of above 800 8C [2,83]. As explained, during the activation process,
carbonization temperature on char yield and pore development of steam or CO2 react with carbon to produce CO, CO2, H2 or CH4. This
palm shell-based char was investigated. It was reported that as the process is referred as ‘‘burn-off’’ [53]. Burn-off is defined as the
temperature was increased from 500 to 900 8C, the char yield weight differences between the char and the activated carbon
gradually decreased from 33 to 24%. The decrease in char yield was divided by the weight of the original char which both weights are
due to the release of carbon, hydrogen and oxygen from the char as on dry basis. The following formula is used to calculate the burn-off
a result of rearrangement of the aromatic ring in the carbon of the activated chars:
structure. They also concluded that the micropore volume W0  W1
increased as the carbonization temperature was gradually Burn-off ¼  100%
W0
increased. Similar experiments were conducted on coconut shell
by Li et al. [55]. They also realized that while increasing the where W0 is the weight of the original char and W1 refers to the
carbonization temperature, the sample diameter was gradually mass of the activated char. Physical activation condition and
lowered and the micropore volume was developed. It was characteristics of the activated char are tabulated in Table 5.
explained that during the pyrolysis, cellulose, hemicelluloses Thermal activation of lignocellulosic chars with steam or CO2
and lignin undergo the dehydration, linkage breaking reaction and causes different effects on the development of microporosity. In
structural ordering of the residual carbon. Finally, polymerization early stages of activation process, CO2 develops narrow micro-
reaction occurs during the carbonization process. As the carboni- pores, while steam widens the initial micropores of the char. At
zation temperature was increased, polymerization reaction was high degrees of burn-off, steam generates activated chars which
developed which resulted in an increase in the micropore volume. exhibit larger meso- and macropore volume than those prepared
They obtained chars with maximum surface area of 702 m2/g at by CO2. As a result, CO2 creates activated chars with larger
1000 8C. It was proposed that high temperature chars offer great micropore volume and narrower micropore size distribution than
potential for fabrication of high capacity activated carbons. those activated by steam [63].
Ahmadpour and Do [56] studied the effects of carbonization Amaya et al. [39] prepared an activated carbon from eucalyptus
temperature on pore volume evolution of macadamia nut shell. char by CO2 activation. In their experiment, CO2 activated carbon
The samples were chemically pretreated with ZnCl2 and KOH with BET surface area of 990 m2/g and micropore volume of
before carbonization. Maximum surface area of 1718 and 1169 m2/ 0.4 cm3/g was obtained. While, in another investigation conducted
g was obtained for ZnCl2 and KOH impregnated samples, while the by Arriagada et al. [77], maximum BET surface area of 801 m2/g
carbonization temperature was set at 500 and 800 8C for the and micropore volume of 0.3 cm3/g was achieved for steam
samples, respectively. In these carbonization temperatures, the activated chars of eucalyptus. Ahmad et al. [11] produced activated
micropore volumes of 0.723 and 0.529 cm3/g for ZnCl2 and KOH carbon from palm shell by steam activation and maximum BET
impregnated samples were achieved. Table 3 summarizes carbon- surface area and pore volume of 1104 m2/g and 0.4067 cm3/g was
ization and activation condition of various lignocellulosic bio- obtained. Guo and Lua [58] carried out similar experiments except
masses. that CO2 was used as gasifying agent instead of steam. As a result,
activated carbon with maximum BET surface area of 1360 m2/g
2.2. Char activation and micropore volume of 0.47 cm3/g was obtained. Li et al. [55]
prepared activated carbon from coconut shell using steam
Generally, there are two main techniques for activation of the activation. They reported maximum BET surface area and pore
chars: physical or thermal activation and chemical activation volume of 1512 m2/g and 0.46 cm3/g. While, in another set of
[33,63,64]. Physical activation involves the use of an oxidizing gas experiment conducted by Guo et al. [81], CO2 was used as
for activation of the chars after carbonization. Chemical activation activating agent for production of activated carbon from coconut
1594 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599

Table 3
Carbonization and activation condition of various lignocellulosic biomasses.

