Renewable and Sustainable Energy Reviews 46 (2015) 218–235

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Agricultural bio-waste materials as potential sustainable precursors

used for activated carbon production: A review
Mohd Adib Yahya a, Z. Al-Qodah b,n, C.W. Zanariah Ngah a
a
Faculty of Science and Technology, Universiti Sains Islam Malaysia, Malaysia
b
Department of Chemical Engineering, Taibah University, Saudi Arabia

art ic l e i nf o a b s t r a c t

Article history: A review on the preparation of the activated carbon from agricultural waste material is presented. The physical
Received 31 October 2014 properties such as proximate and ultimate analysis of agricultural waste material were reviewed. The chemical
Accepted 24 February 2015 compositions such as cellulose, hemicelluloses and lignin contents were also discussed. The effects of various
parameters on the preparation such as carbonization and activation temperature, time, types of activating
Keywords: agents and impregnation ratio were reviewed. Various physical and chemical processes for the activation of
Agricultural wastes the agricultural residues and their effects on the textural properties such as surface area and pore volume were
Activated carbon discussed. The low cost, renewable and relatively less expensive of the agricultural waste were found to be
Carbonization efficiently being converted into wealth. The uses of activated carbon derived from agricultural residues in
Activation
many fields were evidently proven in the review. The reaction kinetic modeling on the pyrolysis and activation
Chemical activation
of agricultural wastes were also reviewed.
Physical activation
Modeling & 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
2. Agricultural waste material as activated carbon precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
3. Activated carbon preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
3.1. Types of activated carbon preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
3.2. Physical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
3.3. Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
3.4. Effect of activating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
3.5. Effect of impregnation ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
3.6. Effect of temperature on surface area and pore volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4. Classification of pores sizes of activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
5. Textural morphology of activated carbon derived from different agricultural waste materials under SEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
5.1. Starting material of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
5.2. Types of activating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
5.3. Concentration of chemical activating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.4. Types of activations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
6. Activated carbon applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
7. Review of formation of activated carbon from agricultural waste material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
7.1. Kinetic model for pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
7.2. Kinetic model for activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

n
Corresponding author.
E-mail addresses: mohd.adib@usim.edu.my (M.A. Yahya),
z_alqodah@hotmail.com (Z. Al-Qodah), cw.zanariah@usim.edu.my (C.W.Z. Ngah).

http://dx.doi.org/10.1016/j.rser.2015.02.051
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235 219

1. Introduction Activated carbon is also called as activated charcoal or activated

The term activated carbon is basically referred as carbonaceous
materials [1], with high porosity [2–6], high physicochemical stability
[7], high adsorptive capacity [8], high mechanical strength [9,10], high
degree of surface reactivity [11,12], with immense surface area [13,14]
which can be differentiated from elemental carbon by the oxidation of
the carbon atoms that found at the outer and inner surfaces [15].
It is basically tasteless [16], amorphous [17–19], microcrystalline
[20,21], non-graphite [22] form of carbon and a black solid substance
which resembles powder or granular charcoal [23,24]. A non-graphite
of activated carbon means that it cannot be converted into crystalline
graphite even at a temperature of above 3000 1C [25].
coal [26] and sometimes called as solid sponge [27]. According to
Cuhadaroglu and Uygun [1], activated carbon cannot be characterized
by any distinctive chemical formula. Based on its physical character-
istic, activated carbon can be classified into several classifications;
powdered activated carbon (PAC), granulated activated carbon (GAC),
extracted activated carbon (EAC) [21], pellet activated carbon [24],
fibrous activated carbon [28], activated carbon cloths [11] and others.
Activated carbon has often been associated with the existence of
the heteroatoms like oxygen, sulfur, hydrogen, nitrogen, halogen and
other elements [29–31] in the forms of functional groups and/or atoms
which bonded chemically to the structure. Oxygen is found to be
predominant which exist in the form of functional groups such as
carboxyl, carbonyl, phenols, lactone and others [32–34]. The nature and
the amount of the oxygen surface groups that found the in the
activated carbon also depend on the precursor and the activation
treatment [11]. These carbon–oxygen groups of acidic (carboxylic,
lactonic) and non-acidic (carbonyl, ether, quinone) evolve as CO2 and
CO, respectively, upon thermal decomposition. The phenol groups also
evolve as CO, similar to those non-acidic, while anhydride gives rise to
both CO and CO2 [35]. Activated carbon have either protonated
(C–OH2 þ ), neutral (COH), or ionized (CO  ) on its surface. Those with
protonated surfaces are called as H-type carbons, while ionized
surfaces are called as L-type carbons [24]. Fig. 1 represents several
IR-active functional groups that can be seen at the edges of and within
grapheme layers of activated carbon after the oxidative treatment.

2. Agricultural waste material as activated carbon precursors

According to Girgis et al. [37], activated carbon can be produced by

Fig. 1. IR-active functional groups on carbon surface: (a) aromatic C ¼ C stretching;
(b) and (c) carboxyl-carbonates; (d) carboxylic acid; (e) lactone (4-membered ring);
(f) lactone (5-membered ring); (g) ether bridge; (h) cyclic ether; (i) cyclic anhydride
(5-membered ring); (j) cyclic anhydride (6-membered-ring); (k) quinine;
(l) phenol; (m) alcohol; and (n) ketene [36].
both naturally occurring and synthetic of carbonaceous solid precur-
sor. It has been classed based on its starting material. The type of
starting material or precursor plays a primary role in influencing the
quality, characteristics and properties of the resulting activated carbon
[18,38–43]. Cagnon et al. [44] has added that structure of the starting
material also could influence the properties of the activated carbon.

Table 1
Proximate and ultimate analysis for agricultural residues.

Agricultural waste Proximate analysis (% w/w) Ultimate analysis (% w/w) References

Moisture Ash Volatiles C H N S O

Palm shell 7.96 1.10 72.47 50.01 6.9 1.9 0.0 41 Adinata et al. [64]
Palm stem 6.06 4.02 72.39 45.56 5.91 0.82 – 47.71 Alothman et al. [65]
Grape stalk 15.69 10.16 51.08 46.14 5.74 0.37 0.0 36.60 Amaya et al. [47]
Bamboo – 3.90 80.6 43.8 6.6 0.4 0.0 – Choy et al. [66]
Coconut shell 8.21 0.1 73.09 48.63 6.51 0.14 0.08 44.64 Daud and Ali [67]
Olive mill o5.0 o 1.0 – 45.64 6.31 1.42 – – Gokce et al. [56]
Almond shell 10.00 0.60 80.30 50.50 6.60 0.20 0.01 42.69 Gonzalez et al. [68]
Wallnut shell 11.00 1.30 71.80 45.10 6.0 0.3 0.0 48.60 Gonzalez et al. [68]
Almond tree pruning 10.60 1.20 72.20 51.30 6.50 0.80 0.04 41.36 Gonzalez et al. [68]
Olive stone 10.40 1.40 74.40 44.80 6.0 0.1 0.01 49.09 Gonzalez et al. [68]
Bamboo 2.44 6.51 69.63 45.53 4.61 0.22 – – Hirunpraditkoon et al. [45]
Durian shell 11.27 4.84 – 39.30 5.90 1.00 0.06 53.74 Jun et al. [69]
Chinese fir sawdust 4.88 0.32 79.92 48.95 6.54 0.11 0.00 39.20 Ke-qiang et al. [70]
Banana empty fruit bunch 5.21 15.73 78.83 41.75 5.10 1.23 0.18 51.73 Sugumaran et al. [16]
Delonix regia fruit pods 0.22 2.80 92.03 34.22 4.50 1.94 0.42 58.91 Sugumaran et al. [16]
Corn cob 4.3 0.90 78.7 46.8 6.0 0.9 – 46.3 Tsai et al. [87]
Pomegranate seed 5.38 1.83 78.71 49.65 7.54 4.03 0.65 38.13 Ucar et al. [63]
Birch 4.4 0.18 – 48.4 5.6 0.2 – 45.8 Zanzi et al. [27]
Salix 7.3 0.75 – 48.8 6.2 1.0 – 43.4 Zanzi et al. [27]
Sugarcane bagasse 6.2 0.90 – 47.3 6.2 0.3 – 46.2 Zanzi et al. [27]
Wheat straw 3.3 3.23 – 46.5 6.3 0.9 – 46.3 Zanzi et al. [27]
Bagasse – 6.2 83.3 41.55 5.55 0.03 – 52.86 Boonpoke et al. [71]
Rice husk – 16.7 67.5 36.52 4.82 0.86 – 41.10 Boonpoke et al. [71]
Cassava peel 11.4 0.3 59.4 59.31 9.78 2.06 0.11 28.74 Sudaryanto et al. [72]
Rice stalk 14.17 14.93 66.33 40.79 7.66 1.17 0.49 49.89 Ai et al. [73]
Woody birch 6.6 0.2 81.2 48.4 5.6 0.2 – 45.8 Budinova et al. [74]
220 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235