Raw material Particle Carbonization Activation Chemical Additional information Reference

size condition condition treatment

Palm shell 1–2 mm N2, 900 8C/1 h 830 8C/30–420 min Steam One-step carbonization/activation [11,32]
burn-off between 0 and 60%
Palm shell 1–2 mm N2, 800 8C/2 h, _ Chemical Impregnation with diluted K2CO3/oven [31]
15 L/min, 10 8C/min (K2CO3) dried at 110 8C for 24 h/one-step
carbonization/rinsing with hot and
cold distilled water/oven dried at 110 8C
Palm shell 2.0–2.8 mm N2, 200–600 8C/2 h, _ Chemical Impregnation with (10–40%) H3PO4 [57]
150 mL/min (H3PO4) for 3–12 h/oven dried at 110 8C
overnight/one-step carbonization/rinsing
with distilled water/oven dried at 110 8C
Palm shell 2.0–2.8 mm N2, 200–600 8C/2 h, 500–900 8C/2 h, CO2 One-step carbonization/activation [57]
150 mL/min 100 mL/min
Palm shell 2.0–2.8 mm N2, 600 8C/3 h 500–900 8C/30 min, CO2 Oven dried at 110 8C for 24 h/one-step [58]
100 mL/min carbonization/activation
Palm shell 1–3 cm N2, 600–1000 8C/1 h, _ _ Drying overnight at 120 8C/one-step [15]
1.5 L/min carbonization/grounding and sieving
into powder of 360 mm
Palm shell 1 mm N2, 600–1000 8C, _ _ One-step carbonization [1]
20 8C/min
Peach stone 2.0–2.8 mm N2, 850 8C/2 h, 8h CO2 Pretreated with a diluted sulfuric [25]
80 mL/min acid/one-step carbonization/activation
Peach stone 2.0–2.8 mm N2, 850 8C/2 h, 800 8C/3 h, 50% CO2/N2 Washing with diluted sulfuric acid and [19]
80 mL/min, 2 8C/min 80 mL/min then rinsing with deionized water/
carbonization with two intermediate
stops/activation
Peach stone 15–35 mesh N2, 450 8C, 100 mL/min – Chemical Impregnation with H3PO4 (6–8 M)/ [52]
(H3PO4) one-step carbonization
Wood (Salix 1 cm Ar, 700–800 8C/1 h – – Thermal pretreatment at 400 8C for [24]
viminalis) 1 h/one-step carbonization
Eucalyptus – N2, 450 8C, 500 mL/min 825 8C N2/CO2, One-step carbonization/addition of [39]
wood 50 mL/min tar to form a paste/drying the pellets
at 105 8C for 2 h/activation by N2
followed by CO2
Eucalyptus wood 5 cm N2, 830–870 8C/2 h, – – One-step carbonization [18]
300 mL/min, 4 8C/min
Coconut shell – N2, 850 8C/30 min 600 8C/30 min CO2 One-step carbonization/activation [16]
Coconut shell <60 mesh N2, 775–900 8C/8 h, 650–900 8C CO2, steam, O2 One-step carbonization/activation [29]
2–10 8C/min
Walnut shell 1–2 mm N2, 800 8C/1 h – Chemical Thermal pretreatment at 250 8C for [28]
(KOH) 3 h/impregnation with KOH/dehydration
at 300 8C for 3 h/one-step carbonization
Spruce wood Cube (1 cm  N2, 700 8C/1 h – Chemical One-step carbonization of fresh [23]
1 cm  1 cm) (HNO3) wood/chemical activation
Spruce wood Cube (1 cm  N2, 700 8C/1 h 900 8C/15 min Steam One-step carbonization of 1 year long [23]
1 cm  1 cm) incubated wood at ambient
temperature/activation
Spruce, beech Cube (1 cm  N2, 700 8C/1 h 900 8C Steam One-step carbonization/activation [23]
and oak wood 1 cm  1 cm)
Oak wood <150 mm N2, 650 8C/1 h – Chemical Impregnation with H3PO4/heat treatment [50]
(H3PO4) at 170 8C for 30 min under N2
flow/one-step carbonization
Cedar nutshell 3–8 mm Ar, 700–800 8C/120 min, – – One-step carbonization/activation [59]
3 8C/min
Macadamia 500–700 mm N2, 700 8C/2 h, 800 8C/0–480 min CO2 One-step carbonization/activation burn-off [13]
nut shell 100 mL/min between 0 and 35%
Hydrolytic 0.1–0.25 mm Ar, 700 8C/120 min, 800 8C/5–120 min Steam Hydrolytic lignin was obtained by chemical [59]
lignin 3 8C/min transformation of native lignin at elevated
temperature (150–190 8C) and pressure
(0.8–1 MPa)/one-step carbonization/
activation by Ar at 800 8C followed by steam
Macadamia 0.4–1.4 mm N2, 950 8C/14 min – Chemical One-step carbonization/chemical activation [4]
nutshell (H2O2) with H2O2 (0.05–0.15 M)/one-step
carbonization
Apricot stone 1.2–1.7 mm N2, 400 8C – Chemical Impregnation with H3PO4 for 24 h in oven [60]
(H3PO4) at 100 8C/carbonization/rinsing with distilled
water to pH of 5/oven dried at 100 8C
Coconut shell 150 mm N2, 800 8C/60 min, 800 8C/30 min CO2 Impregnation with nitrate salt of Mg, Ca, Ni, [14]
mixed with 2 8C/min Co and Cu separately for 72 h/one-step
coal tar pitch carbonization/activation
Grain sorghum Powder N2, 300 8C/15 min – Chemical One-step carbonization/chemical activation [61]
(H3PO4) by 35 wt% H3PO4 with small amount of
sulfonate lignin at 500 8C for 15 min
Lignin – N2, 400 8C/2 h – Chemical Impregnation with ZnCl2 (ratio of ZnCl2/ [62]
(ZnCl2) lignin was 2.3)/heat treatment with N2
at 800 8C for 2 h
 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599 1595

Table 4
Various activation conditions of the lignocellulosic chars.

Activation method Biomass Reference

Chemical Coconut shell, macadamia nut shell, apricot stone, and lignin ZnCl2 [56,62,69,70]
Palm shell H2SO4 [71]
Wood Commercial waterglass [72]
Walnut shell ZnCl2/HCl/NaOH [73]
Wood, peach stone, oak, apricot stone, walnut shell, apricot stone, H3PO4 [50–52,60,61,70,74,75]
and grain sorghum
Wood, apricot stone, and macadamia nut shell KOH [28,56,76]
Walnut, coconut, and palm shell K2CO3 [31,65]

Physical Apricot stone, peach stone, spruce, oak, beech, eucalyptus wood, Steam [3,17,23,29,33,39,49,55,70,77–80]
walnut shell, coconut shell, palm shell, and lignin
Coconut shell, palm shell, eucalyptus wood, macadamia CO2 [3,13,16,29,40,58,81]
nut shell, and lignin

Physiochemical Wood H3PO4/steam [82]

Peach stone H3PO4/CO2 [64]
Coconut shell ZnCl2/CO2 [66]
Peach stone H2SO4/CO2 [25]
Coconut shell Nitrate salt of metal/CO2 [14]

shell and maximum char BET surface area and pore volume of
1700 m2/g and 0.882 cm3/g was achieved. Carrott et al. [3]
compared the porosity of the activated carbons obtained from
lignin by steam and CO2 activation. They realized that the activated
carbons prepared by CO2 activation possessed larger surface area
and microporosity in comparison to those obtained by steam
activation. Maximum char BET surface area of 1644 and 1008 m2/g
and pore volume of 0.61 and 0.29 cm3/g were achieved for the CO2
and steam activated samples, respectively.
2.2.2. Chemical activation
Chemical activation is usually applied for the degradation of the
lignocellulosic materials. Various dehydrating agents such as
phosphoric acid, sulfuric acid, zinc chloride, potassium hydroxide,
etc are applied in chemical activation process [73,83,84]. The
impregnation of the raw material with dehydrating agent is
followed by heat treatment under inert atmosphere to form the
final porous structure of the activated carbon. Chemical activation
does not require as high temperatures as physical activation
[76,83]. The dehydrating agents inhibit the formation of tar and
other undesired products during the carbonization process. This is
the main concept of the higher carbon yield achieved in chemical
activation in comparison to physical activation process [83].
Generally, the chemical activating agent plays two major roles
during the impregnation stage. It leads to the hydrolysis of the
lignocellulosic material and also causes its swelling. Besides, it
occupies some volume which inhibits the narrowing of the particle
during heat treatment. While the chemical agent is washed from
the carbonaceous material after carbonization, leaves some
porosity inside the activated char [64]. Table 6 summarizes
chemical activation condition and characteristics of the activated
char.
In the chemical activation process, the pore size distribution
and surface area are determined by the impregnation degree which
is the ratio between the mass of the chemical agent and the raw
material. Besides, carbonization temperature and time are impor-
tant preparation variables. Ahmadpour and Do [56] studied the
chemical activation of macadamia nutshell using KOH as a strong
base and ZnCl2 as a Lewis acid. They reported the impregnation
ratio of 1:1, carbonization time of 1 h and pyrolysis temperature of
500 8C for ZnCl2 and 800 8C for KOH as the optimum operation
conditions. Another investigation was conducted by Youssef et al.
[70] to evaluate the effect of impregnation ratio of ZnCl2 on
textural properties of the activated carbon obtained from apricot
stone. It was observed that as the impregnation ratio was increase
from 25 to 75%, the carbon BET surface area increased from 311 to
728 m2/g. In their experiments, maximum BET surface area of
728 m2/g and micropore volume of 0.3 cm3/g were achieved at
impregnation ratio of 75% and carbonization temperature of
600 8C. Munoz-Gonzalez et al. [52] investigated the preparation of
activated carbon from peach stone by phosphoric acid activation.
They also concluded that as the concentration of H3PO4 in the
solution was increased from 2 to 8 mol/L, the porosity of the carbon
was improved. Maximum micropore volume of 0.4 cm3/g was