In addition, the properties of the resulting activated carbon will also activating reagent and followed by heating process under an inert
be influenced by types of activating reagents [45], time [46], impreg- atmosphere [58,116–122].
nation condition, carbonization temperature [47–50], inorganic impu- The activating reagents could dissolve the cellulosic compo-
rities [51] and others. nents of the precursor [18] and promoting the formation of cross-
Activated carbon can be produced by a variety of raw materials links [88]. Nevertheless, chemical activation has shown more
from animal, mineral and vegetables [12,52–54]. The raw materials advantages over physical activation. It needs lower temperatures,
chosen for activated carbon production basically depend on its price, produces higher yield [86], has higher surface area [7,74], only
purity, potential extent of its activation and also stability of its supply involves one step, creates well developed micro porosities
[3]. The raw materials also have to be easily activated and have [45,109], and reduction of mineral matter content as compared
properties of low degradation by aging [11]. According to Adeyi and to the physical activation [123]. However, there are also some
Oladayo [55], raw materials for activated carbon are basically of disadvantages in chemical activation such as, washing is needed to
inherent porosity, filterability, and high carbon content. The use of remove the impurities that coming from the activating agents and
natural or synthetic fibers as has also been noted [52]. also the corrosiveness properties of the agents [113].
The use of agricultural by-products for activated carbon pro-
duction has been noticed by many researchers. The waste can be
3.2. Physical activation
converted into activated carbon through pyrolysis under con-
trolled conditions with or without some chemical activating
Physical or “thermal” treatment is a two-step process; i.e. carbo-
agents [56,57]. The use of agricultural waste as activated carbon
nization and activation [59,124,125]. It is basically referred to dry
precursors has also been found to be renewable and relatively less
oxidation which involves the reaction between the samples and
expensive [45] and ultimately could utilize the waste effectively
gaseous (CO2 and air), steam or mixture of gaseous and steam [104]
into wealth [58]. Any inexpensive material that has a high carbon
at temperature reaching above 700 1C [15]. The use of CO2 has been
and a low inorganic content can be utilized as a precursor for
commonly preferred due to its clean, easy to be handled and the
activated carbon productions [59]. Subsequently, any lignocellu-
activation process can be easily controlled at temperature around
losic material can be used for activated carbon purpose [60–63].
800 1C due to its slow reaction rate [59]. A greater uniformity of pore
Table 1 presents the proximate and ultimate analysis of various
also can be achieved with the activation of CO2 as compared to steam
agricultural residues.
[126].
In general, there are two main sources of activated carbon pro-
Carbonization temperature usually ranges between 400 and 850 1C
duction; coal and agricultural by products or lignocelullosic materials
and activation temperature generally around 600–900 1C [59]. Cuha-
[75,76]. Commercially activated carbon basically uses precursors such
daroglu and Uygun [1] has reported that carbonization is a process of
as petroleum residues, wood [77], coal, peat and lignite which are very
obtaining charcoal from the starting material. The resulting charcoal
expensive and non-renewable [78–84]. Therefore, in recent years,
has a low surface area and is not an active product. According to
people have been focusing on the activated carbon preparation based
McDougall [104], the purpose of the carbonization is to reduce the
on agricultural waste and lignocelluloses materials which are effective
volatile content of the starting material to convert the resulting char
and very inexpensive [16,85], such as corn cob [86,87], hazelnut shell
with higher content of fixed carbon for activation purpose. During
[88], pruning mulberry shoot [89], olive stone [43,90], Jojoba seed
carbonization, carbon atoms rearrangement into graphitic-like
[91], Chinese fir sawdust [70], coconut shell [22,92,93], wood [93],
hazelnut bagasse [94], kenaf fiber [95], bamboo [66,96], rice husk [97],
Table 2
petai [98], groundnut shell [14,99], paper mill sludge [100], prosopis Lignocellulosic compositions of agricultural residues.
(Prosopis juliflora) [80], coconut husk [84], Jatropha husk [101],
tamarind wood [10], pistachio-nut [39], sugarcane bagasse [102], Agricultural waste Cellulose Hemicellulose Lignin References
jackfruit peel [103], and many others.
Palm shell 29.0 47.7 53.4 Adinata et al. [64]
The carbon contents of these kinds of by-products are lower as
Coconut shell 19.8 68.7 30.1 Daud and Ali [67]
compared to anthracite, coal or peat. Therefore the yields of the acti- Almond shell 32.5 25.5 24.8 Gonzalez et al. [68]
vated carbon from these precursors are expected to be lower. Wallnut shell 40.1 20.7 18.2 Gonzalez et al. [68]
However, its lower cost gives significant impact more than its lower Almond tree pruning 33.7 20.1 25.0 Gonzalez et al. [68]
yield [99,104]. The high content of volatile matters exists in the Olive stone 30.8 17.1 32.6 Gonzalez et al. [68]
Banana empty fruit 8.30 21.23 19.06 Sugumaran et al.
biomass has been ideal to produce a highly porous structure of bunch [16]
activated carbon [105]. The useful of the end products of the waste, Delonix regia fruit pod 13.90 24.13 23.36 Sugumaran et al.
particularly activated carbon, and the economic input that can be [16]
derived from these useful products eventually can off-set the costs of Pomegranate seed 26.98 25.52 39.67 Ucar et al. [63]
Coconut husk 0.52 23.70 3.54 Adeyi and Oladayo
treatment and disposal [106,107]. The lignocellulosic compositions of
[55]
agricultural residues are tabulated in Table 2. Cocoa pods 41.92 35.26 0.95 Adeyi and Oladayo
[55]
Kola nut pod 38.72 40.41 21.29 Adeyi and Oladayo
[55]
Plantain peel (ripe) 13.87 15.07 1.75 Adeyi and Oladayo
3. Activated carbon preparation [55]
Plantain peel (unripe) 10.15 11.38 1.75 Adeyi and Oladayo
3.1. Types of activated carbon preparation [55]
Coconut shell 15.0 35.0 50.0 Cagnon et al. [108]
Apple pulp 16.0 16.0 21.0 Cagnon et al. [44]
There are two different processes for activated carbon preparation;
Plum pulp 6.5 14.5 39.0 Cagnon et al. [44]
chemical and physical treatment [8,58,69,110–114]. Both treatments Plum stone 23.0 20.0 49.0 Cagnon et al. [44]
are responsible in varying the shapes and the sizes [115]. In physical Olive stone 14.0 15.0 42.0 Cagnon et al. [44]
treatment, precursors will be first carbonized followed by activation Soft wood 36.0 18.5 30.5 Cagnon et al. [44]
step by steam or carbon dioxide. It means that this physical activation Coconut shell 14.0 32.0 46.0 Cagnon et al. [44]
Sugarcane bagasse 42.16 36.0 19.30 Chen et al. [102]
involves two steps; carbonization step and activation step. On the Cocoa pod husk 41.92 35.26 0.95 Cruz et al. [109]
other hand, in chemical treatment, precursors are impregnated by an
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235
Fig. 2. Gradual activation process of carbon during thermal treatment [12].
structure occurs. Rodriguez-Reinoso and Molina-Sabio [127] reported
that, the pyrolysis of the polymeric cellulose or lignin in carbonization
process releases most of the non-carbon elements particularly hydro-
gen, oxygen, and nitrogen, in the form of gases and tars. This process
will then produce a carbon skeleton which formed by aromatic sheets
and strips and resembles a mixture of wood shavings and crum-
pled paper.
The carbonization process also is intended to create initial porosity
in the char [128]. The porosity development in this treatment occurs
through the selective elimination of the more reactive carbon of the
structure [129]. Further gasification will then produce the activated
carbon with high porosity [23,48,121,130].
The steps of physical activation by steam oxidation involve
preoxidation, pyrolysis, and steam activation. In preoxidation, the
air is diluted in half using N2 initially. It is of paramount to reduce
the concentration of oxygen to avoid the increasing temperature
from an exothermic reaction between oxygen and coal. Therefore,
preoxidation step could minimize the coal caking formation and
agglomeration during pyrolysis step. The sample will undergo the
pyrolysis step and followed by steam activation by replacing the
N2 flow with a mixture of 50% H2O and 50% N2 [131].
Carbonization is basically involved the pyrolytic decomposition of
the precursor and non-carbon species elimination. The low molecular
weight volatiles will be first released and followed by light aromatics
and hydrogen gas. This process will result in a fixed carbonaceous char
produced. The tarry pyrolysis residues will fill the pores which formed
during carbonization. This carbonaceous form will be activated by
activation process [115]. In the process, there are formations of pores
and vessels due to the entrance of the oxidizing gases into the char
and removal of the reaction products through particles [1]. The
gasification process will first eliminate the more reactive carbon
atoms hence generating porosity. Further gasification will finally
produce activated carbon with high porosity [127]. The type and
degree of activation could affect the physical and chemical properties
of the activated carbon [92]. The purpose of activation is basically to
develop further porosity and creating some ordering of the structure
which results in a highly porous solid of the activated carbon [9]. The
pore development in activation process has been divided into three
phases; opening of previously inaccessible pores, new pore develop-
ment by selective activation, and widening of the existing pores [92].
Fig. 2 represents the gradual activation process during the thermal
treatment of the activated carbon. Table 3 summarizes carbonization
and activation condition of various agricultural residues.
3.3. Chemical activation
Chemical activation is also called as wet oxidation [15] requires
catalyst to be impregnated into the precursor and washed to
221
produce the activated carbon [23,141–143]. This activation basi-
cally involves a relatively low temperature range from 300 to
700 1C [117] or 400 to 700 1C [37] or 400 to 800 1C [17] or 500 to
800 1C [8,144] and basically depends on the action of the inorganic
additives to degrade and dehydrate the cellulosic materials found
in the precursor [145]. According to Molino-Sabio and Rodriguez-
Reinoso [146], chemical activation has been commonly done at
450–600 1C. Activating agents basically act as dehydrating agents
and oxidants [59,147] which could influence the pyrolytic decom-
position. It also could prevent the formation of the tar or ash hence
developing the carbon yield [40,99,148].
The chemical catalysts (oxidizing agents) that usually used are
ZnCl2, H3PO4 [109,149,150], H2SO4, K2S, KCNS [94], HNO3, H2O2,
KMnO4, (NH4)2S2O8 [15], NaOH, KOH [151], and K2CO3 [58,64]. The
surface oxygen functional groups can be introduced to the carbon
of the precursor when react with activating agents [20].
Always, the final stage in activated carbon preparation in
chemical activation is the washing step. In this step, the activated
carbon is basically washed with acid or alkali, depending on the
chemical reagents used in the preparation, and followed by
washing with water. The washing step would remove the chemical
components in the activated carbon. The porosity of the resulting
activated carbon is basically occupied by the chemicals in the
carbon structure. Hence, washing step is one of the most impor-
tant steps in the chemical activation to develop porosity in the
activated carbon [75]. Table 4 presents various activation condi-
tions of the agricultural residues.
3.4. Effect of activating agents
Among the chemical activating agents, ZnCl2 and H3PO4 are
commonly used for activation purpose for lignocellulosic materials
[125]. The use of ZnCl2 could produce higher surface area as compared
to H3PO4 [15]. Donald et al. [150] reported that ZnCl2 is efficient in
producing microporous structure in the activated carbon and produ-
cing greater surface area. Whereas, H3PO4 is effectively producing the
mesopores, and resulting in higher pore volumes and diameter.
Nevertheless, H3PO4 is more preferred since ZnCl2 could give
unfriendly environmental impact [149] and the activated carbon
which produced using ZnCl2 cannot be used in food and pharmaceu-
tical industries [15]. The use of H3PO4 also provides easier way to
recover the carbon product during processing stage which only rinsing
with water is needed [89,98]. It also gives higher yield of activated
carbon and has non-toxic properties [42].
Mechanisms involved by different catalysts are different. For
instance, the use of ZnCl2 could promote the water molecules
extraction from the lignocellulosic structures of the parent materials
or the precursors, whereas H3PO4 could combine chemically within
222 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235

Table 3
Carbonization and activation condition of various agricultural residues.

Starting Particle Carbonization Activation Chemical Additional information References

material size condition condition treatment

Pistachio-nut 2.0– N2, 250– 900 1C/30 min CO2 One-step pyrolysis/activation Lua et al. [132]
shell 2.8 mm 1000 1C/2 h
Palm kernel 0.22 mm N2, 250–750 1C/ 500–900 1C/ K2CO3 Chemical activation, impregnation ratio 1:1 Olowoyo and Orere
nut shell 1h 15 min [133]
Coconut shell 0.22 mm N2, 250–750 1C/ 500–900 1C/ K2CO3 Chemical activation, impregnation ratio 1:1 Olowoyo and Orere
1h 15 min [133]
Ground nut 0.22 mm N2, 250–750 1C/ 500–900 1C/ K2CO3 Chemical activation, impregnation ratio 1:1 Olowoyo and Orere
shell 1h 15 min [133]
Obeche wood 0.22 mm N2, 250–750 1C/ 500–900 1C/ K2CO3 Chemical activation, impregnation ratio 1:1 Olowoyo and Orere
1h 15 min [133]
Gelam wood 0.5– N2, 500 1C/3 h 500 1C/1 h CO2/ZnCl2 5–40% w/w of ZnCl2 concentration Abdullah et al. [23]
bark 1.0 cm
Palm kernel 1.18 mm N2, 400 1C/1 h 800–1000 1C/ KOH Carbonization followed by impregnation with char with ratio 1:1 Abechi et al. [38]
shell 15–40 min for 2 h
Bamboo N2, 400–500 1C/ 800 1C/2 h HCl 0.1 M HCl, impregnated until form a paste Ademiluyi et al.
2h (2009)
Palm shell 1–2 mm N2, 600– – K2CO3 One-step carbonization-activation, impregnation ratio 0.5–2.0 Adinata et al. [64]
1000 1C/2 h
Mango seed 2–4 cm N2, 500 1C/1 h – ZnCl2 One step carbonization-activation, impregnation ratio 1:2 and 1:3 Akpen et al. [134]
shell
Neem husk – N2, 200–500 1C/ – H3PO4 One-step carbonization-activation, optimum at 500 1C Alau et al. [135]
10 min
Neem husk – N2, 200–500 1C/ – KOH One-step carbonization-activation, optimum at 350 1C Alau et al. [135]
10 min
Neem husk – N2, 200–500 1C/ – ZnCl2 One-step carbonization-activation, optimum at 400 1C Alau et al. [135]
10 min
Palm shell 0.5– N2, 400–800 1C/ 400–800 1C/ CO2/ZnCl2 65% ZnCl2, physicochemical activation Allwar et al. [136]
1.5 mm 3h 90 min
Olive waste o 1.5 mm N2, 350–650 1C/ – H3PO4 One step carbonization-activation Baccar et al. [137]
cake 2h
Date tree – N2, 400 1C/3 h – H3PO4 One step carbonization-activation Al-Swaidan and
frond Ahmad [110]
Rice husk – N2, 500 1C/1 h – ZnCl2 One step carbonization-activation, impregnation ratio 1:1 Boonpoke et al. [71]
Bagasse – N2, 500 1C/1 h – ZnCl2 One step carbonization-activation, impregnation ratio 1:1 Boonpoke et al. [71]
Woody birch 0.5– N2, 600 1C/1 h 600 1C/1 h Steam/H3PO4 Impregnated samples were heated in nitrogen flow and submitted Budinova et al. [74]
1 mm to a steam flow
Woody birch 0.5– – 700 1C/2 h Steam/H3PO4 Impregnated samples were directly pyrolized in a steam flow Budinova et al. [74]
1 mm
Coconut shell – N2, 400–800 1C/ 800 1C/60– Steam Chars were subsequently into contact with N2 þH2O mixture Cagnon et al. [108]
1h 270 min
Coconut shell – N2, 400–800 1C/ 800 1C/60– N2 þ steam Chars were cooled to room temperature before further activated Cagnon et al. [108]
1h 270 min with N2 þ H2O mixture
Kenaf fiber 1–2 mm N2, 400 1C/2 h 700 1C/ 1 h CO2/KOH Char was impregnated with KOH with ratio of 1.4, heating rate Chowdhury et al. [95]
constant at 10 1C/min
Palm shell 1–2 mm N2, 850 1C/1 h 850 1C/5– CO2 One-step pyrolysis/activation Daud and Ali [67]
80 min
Coconut shell 1–2 mm N2, 850 1C/1 h 850 1C/5– CO2 One-step pyrolysis/activation Daud and Ali [67]
80 min
Palm shell 1–2 mm N2, 500–900 1C/ 820 1C/20– N2 þ steam Char was activated in a mixture of N2 þ H2O Daud et al. [128]
1h 250 min
Hazelnut 0.6– N2, 500–700 1C/ – KOH One step carbonization/activation Demiral et al. [94]
bagasse 0.8 mm 2h
Hazelnut 0.6– N2, 500–700 1C/ – ZnCl2 One step carbonization/activation Demiral et al. [94]
bagasse 0.8 mm 2h
Stink bean 125 mm N2, 450–650 1C/ – H3PO4 One step carbonization/activation Foo and Lee [98]
(petai) 1h
Groundnut 2 mm N2, 800 1C/ – H3PO4 One and two steps activation Gimba et al. [138]
shell 5 min
Groundnut 2 mm N2, 800 1C/ – KOH One and two steps activation Gimba et al. [138]
shell 5 min
Groundnut 2 mm N2, 800 1C/ – ZnCl2 One and two steps activation Gimba et al. [138]
shell 5 min
Coffee waste 1–2 mm N2, 700 1C 700 1C/2–3 h CO2/ZnCl2 Impregnation ratio 2:1 to 3:1, heating rate at 10 1C/min Giraldo and Moreno-
Pirajan [117]
Coffee waste 1–2 mm N2, 700 1C 700 1C/2–3 h CO2/KOH Impregnation ratio 2:1 to 3:1, heating rate at 10 1C/min Giraldo and Moreno-
Pirajan [117]
Almond shell 1–2 mm N2, 600 1C/1 h 850 1C/30 min Steam Chars were subsequently into contact with diluted N2 þH2O, Gonzalez et al. [68]
steam partial pressure equal to 0.61
Walnut shell 1–2 mm N2, 600 1C/1 h 850 1C/30 min Steam Chars were subsequently into contact with diluted N2 þH2O, Gonzalez et al. [68]
steam partial pressure equal to 0.61
Almond tree 1–2 mm N2, 600 1C/1 h 850 1C/30 min Steam Chars were subsequently into contact with diluted N2 þH2O, Gonzalez et al. [68]
pruning steam partial pressure equal to 0.61
Olive stone 1–2 mm N2, 600 1C/1 h 850 1C/30 min Steam Chars were subsequently into contact with diluted N2 þH2O, Gonzalez et al. [68]
steam partial pressure equal to 0.61
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235 223