Table 5
Physical activation condition and characteristics of the activated char.

Biomass type Activation condition Burn-off SBET (m2/g) Vmic (cm3/g) Vt (cm3/g) Reference

Palm shell Steam, 900 8C, 250 min 53.2% 1104 0.4067 0.5138 [11]
Palm shell CO2, 900 8C, 30 min – 1360 0.47 0.69 [58]
Eucalyptus wood Steam, 800 8C, 600 min 64% 801 0.34 – [77]
Eucalyptus wood CO2, 900 8C, 60 min 83% 1491 0.66 0.8 [49]
Peach stone Steam, 824 8C, 960 min 59% 1247 0.44 – [77]
Apricot stone Steam, 850 8C, 120 min – 900 0.38 0.55 [78]
Apricot stone Steam, 900 8C 35% 683 0.160 0.747 [70]
Apricot stone Steam, 800 8C, 4 h – 1092 0.37 – [79]
Wood CO2, 850 8C, 6 h – 1257 0.39 – [76]
Coconut shell CO2, 900 8C, 240 min – 1700 0.882 1.135 [81]
Coconut shell Steam, 800 8C, 120 min – 1512 0.46 0.618 [55]
Oak wood CO2, 800 8C, 120 min 51.4% 985 0.379 0.640 [80]
Hydrolytic lignin CO2, 750 8C, 1080 min 72% 1644 0.61 0.51 [3]
Hydrolytic lignin N2 saturated with steam, 750 8C 65% 1008 0.29 0.31 [3]
Macadamia nut shell CO2, 800 8C, 480 min 34% 802 0.3 – [13]
1596 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599
Table 6
Chemical activation condition and characteristics of the activated char.
Biomass type Activation condition SBET (m2/g)
Palm shell H2SO4, 30 wt% 1014
Wood H3PO4, 50 wt% 761
Wood H3PO4, 50 wt% 1910
Apricot stone H3PO4, 75 wt% 728
Apricot stone ZnCl2 728
Apricot stone H3PO4 1387
Macadamia nut shell ZnCl2 1718
Macadamia nut shell KOH 1169
Wood KOH (concentrated) 1589
Peach stone H3PO4 (8 M) – 0.52
Grain sorghum H3PO4, 35 wt% 2027
Lignin ZnCl2 724
obtained at carbonization temperature of 450 8C. Similar result
was reported by Zuo et al. [75]. They observed that increasing the
impregnation ratio of H3PO4 during the activation of lignocellu-
losic material remarkably enhanced the porosity development. It
was explained that increasing the impregnation ratio not only
raised the amount of phosphoric acid incorporated into the interior
structure of the lignocellulosic particles, but also enhanced the
carbonization of the volatile maters and consequently improved
the microporosity of the activated carbon. Molina-Sabio and
Rodriguez-Reinoso [85] investigated the role of chemical activa-
tion in the development of carbon porosity on peach stone. Three
chemical compounds of KOH, ZnCl2 and H3PO4 were used as
activating agent. They realized that KOH caused the widening of
the micropore volume, ZnCl2 developed some mesoporosity and
H3PO4 led to more heterogeneous pore size distribution. The
micropore volumes of 0.4, 0.5 and 0.6 cm3/g were obtained for
KOH, ZnCl2 and H3PO4, respectively.
2.3. Preparation of carbon molecular sieve (CMS)
CMSs are a special group of activated carbons with homoge-
neous pore size distribution and pore size is the range of several
angstroms [86]. The pore surface area of CMS is less, and its pore
size distribution is narrower than that of activated carbon [32].
They have a sharp and excellent selectivity for the adsorption of
planar molecules. This is due to their slit shape pores with high
hydrophobicity. Therefore, CMS has the potential to perform the
separation in the presence of polar molecules [87].
Efficiency of CMS is defined by its selectivity and adsorption
capacity. Selectivity which refers to the tendency of CMS to adsorb
one of the species from a gaseous mixture is provided by pore size
distribution. While, adsorption capacity of the CMS is related to the
high micropore volume [88]. Adsorption capacity is developed
during the production of activated carbon while selectivity is
introduced by tailoring the pore entrance [31]. Selectivity of CMS
arises from differences in dimensions and shapes of the adsorbing
molecules which results in different sorption kinetics. As some
researchers stated, separation process is based on the differences
in the diffusion rates of the involved species [20,89]. CMS exhibits