Table 3 (continued )

Starting Particle Carbonization Activation Chemical Additional information References

material size condition condition treatment

Bamboo 1–2 mm N2, 700 1C/1 h 850 1C/2 h CO2/KOH Impregnation ratio of 1:1 Hameed et al. [139]
Corn cob 0.7– N2, 600–900 1C/ – KOH One step carbonization/activation Hiremath et al. [26]
1.2 mm 2h
Coconut shell 1–2 mm N2, 800 1C 800 1C/2–3 h CO2/ZnCl2 Impregnation ratio varied from 0.25–3 by weight Hu and Srinivasan [8]
Palm seed 1–2 mm N2, 800 1C 800 1C/2–3 h CO2/ZnCl2 Impregnation ratio varied from 0.25–3 by weight Hu and Srinivasan [8]

Table 4
Various activation conditions of the agricultural residues.

Activation Material Activating References

method agent

Chemical Palm shell, mango peel, palm kernel shell, coconut shell, ground K2CO3 Adinata et al. [64], Bello and Ahmad [145], Olowoyo and Orere [133],
nut shell, obeche wood, cocoa pod husk Cruz et al. [109], Gimba and Turoti [152]
Mango seed shell, palm stem, wood apple outer shell, rice husk, ZnCl2 Akpen et al. [134], Alothman et al. [65], Bhadusha and
coconut shell, olive mill waste, ground nut shell, prosopis, maize Ananthabaskaran [153], Daffalla et al. [154], Gimba and Turoti [152],
cob, cocoa pod husk Gokce et al. [56], Hassan et al. [19], Kailappan et al. [80], Ketcha et al.
[124], Cruz et al. [109]
Vetiver root, grape stalk, olive waste, sugarcane bagasse, rice H3PO4 Altenor et al. [77], Amaya et al. [47], Baccar et al. [137], Chen et al. [102],
husk, stink bean (petai), groundnut shell, date palm tree, durian Daffalla et al. [154], Foo and Lee [98], Hassan et al. [19], Houache et al.
shell [155], Jun et al. [69]
Almond husk, flame tree pod, groundnut shell H2SO4 Hasar [156], Ho et al. [13], Idris et al. [14]
Corn cob, bamboo, date palm tree, oil palm shell, coconut husk, KOH Hiremath et al. [26], Hirunpraditkoon et al. [45], Houache et al. [155],
coconut shell, cocoa pod husk Joseph et al. [148], Lee et al. [76], Cruz et al. [109]
Tobacco stem CaCl2 Jambulingam et al. [157]
Tobacco stem Na2SO4 Jambulingam et al. [157]
Tobacco stem Na2CO3 Jambulingam et al. [157]

Physical Vetiver root, jute stick, coconut shell, sugarcane bagasse, almond Steam
shell, walnut shell, almond tree pruning, olive stone, hazelnut
shell
Rice straw, rice hull, sugarcane bagasse, pecan shell, palm shell, CO2
coconut shell, almond husk, pistachio-nut shell
Altenor et al. [77], Asadullah et al. [149], Cagnon et al. [108], Devnarain
et al. [116], Gonzalez et al. [68], Khalkhali and Omidvari [53], Li et al.
[92]
Ahmedna et al. [78], Daud and Ali [67], Guo et al. [9], Hasar [156], Lua
et al. [132]

Physicochemical Oil palm shell, coconut shell, palms seed, gelam wood bark ZnCl2/CO2 Allwar et al. [136], Hu and Srinivasan [8], Hu et al. [140], Abdullah et al.
[23]
Woody birch H3PO4/ Budinova et al. [74]
steam
Kenaf fiber KOH/CO2 Chowdhury et al. [95]

the lignocellulosic structures. Donald et al. [150] proposed that the
activation by H3PO4 involves the formation of cross-link structures in
phosphate ester form which directly related to the porosity develop-
ment. These cross-links reach the limit of thermal stability at
temperature of 450–500 1C. These cross-links would cause contraction
at higher temperature hence reducing the porosity development.
Wang et al. [89] reported that H3PO4 promotes the pyrolictic
decomposition and cross-link structure. The decomposition pro-
cess was attributed to the catalytic effect of the H3PO4 on the bond
cleavage reactions, while cross-link phenomenon was attributed to
H3PO4 and biomass interactions which resulting in phosphate
linkage formation between the fragments present in the biomass.
Meanwhile, in ZnCl2 activation, the “swelling” effects of the ZnCl2
occur by lateral bonds breaking in the cellulose molecules leading
to an increased inter- and intra-voids. The interspaces between
carbon layers created by ZnCl2 would develop the microporosity.
The use of high temperatures is basically to develop the porosity of
the samples by removing the low-molecular-weight volatile com-
pounds from the matrix structure [136]. The chemical treatment
has been known to be the most commonly used to produce
activated carbon due to its lower activation temperature and
produce better properties of the product as compared to the
physical treatment [136].
Bello and Ahmad [145] had also stated that chemical activation
could improve the pore development in the carbon structure.
Allwar et al. [136] explained that the use of ZnCl2 could increase
the heat of energy on the pyrolysis process which could help the
porosity development of the activated carbon. Alothman et al. [65]
reported that, ZnCl2 also could act as a Lewis acid. It increases the
reactions of aromatic condensation by allowing the evolution of
the molecular hydrogen from the hydroaromatic structure of the
precursor, hence leaving the active sites on the adjacent molecules
which will undergo the polymerization (aromatization) reactions.
In short, ZnCl2 gives inhibiting effects on the volatile matter which
will stabilize the volatile matter and eventually will produce the
carbon yield. Cecen [158] stated that high mechanical strength and
high capacities of adsorptive for gases and vapor could be
produced by activated carbon treated with ZnCl2. Al-Swaidan
and Ahmad [110] found that the use of H3PO4 basically requires
low activation temperature (usually about 400 1C) and could still
produce a higher grade of activated carbon. Other than that, H3PO4
has a good cation-exchange capability, chemical and thermal
stability.
The use of KOH as activating agents has been found to be effective
in activated carbon production with a narrow pore size distribution
and well-developed porosity [126,159]. It has been proposed that
mechanism of activation involving alkaline metal such as KOH; in
which the alkali metal intercalates in the carbon lattice and will act as
electron donor that sparks the reaction during gasification. The
presence of oxygen in the alkali could remove the carbon atoms
cross-linking in the crystallites. The liberation of potassium metal at
high temperature intercalates and forcing a part of the separate
lamellae of the crystallite [126]. The use of KOH was suggested to
be more eco-friendly as compared to the ZnCl2 [38].
224 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235
3.5. Effect of impregnation ratio
Impregnation ratio is defined as the ratio of the weight of the
activating agent to the precursor [17]. Impregnation ratio has been
identified as one of the most important factors in the chemical
activation process [75]. According to Giraldo and Moreno-Pirajan
[117], impregnation ratio has significant effect on the porosity devel-
opment. They used ZnCl2 and KOH as activating agents and varied the
ratio of the activating agents and precursor from 2:1 and 3:1. With the
increased of ratio from 2 to 3, the surface area and the total pore
volumes also increased. The increase in porosity was attributed to the
release of the tars that exist from the cross-linked framework which
due to the chemical reagents.
Akpen et al. [134] had studied the removal of colour from waste
water by activated carbon produced from seed of two kinds of
mangos which were local and dausha. They used anhydrous ZnCl2
as a chemical treatment. The impregnation ratios were 1:2 and
1:3. The efficiency of the activated carbons were in the order of
local 1:2 4local 1:34 dausha 1:2 4 dausha 1:3. They found that
the impregnation ratio could affect the efficiency of the activated
carbon.
Ucar et al. [63] also found that impregnation ratio had strong effect
on the surface area of the activated carbon produced from pome-
granate seeds, using ZnCl2 as an activating agent. Wang et al. [89]
prepared activated carbon from pruning mulberry shoot which they
found that impregnation ratio significant effect on the yield and iodine
adsorption capacity of the activated carbon. The yield and iodine
number increased from 35.59% to 37.80% and 886.14 mg/g to
1067.77 mg/g, respectively from the ratio of 1:1 to 2:1 with H3PO4
as activating agents. However both yield and iodine number decreased
for impregnation ratio of 3:1.
A study done by Malik et al. [99] also produced the similar
result in which the increased ratio of ZnCl2 caused the increased
surface area, pore volume, iodine number and methylene blue.
However the yield of the activated carbon decreased. Mdoe and
Mkayula [160] studied the properties of activated carbon derived
from rice husks prepared by KOH chemical activation. The vari-
ables studied were impregnation ratio and temperature. They also
found that when both variables were increased, the surface area
and adsorption capacity of activated carbon were also increased.
The yield also decreased with the increased of the variables.
3.6. Effect of temperature on surface area and pore volume
Carbonization temperature affects the activated carbon pro-
duced, followed by heating rate, nitrogen flow rate and carboniza-
tion time. In general, the increased of the temperature would
decrease the chars and activated carbons productions. It leads to a
decreased of the solid yield and an increased of the liquid and
gases. The increased of the temperature would increase the ash
and fixed carbon percentage and decrease the volatile matter,
respectively [59].
Asadullah et al. [149] studied the effect of temperature on the yield
and the properties of activated carbon prepared from jute stick char by
physical activation. They studied on five different temperatures:
700 1C, 750 1C, 800 1C, 850 1C, and 900 1C. They found that tempera-
ture could affect the yield of activated carbon. The higher temperature
produced higher activation burn-off which eventually reduced the
yield of activated carbon. They reported that, the activation burn-off
occurred due to the steam reforming of char and forming carbon
monoxide and hydrogen. They also found that there was no relation-
ship between activation burn-off and either BET surface area or the
iodine number. However, the BET surface area and the iodine number
decreased after 750 1C. They found that the temperature of 750 1C
gave the highest BET surface and iodine number compared to others.
Mozammel et al. [40] studied the effects of temperature, time,
and impregnation ratio on the yield of activated carbon produced
from coconut shell using ZnCl2 as activating agent. The study
found that the higher temperature had produced better activation
but with lower yield. Tsai et al. [87] prepared activated carbon
from corn cob. They found also that higher temperature was
favorable for activated carbon in terms of surface area, total pore
volume, true density and porosity, but with lower yield.
Hayashi et al. [2] investigated the effect of the carbonization
and activating chemicals (ZnCl2, H3PO4, K2CO3 and other alkali
metals compound) onto the pore structure of activated carbon
produced from lignin. They found that both ZnCl2 and H3PO4
treatment had obtained maximum surface area at carbonization
temperature of 600 1C. They also found that maximum surface
area of activated carbon treated with alkali metal compounds was
obtained at temperature of 800 1C. It was concluded that ZnCl2
worked as dehydrating reagents at temperature of below 600 1C.
Meanwhile, K2CO3 acted as dehydrogenation reagents at carboni-
zation temperature below 500 1C.
Hayashi et al. [58] prepared activated carbon on five different
samples of nutshells and varied the temperature between 773 K
and 1173 K by using K2CO3 as activating agents. They found that
specific area for every five samples studied increased with the
increased temperature between 773 K and 1073 K and decreased
at the temperature of 1173 K. They also studied the influence of the
temperature on the pore volume development on the two differ-
ent samples studied. Micropore volumes were higher as compared
to the mesopore volume at all carbonization temperatures. How-
ever, micropore volumes decreased for both samples at 1173 K.
They had concluded that there was combination of the micropores
taking place at temperature of beyond 1073 K. Hence, the micro-
pore volumes and mesopore volumes decreased and increased
respectively and caused the decrease of the surface area.
Alau et al. [135] studied the effect of the preparation conditions
on the yield and quantity of the activated carbon produced from
neem husk (Azadirachta indica) by using three different activating
agents which were ZnCl2, H3PO4, and KOH. They found that every
chemical agent had different optimum activation temperatures
which were 400 1C, 500 1C, and 350 1C for ZnCl2, H3PO4, and KOH
respectively.
Allwar et al. [136] studied the textural characteristics of activated
carbon produced from oil palm shells. They used ZnCl2 as an activating
agent. The pyrolysis was done at different activation temperatures in
the range of 400–800 1C. They found that the micropores volume of
the activated carbon increased with the increased temperature from
400 1C to 500 1C, and decreased with further increased activation
temperature. The maximum micropore volume was 0.74 cm3 g  1, at
temperature of 500 1C. They stated that the use of 400 1C was not
sufficiently enough to develop the porosity and eventually producing
low micropore volume of activated carbon. Nevertheless, when the
temperature was increased in the range of 600–800 1C, the micropore
volume was decreased due to contraction or breaking some of the
porous wall of activated carbon which could block the pores.
Foo and Lee [98] studied the properties of the activated carbon
prepared from “petai” by varying temperature from 450 1C to 600 1C.
They used H3PO4 as activating agent and the impregnation ratios were
1:1 and 2:1. They found that the surface area was gradually increased
from 450 1C to 600 1C and started to decrease from 650 1C onwards.
The porosity also increased with the increased of temperature. They
concluded that it was attributed to the release of the tars from the
cross-linked framework generated by the activating agent used. They
also found that the ratio of 1:1 had higher surface area and pore
volume as compared to the ratio of 2:1.
Baseri et al. [130] has used Thevetia peruviana as a precursor to
produce activated carbon with different treatments using physical
and chemical treatments. The physical treatments were done from
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235
direct pyrolysis and dolomite process. The chemical treatments were
done by using chemicals such as KOH, ZnCl2, H3PO4, and H2SO4.
Comparative studies were performed based on the iodine number,
porosity, conductivity, bulk density, fixed carbon etc. The studies found
that, chemical treatment produced from impregnation of H3PO4 had
given the best activated carbon based on its high porosity, high iodine
number, low ash content, low moisture content etc.
Daffalla et al. [154] used rice husk as precursor to prepare
activated carbon using ZnCl2 and H3PO4 as activating agents to
remove phenol. They carried out at different chemical ratios of
activating agents and precursors. They found that carbonization
temperature had significant effects on the pore structure of
carbon. The carbon yield also increased with the increased of the
ratio of the activating agents. The temperature used was 500 1C
and 600 1C for 1 h of time. The ratios for rice husk to activating
agents were varied from 1:1 to 1:2. They also stated that the use of
high temperature could decrease the yield of carbon since the high
temperature could release the increasing volatiles, hence reducing
the yield. The impregnation ratio of 1:2 found to be better as
compared to 1:1 for both types of activating agents. They also
found that the use of H3PO4 produces a well-developed of the
porosity and high yield of carbon as compared to ZnCl2. The study
showed that the increased of temperature from 500 1C to 600 1C
could decreased the removal of phenol. The phenomenon occurred
due to the fact that, when activation temperature was higher than
500 1C, violent gasification reaction occurred and caused the
damage of the micropore structure by collapsing or combining
together hence reduced the removal efficiency of phenol.
A study by Gonzalez-Serrano et al. [35] showed that the activation
temperature did not have a significant effect on the mesopore size of
distribution. They also reported that the impregnation ratio affected
significantly on the distribution of porosity but did not have an effect
on the BET surface of the activated carbon produced. They also found
that the increased in the activation temperature increased the total
amount of the carbon–oxygen surface groups in the activated carbon
which produced from precursor of kraft black liquors.
Daud and Ali [67] compared the pore development of activated
carbon prepared from two types of lignocellulosic materials; palm
shell and coconut shell. Both types were prepared from identical
experimental conditions. They found that, within the burn-off range,
the micropore and mesopore volumes in palm shell activated carbon
were higher than that of coconut shell. Based on macropore volume,
for palm shell activated carbon, the volume of macropore was
increased with the increased of the burn-off up to 30% and finally
decreased. In comparison, coconut shell activated carbon the change
of macropore volume with burn-off was negligible. They also found
that absolute mcaropore volume of coconut shell activated carbon
decreased with burn-off. The micropore volume of palm-shell acti-
vated carbon was always higher than that of coconut shell activated
carbon. The similar trend was also observed in mesopore volume. The
author concluded that this phenomenon was attributed to the
inherent characteristic of the starting material such as lignocellulosic
composition, texture and botanical family of the starting material.
Daud et al. [128] studied the effects of carbonization temperature
on the pore development of activated carbon derived from palm shell.
The palm shell was first carbonized at three different temperatures;
500, 800 and 900 1C, and followed by activation at 820 1C. They found
that activated carbon that prepared from char at higher temperature
had a significant amount of micropore volume. They also identified
that, for all three carbonization temperatures, both micropore and
mesopore volumes had the maximum values at intermediate carbon
burn-off. The study also found that the development of micropore
volume varied almost proportionally with the burn-off values. As the
burn-off increased, there was a rapid development of the mesopore.
The author concluded that at higher carbonization temperature, there
was a development of a more order structure in the char which
225
resulted in slower gasification rate in the interior part of the particle.
The author also found that there was no clear pattern of the effects of
the carbonization temperature on the mesopore and macropore
volume.
Li et al. [92] also investigated the effects of carbonization
temperature on the porosity development in coconut shell chars
and activated carbon derived from coconut shell char. The coconut
shell was carbonized at four different temperatures; 400, 600, 800,
and 1000 1C followed by physical activation of the chars at 900 1C
at four different activation times; 30, 60, 90 and 120 min. The
study found the similar results in which both char and activated
carbon had higher BET surface area, total volume, micropore
volume and yield, at higher temperature. Tables 5 and 6 summar-
ize the chemical and physical condition and characteristics of the
activated carbon derived from agricultural residues, respectively.
4. Classification of pores sizes of activated carbon
According to International Union of Pure and Applied Chemistry
(IUPAC), the pore size of the activated carbon has been categorized
into three types; micropore (pore sizeo2 nm), mesopore (2 nmo-
pore sizeo50 nm), and macropore (pore size450 nm) [107,125].
Micropore can further be subdivided into ultramicropore (o0.5 nm)
and supermicropore (1–2 nm) [106]. In angstroms unit, the pore size
has been defined as micropore (8–100 Å), mesopore (100–500 Å), and
macropore (500–20,000 Å). These values generally indicate the width;
the distance between the radius for cylindrical pores and distance
between the walls for slit-shaped pores [67]. Fig. 3 presents a model
for the microstructure of microporous carbon.
The shape of the pore of activated carbon, in cross section view,
seems to be cylindrical or rectangular, and sometimes can be irregular
[104]. Teng and Yeh [164] reported that, pore structure, in terms of
surface area and pore volume is an important property of activated
carbon. The pore size requirements of activated carbon generally
depend on the types of applications. For instance, a higher pore
volume in the macropore (450 nm) range is needed to avoid
diffusing of the liquid into the mesopore (2–50 nm) and micropore
(o2 nm) region. In gas-phase applications, pore volumes of mesopore
and micropore regions are appropriate [150]. Micropores basically
contribute to mainly surface area, while macropores contribute as
channel to micropore surfaces [116].
Pore size distribution of the resulting activated carbon basically
depends on the degree of initial impregnation of the catalyst used.
The shapes and the sizes also depend on the mechanism of
activations involved. The porosity produced is due to increasing
burn-off of the disorganized carbon [115]. Daud and Ali [67]
reported that the pore structure of the activated carbon and its
pore size distribution is mainly dependent on the nature of the
starting material. According to Laine and Yunes [165], the porosity
of an activated carbon is influenced by its starting material and its
pore size distribution depends on the activation method. Li et al.
[92] stated that activated carbon with different pore characteristics
can also be produced even from the same starting material. This
can be achieved by varying the operating variables and activation
agents. It shows that, starting material and the condition of
carbonization and activation are the most important factors the
affect the types of porosity of the resulting activated carbon
[75,155].
5. Textural morphology of activated carbon derived from
different agricultural waste materials under SEM
Scanning electron microscope (SEM) is a fundamental instrument
to study the textural surface morphology of the resulting activated
226 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235