preferable adsorption to species which have smaller molecular size
than that of the pore entrance. These special molecules which are
called adsorbate, penetrate into the microporous structure of the
CMS. As the time progresses, the adsorbate fills up the micropores
until a sorption equilibrium is achieved [13]. Therefore, the kinetic
of the process is controlled either by the adsorption equilibrium or
diffusion [90].
In general there are two major approaches to prepare CMS:
controlled pyrolysis of carbon precursor and modification of the
existing porosity of an activated carbon through chemical vapor
deposition (CVD) technique [11,87]. Although there are some other
Vmic (cm3/g) Vt (cm3/g) Reference
– – [71]
0.297 0.618 [82]
0.582 2.126 [75]
0.301 0.327 [70]
0.310 0.358 [70]
– 0.954 [60]
0.723 – [56]
0.529 – [56]
0.564 – [76]
0.53 [52]
0.76 0.62 [61]
0.377 – [62]
methods for preparation of CMS such as microwave heating [91]
and plasma [92], but preparation of biomass-based CMS by these
techniques has not been reported yet.
2.3.1. Chemical vapor deposition (CVD)
Among various preparation methods, considerable attention
has been paid to the chemical vapor deposition (CVD) technique. It
has been stated that the CMS produced from CVD benefits the
advantages such as high adsorption capacity and micropore
volume [11]. CVD deals with deposition of pyrolytic carbon at
the mouth of the pore to reduce the pore entrance to match the size
of the desired adsorbate. Pyrolytic carbon or pyrocarbon is
obtained from thermal decomposition of volatile unsaturated
hydrocarbons [25]. A variety of hydrocarbons such as benzene
[11,17,27,31,32], methylpentane [28] and methane [61] have been
used as hydrocarbon depositing agent.
Although CVD has been extensively used for preparation of
CMSs, it requires exact control of the process to prevent the
blockage of the pore entrance. Deposition of carbon at the pore
mouth may block the narrow pore entrance and consequently
reduces the adsorption capacity of CMS [2,93]. Deposition of
chemicals has been analyzed in terms of reaction and diffusion in a
single pore [12]. Three distinct results were concluded. At low
temperatures that diffusion through the pore is faster than
reaction, there is no diffusion limitation and carbon deposits
uniformly over the entire pore surface. At high temperatures that
reaction is faster than diffusion, the reactant cannot reach the
interior pore surface due to the strong pore diffusion limitations.
Thus, carbon deposition occurs mainly at the pore entrance. As the
temperature is increased to higher than that of the second case, the
kinetic is controlled by mass transfer and carbon deposits on the
external surface of the activated carbon. Therefore, carbon
deposition must be carried out in the kinetic regime to match
the desired effects for CMSs.
Although various hydrocarbons have been employed to
perform the carbon deposition, considerable attention has been
paid to benzene. Benzene does not generate intermediate
compounds during the cracking process which makes the
deposition process controllable [88]. Ahmad et al. [11] investigated
the optimum operation condition for preparation of CMS from
palm shell by CVD of benzene. In their experiments, deposition
temperature was varied from 600 to 900 8C. It was observed that
the micropore volume increased up to 800 8C and then significant-
ly dropped as the deposition temperature was increased to 900 8C.
It was suggested that the deposition occurs on the entire pore wall
at low temperatures which results in low micropore volume. At
moderate temperatures, carbon deposits at the pore mouth
without diffusing into the pore wall and such phenomena
increases the pore volume. At elevated temperatures, benzene
pyrolysis in the gas phase and carbon deposition occurs at the
 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599 1597