Table 5
Chemical activation conditions and characteristics of the activated carbon.

Starting material Activation condition SBET (m2/g) Vmic (cm3/g) Vt (cm3/g) Pore size (nm) References

Cotton stalk H3PO4 1720 0.71 0.89 – Nahil and William [161]
Wood apple outer shell ZnCl2 794 – 0.47 – Bhadusha and Ananthabaskaran [153]
Hazelnut shell ZnCl2 647 – 0.35 34.0 Ozcimen and Ersoy-Mericboyu [162]
Apricot stone ZnCl2 814 – 0.43 34.7 Ozcimen and Ersoy-Mericboyu [162]
Coir pith ZnCl2 910 0.13 0.36 1.60 Subha and Namasivayam [163]
Palm kernel shell KOH 217 0.11 0.12 – Abechi et al. [38]
Bagasse ZnCl2 923 – 0.53 0.80 Boonpoke et al. [71]
Rice husk ZnCl2 927 – 0.56 0.80 Boonpoke et al. [71]
Cocoa pod husk KOH 490 – 0.24 2.0 Cruz et al. [109]
Cocoa pod husk K2CO3 615 – 0.31 2.0 Cruz et al. [109]
Cocoa pod husk ZnCl2 780 – 0.58 2.9 Cruz et al. [109]
Acacia mangim wood KOH 5.25 – 0.015 11.79 Danish et al. [111]
Hazelnut bagasse KOH 1642 0.60 0.96 – Demiral et al. [94]
Hazelnut bagasse ZnCl2 1489 0.45 0.93 – Demiral et al. [94]
Bamboo KOH 1533 – 0.5 – Hirunpraditkoon et al. [45]
Durian shell H3PO4 1024 0.21 0.35 2.5 Jun et al. [69]

Table 6
Physical activation conditions and characteristics of the activated carbon.

Starting material Activation condition SBET (m2/g) Vmic (cm3/g) Vt (cm3/g) Pore size (nm) References

Pistachio-nut shell CO2, 900 1C/30 min 778.1 0.22 0.47 – Lua et al. [132]
Sugarcane bagasse Steam, 900 1C/2 h 320 – 0.17 2.1 Devnarain et al. [116]
Peanut hull Steam, 600 1C/2 h 253 0.09 0.22 – Girgis et al. [37]
Almond shell Steam, 850 1C/30 min 601 0.34 0.37 – Gonzalez et al. [68]
Walnut shell Steam, 850 1C/30 min 792 0.44 0.52 – Gonzalez et al. [68]
Almond tree pruning Steam, 850 1C/30 min 1080 0.57 0.95 – Gonzalez et al. [68]
Olive stone Steam, 850 1C/30 min 813 0.45 0.55 – Gonzalez et al. [68]
Coconut shell CO2, 600 1C/2 h 1700 0.88 1.14 2.7 Guo et al. [9]
Coconut shell Steam, 1000 1C/120 min 1926 0.93 1.26 2.6 Li et al. [92]

biomass. Different biomass would produce different texture mor-

Fig. 3. A model of the microstructure of a microporous carbon [36].
carbon. Porosity parameters of activated carbon from different types of
agricultural residues generally imply that the difference in lignin and
cellulose content of the starting materials could affect the porous
structure of the activated carbon. A higher lignin contents and
cellulose produce activated carbons with macroporous and micropor-
ous structure respectively [162]. In general, the texture of the activated
carbon can be influenced by many factors including starting materials,
experimental conditions, types of activations, and types of chemical
agents as well as its impregnation ratio or concentration.
5.1. Starting material of biomass
Studies have shown that the most important factors that influ-
ence the texture of activated carbon are its starting material of
phology although with similar types of treatments. Martinez et al.
[166] reported that the texture of the carbon as well as porosity
development is strongly affected by its starting material character-
istic. The author investigated two different biomass i.e. walnut shells
and olive pits. The former one had a homogeneous structure of
carbon whereas the latter had rougher textures of carbon with
heterogeneous surfaces. The study also found that there was no
major difference in the external surface characteristics for both
biomasses under different concentration of chemical activating
agents (KOH) as shown in Fig. 4(a) and (b). Yahaya et al. [168,169]
produced activated carbon from rice husk with chemical activation
and physicochemical activation respectively. The studies also showed
that both different types of activation produced homogenous types
pore structure distribution.
Khalil et al. [167] also found that different starting materials of raw
materials produced different textural surface morphology. They pre-
pared activated carbon produced from three different biomass; oil
palm empty fruit bunch (EFB), bamboo stem (BS), and coconut shell
(CNS) using potassium hydroxide under nitrogen atmosphere. Never-
theless all the activated carbons showed irregular cavities and have
cracks and small pits that distributed over the surface due to strong
interaction with chemical agents used as shown in Fig. 4(c)–(e). Okibe
et al. [82] studied two different types of seed hulls; Brachystegia
eurycoma (BESH) and Prosopis africana (PASH) derived activated
carbon by chemical activation (H3PO4) at 400 1C. It was found that
the surface morphology of both activated carbon were dependent on it
starting materials. Both precursors had smooth surface and there were
developments of pores after chemical activations as shown in the
figure.
Ash et al. [170] characterized activated carbon from coir pith
with H3PO4 and NaOH which found that both types of activated
carbons showed canal like structures, pitted and fragmented
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235 227

formed on the surface. Ramakrishnan and Namasivayam [101] had
prepared activated carbons prepared from different types of acti-
vating agents (H2SO4, HNO3, HCl, H3PO4, H2SO4 þH2O2, H2SO4 þ
(NH4)2S2O8, NaOH and ZnCl2) that derived from Jatropha husk.
Generally all the micrographs showed honeycomb like structure
but with different pore structures. Pragya et al. [144] had prepared
activated carbon from two different types of biomass; almond
shell and walnut shell using ortho-phosphoric acid which found
that the surface morphology for both almond and walnut shell
showed grooves, cracks as well as crevices and regularly smaller
pores size respectively.
5.2. Types of activating agents
Demiral et al. [94] produced activated carbon by two different
chemical agents; ZnCl2 and KOH from hazelnut bagasse. Fig. 5(a) and
(b) shows the SEM photographs of the resulting activated carbon.
They found that different activating agents could produce different

Fig. 4. Scanning electron microscopy of activated carbon of (a) walnut shell (b) olive pit [166], (c) oil palm fruit bunch, (d) coconut shell and (e) bamboo stem [167].

Fig. 5. Scanning electron microscopy of (a) ZnCl2 activated carbon, (b) KOH activated carbon [94], (c) K2CO3 activated carbon and (d) ZnCl2 activated carbon [6].
228 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235
textural of surface morphology of activated carbon. There were full of
cavities found in the ZnCl2 activated carbon due to its evaporation
during carbonization. However, the external surface of KOH activated
carbon was smoother with numerous small pores distributed. Timur
et al. [171] also studied activated carbon derived from oak cups pulp
with two different chemical activating agents; ZnCl2 and H3PO4. On
the morphology under scanning electron microscopes, it was
observed that ZnCl2 activated carbon were full of cavities while for
H3PO4 activated carbon the external structure was intact. Yacob et al.
[6] had prepared activated carbon from palm kernel shells with
chemical activations using ZnCl2 and K2CO3 as activating agents.
Under SEM observation as shown in Fig. 5(c) and (d) it was found
that activated carbon derived from ZnCl2 showed highly defined
pores and cavities. The pore size distribution of the activated carbon
derived from K2CO3 was non-uniform due to rapid development of
the pore which resulted in formation of too much cavities and cracks.
Nevertheless, both activated carbons have cleaner and smoother
surfaces compared to its raw material. Sugumuran et al. [16]
characterized activated carbon from banana empty fruit bunch
(BEFB) and Delonix regia fruit pod (DRFP) with both KOH and
H3PO4. Results showed that both KOH and H3PO4 treated activated
carbons showed many holes on the surface with broken edges and
larger pores structures than pore size, respectively.
5.3. Concentration of chemical activating agents
Porosity development of activated carbon may also be influ-
enced by the concentration or impregnation ratio of chemical
activating agents used. Vicinisvarri et al. [122] studied the effect of
H3PO4 concentration on the surface morphology of the nutshell
derived activated carbon. It was shown that the increased in H3PO4
affected the porosity development in which there were cracks
found in the activated surface at the highest concentration of
H3PO4 (80 wt%) due to aggressive attack and rapid development of
pores. Ucar et al. [63] also used different concentration of ZnCl2 to
study the development of porosity on the activated carbon derived
from pomegranate seeds. The external surface of the activated
carbons had different pores and size dependent upon its impreg-
nation ratio and carbonization temperatures. All the activated
carbons were full of cavities and in irregular formed.
5.4. Types of activations
Williams and Reed [107] has studied pore structure develop-
ment of biomass fiber waste through physical and chemical
activations. Fig. 6 shows the scanning electron micrographs of
both physically and chemically treated activated carbon. The initial
Fig. 6. Scanning electron microscopy of (a) physically activated carbon and (b) chemically activated carbon [107].
study found that the surface morphology of the original biomass
was not significantly affected by both types of treatments. How-
ever, under higher magnifications, they found that for physically
treated the surface of activated carbons were found pitted and
cracked but for chemically activated carbon was smoothly surface.
6. Activated carbon applications
Activated carbon has many applications including water treat-
ment [172,173], chemical and petroleum industries [91], separa-
tion, purification [174], catalysis [101,175], energy storage [159],
batteries, fuel cells [176], nuclear power stations [177], electrodes
for electric double layer capacitors [178], pharmaceutical [163],
hydrometallurgy [104,179] and others.
In food industries, activated can be used for decolourization,
deodorization and taste removal purposes [10]. In medicine field, it
is used for harmful chemical and drug adsorption purpose. In gas
cleaning applications, activated carbon is used for air filters and air
conditioning purpose [93]. In mineral industry, for example, activated
carbon has been used for gold recovery from leached liquors [61].
Physical properties of activated carbon are crucial in determining its
best application. For example, if the activated carbon is intended for an
application in which frequent back-washing is needed, the hardness or
abrasion resistance properties are very important for the activated
carbon [93]. If the activated carbon is used for gaseous and vapors, its
porosity with radii less than 16–20 Å is required. If the activated
carbon is intended for color removal in liquid phase system, its
porosity with radii in the range of 20–500 Å is needed [100]. In short,
activated carbon has been very useful in adsorption process from
liquid to gaseous phase applications [93,126,180] including chemical,
pharmaceutical and food industries [9]. Table 7 presents different
applications of activated carbon produced from agricultural waste
materials.
7. Review of formation of activated carbon from agricultural
waste material
Kinetic study of the activated carbon preparation has been
found to be important in obtaining the process optimization which
involves kinetic model for pyrolysis and kinetic model for activa-
tion. The pyrolysis of the agricultural waste material i.e., biomass is
such a complex process which is very difficult to find the kinetic
model that describe thermal decomposition mechanism [59] since
it involves a large number of reactions in parallel and series [192].
It basically involves mass, heat transfer phenomena, and chemical
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235 229