exterior surface of the particle which results in some pore blockages.
It was also realized that the effect of benzene concentration on the
selectivity of the CMS was not significant in comparison to
deposition temperature. In another set of experiment conducted
by the same researchers [32], the effect of deposition time on
micropore development was studied while the deposition time was
varied from 15 to 60 min. It was observed that the micropore volume
increased up to 30 min and then gradually decreased at 45 and
60 min. They concluded that some of the pores were clogged due to
the excessive filling of the pores. Maximum CO2/CH4 and O2/N2
selectivity of 16 and 7.06 was obtained in their experiments.
Preparation of CMS from peach stone by CVD of benzene was
investigated by Gomez-de-Salazar et al. [25]. The deposition
temperature was varied from 525 to 725 8C. It was observed that
the CO2/CH4 selectivity was significantly improved as the tempera-
ture was increased to 700 8C and then gradually decreased.
Maximum CO2/CH4 selectivity of 13 was achieved at deposition
temperature of 700 8C. Zhang et al. [61] prepared CMS from grain
sorghum by CVD of methane. It was observed that heat treatment of
activated carbon during CVD of methane at 800 8C, decreased the
surface area from 2027 to 1230 m2/g (by 39.32%) and the micropore
volume from 0.76 to 0.48 cm3/g (by 36.84%). It was suggested that
such phenomena was due to the destruction of the pore structure by
sintering. Preparation of CMS from acidified coconut char was
investigated by CVD of benzene by Vijaya lakshmi and Patwardhan
[16]. Three different samples were prepared by acidifying the CO2
activated char with 1% hydrochloric acid, 1% nitric acid and 0.4%
hydrofluoric acid. The acidified char then subjected to CVD of
benzene. It was observed that hydrofluoric acid was better agent to
create active site for benzene deposition. Son et al. [14] prepared
CMS from coconut shell by metal impregnation (Mg, Ca, Cu, Co and
Ni) followed by CO2 activation and CVD of benzene. Out of the five
samples, Co impregnated one was found to be the best for carbon
deposition. Maximum selectivity of 400 and 200 was achieved for
CO2/CH4 and CO2/N2, respectively.
2.3.2. Controlled pyrolysis of carbon precursor
In controlled pyrolysis process, the carbon precursor is
pyrolyzed under suitable temperature and environment and the
adsorption capacity is increased through creation of micropores
[11]. Sometimes, the carbonized porous material is mixed with a
chemical species. Then, the mixture is further pyrolyzed to reduce
the pore size by deposition of pyrolytic carbon at the pore entrance
[87]. The carbonization process must be conducted carefully to
avoid excess widening of the porosity, which can be detrimental to
selectivity [11].
Bello et al. [18] prepared CMS by mixing the eucalyptus char
with tar as an organic binder followed by thermal treatment using
CO2. It was reported that thermal treatment of the pellets prepared
from char and tar tailored the micropore entrance so that methane
diffusion (kinetic diameter of 0.38 nm) was hindered but CO2
(kinetic diameter of 0.33 nm) could diffuse into the micropores.
High selectivity of 20 was obtained for separation of CO2/CH4 from
the gas mixture. In another investigation conducted by the same
researchers [21], the effect of carbonization temperature (600–
1100 8C) on the micropore development of CMS was investigated.
They realized that the carbonization temperature had a significant
effect on the separation properties of the CMS. An increase in the
carbonization temperature reduced the micropore size distribu-
tion of CMS. The highest selectivity for separation of CH4/CO2 and
C3H6/C3H8 was obtained at carbonization temperature of 1000 and
700 8C, respectively. Gomez-de-Salazar et al. [19] investigated the
production of CMS by controlled oxidation treatments. Oxidizing
treatment of peach stone char was conducted using pure O2 at
850 8C for 20 min. High selectivity of 30.1 for CO2/CH4 was
obtained for this sample. They also prepared CMS by impregnation
of peach stone char in HNO3 (5N) for 3 h followed by heat
treatment at 625 8C. Maximum selectivity of 127.9 for CO2/CH4
was achieved for the prepared CMS. In another experiment, they
activated the peach stone char by a flow of 50% CO2/N2 at 800 8C
and this activated carbon was treated (as explained for the second
sample) to obtain CMS. They obtained maximum selectivity of 14.2
for O2/N2 in their investigation.
2.3.3. Characterization of CMS
Adsorption of gases and vapor is a conventional approach for
the characterization of the microporosity in carbonaceous
adsorbents. Adsorption isotherms of the CMS which are a plot
of the amount of adsorbate with respect to relative pressure are
used to interpret the adsorption data and yield a complete set of
information to characterize the porous structure of the CMSs. Once
the adsorption isotherm obtained, some methods are implemented
to evaluate the microporosity of the CMS. The most common model
is provided by Brunauer–Emmett–Teller (BET) equation which is
used to calculate the surface area. Microporosity is successfully
assessed by Dubinin–Radushkevich (DR) equation and pore size
distribution is simply obtained from Horvath–Kawazoe (HK)
analysis [83,94]. Usually, the sieving property of CMS is evaluated
by comparing the adsorption kinetic of N2, CH4, O2 and CO2 with
kinetic diameters of 0.36, 0.38, 0.34 and 0.33 nm, respectively [11].
Various preparation methods of lignocellulosic CMS and the
textural characterizations are summarized in Table 7.

Table 7
Various preparation methods of lignocellulosic CMS.

Biomass type Pore modification condition SBET Vmic Selectivity Reference

(m2/g) (cm3/g)
O2/N2 CO2/CH4

Palm shell CVD of benzene (30 vol% in N2), 800 8C, 30 min 704 0.412 7.06 16 [11,17]
Lignin CVD of benzene (5.5 vol% in He), 800 8C 724 0.377 – – [62]
Macadamia nut shell CVD of benzene, 800 8C, 60 min 471a 0.17a – – [13]
Walnut shell CVD of benzene (3.5  104 g/mL in N2), 800 8C, 30 min 291 0.47 – – [27]
Walnut shell CVD of 3-methylpentane, 700 8C, 60 min 333.1 0.17 1.22 – [28]
Coconut shell CVD of benzene on hydrofluoric acidified char, 600 8C, 120 min – – 9.7 – [16]
Coconut shell CVD of benzene (N2 was bubbled through a benzene container), 650 8C, 60 min – – 10 >400 [14]
Grain sorghum CVD of methane (5 mL/min CH4 and 100 mL/min N2), 800 8C, 60 min 1247 0.51 – – [61]
Eucalyptus wood Controlled pyrolysis by CO2, 600 8C, (8 8C/min), 30 min – 0.018 – 20 [18]
Nut shell Controlled pyrolysis of char blended with tar and boiling in benzene 2351 – – – [95]
for 1 h/oven drying at 105 8C for 3 h/carbonization at 700 8C for 30 min
Peach stone Controlled pyrolysis by O2, 850 8C, 50 mL/min, 20 min – – – 30.1 [19]
Peach stone Controlled pyrolysis of char impregnated in HNO3 (5N) at 625 8C – – – 127.9 [19]
Lignin Controlled pyrolysis of chemically activated chars with N2 at 800 8C for 2 h 854 0.499 – – [22]
a
The pores were reopened by CO2 gasification after CVD for 50 min.
1598 A.R. Mohamed et al. / Renewable and Sustainable Energy Reviews 14 (2010) 1591–1599
3. Conclusion
Recently, biomass-based technologies have attracted consider-
able attention due to their probable waste to energy applications
and it is expected to see extensive and flourishing progress in this
area in the future. So far, little work has been published on the
preparation and characterization of lignocellulosic CMS. But, the
high potential of lignocellulosic biomass for production of
carbonaceous materials has been confirmed by many researchers.
Promising results on production of lignocellulosic CMS with large
surface area, high microporosity and selectivity have been
achieved. Successful applications of biomass-based CMSs in gas
separation systems and PSA process have been reported. It is clear
that more detailed investigations on the production, optimization
and PSA applications of lignocellulosic CMSs are required to prove
the worthiness of these biomass-based products.
Acknowledgments
The authors gratefully acknowledge the Universiti Sains
Malaysia and the Ministry of Science, Technology and Innovation
Malaysia for funding this project in the form of the USM Research
University Grant (1001/PJKIMIA/814004) and the Science Fund
Grant (305/PJKIMIA/6013327), respectively.
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