Table 7
Different applications of activated carbon from agricultural waste material.

Starting material Applications References

Coconut shell Reduction of hexamine cobalt (III) Sodeinde [181]

Hazelnut shell and apricot stone Adsorption of Cu (II) Ozcimen and Ersoy-Mericboyu [162]
Rice husk Adsorption of Cu (II) Yahaya et al. [168]
Peach stone Adsorption of gold Masiya and Gudyanga [182]
Hazelnut shell Adsorption of Hg (II) Khalkhali and Omidvari [53]
Tamarind seed Uptake of methane for storage Munusamy et al. [184]
Pomegranate rind (Punica granatum) Adsorption of Direct red-28 dye Venckatesh et al. [185]
Sugarcane bagasse Decolourization of sugar Qureshi et al. [61]
Coir pith Removal of metal ions and toxic coloring material Ash et al. [170]
Olive oil mill residue Removal of colour from textile wastewater Pala et al. [186]
Eichornia crassipes Removal of dyes from aqueous solution Sivaraj et al. [187]
Coir pith Removal of 2,4-dichlorophenol (2,4-DCP) Subha and Namasivayam [163]
Rice husk Removal of Cu (II) Yahaya et al. [169]
Bagasse, pericarp of rubber, coconut shell Removal of iron (III) Sirichote et al. [173]
Eucalyptus wood Removal of phenol Tancredi et al. [54]
Coconut shell Adsorption of oxalic acid and maleic acid Rahman et al. [188]
Woody birch Adsorption of Hg (II) Budinova et al. [74]
Guava peel Removal of congo dye red Singh et al. [83]
Peanut shell Adsorption of Pb (II) Tao and Xiaoqin [189]
Empty fruit bunch Phenol removal Alam et al. [190]
Oil palm shell Methane adsorption Arami-Niya et al. [191]
Kenaf fiber Pb (II) removal from waste water Chowdhury et al. [95]
Groundnut shell Pesticide (Dichlorvos) removal Gimba et al. [138]
Coffee waste Adsorption of Zn (II) and Hg (II) from aqueous solution Giraldo and Moreno-Pirajan. [117]
Bamboo Adsorption of methylene blue Hameed et al. [139]
Almond husk Adsorption of Ni (II) from aqueous solution Hasar [156]
Groundnut shell Adsorption of malachite green Hassan et al. [19]
Nutshell Methylene blue adsorption Vicinisvarri et al. [122]

reactions. The chemical reactions during pyrolysis can be focused methods used in thermal analysis are differential thermal analysis
on three different criteria [193]: (DTA) and differential scanning calorimetry (DSC) [194].

(1) Biomass devolatilization: solid decomposition into gas, tar and
solid residue (char).
(2) Secondary phase reaction of the species of gas and tar that
released.
(3) Heterogeneous reaction between gas and solid.
The dynamics of reaction and chemical kinetics of this hetero-
geneous can be affected by three factors [194]:
(1) Chemical bonds breakage and redistribution.
(2) Change of reaction geometry.
(3) Interfacial diffusion of reactants and products.
The chemical reactions as well as the yield of the final product are
generally affected by operating conditions and possible heat and mass
transfer resistance [193]. Different researchers have basically pre-
sented different kinetic modeling of pyrolysis.
Kinetic data of solid state pyrolysis reactions can be obtained by
isothermal and non-isothermal techniques. Thermogravimetric
analysis (TGA) has been the most commonly used in thermoana-
lytical technique for solid phase thermal degradation studies. It
measures the mass decrease in substrate by devolatilization
process during thermal decomposition. The mass of substrate that
is being heated or cooled in TGA is basically monitored as a
function of time or temperature. Taking the first derivative of the
TGA curve (i.e.,  dm/dt) or also known as derivative thermogra-
vimetry (DTG), provides the maximum rate of reaction. The other
7.1. Kinetic model for pyrolysis
White et al. [194] reported that every kinetic model follows a
rate law that obeys the fundamental Arrhenius rate expression:
kðT Þ ¼ Aexpð  Ea =RTÞ ð1Þ
where T is the absolute temperature in K, R is the universal gas
constant, k(T) is the temperature-dependant reaction rate con-
stant, A is pre-exponential or frequency factor, and Ea is the
activation energy.
The biomass decomposition kinetics is generally assumed as a
single reaction which can be expressed under isothermal condi-
tions by the canonical equation, as follows:
dα
¼ kðT Þf ðαÞ ¼ Aexpð  Ea =RTÞf ðαÞ ð2Þ
dt
where t is time, α is degree of conversion or extent reaction, dα/dt
denotes rate of isothermal process, and f(α) signifies conversion
function which represents the reaction model and depending on
the controlling mechanism.
The degree of conversion (α), can further be defined as either
the mass fraction that decomposed or mass fraction of the volatile
evolves which can be expressed as follows:
Wo W v
α¼ ¼ ð3Þ
W o  W f vf
where, w is the mass at any time t, wo denotes initial substrate
230 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235

mass, wf denotes final mass remaining (residue and non reacted The kinetic parameters can be determined from thermogravi-
substrate), v signifies volatile mass at any time t, vf is the total metric data curve by using Arrhenius equation. The values of A, E
mass of volatile evolved. The combination of A, Ea, and f(α) can and n can be determined from linearized form of the equation by
finally be used to characterize the biomass pyrolysis reaction. applying least squares (multiple linear regression) technique. The
For non-isothermal, reactions rate are defined as a function of linearized rate equation is as follows [192]:
temperature at a linear heating rate, β, which can be expressed by y ¼ B þ Cx þ Dz ð13Þ
an ostensibly superficial transformation of Eq. (2):
where y represents ln{[/(w wf)][dw=dt]}, x represents1/(RT),
dα dα dt
¼ ð4Þ z represents ln[(w wf)/(wo  wf)], B represents lnA, represents –E and
dT dt dT
D represents n.
where dt/dT signifies the inverse of the heating rate, 1/β, dα/dt Zabaniotou et al. [197] used a single reaction and first-order
denotes the isothermal reaction rate, and dα/dT represents non- kinetic to describe their model, such following equation:
isothermal reaction rate.
dVi
By substituting Eq. (2) into Eq. (4), the rate law for non-  ¼ K i ðV 1  V i Þn ð14Þ
dt
isothermal conditions can be obtained, as follows:
where Ki represents Arrhenius kinetic constant, Vi represents
dα kðTÞ A
¼ f ðαÞ ¼ expð  Ea =RTÞf ðαÞ ð5Þ volatile percentage in time t, and V1 denotes ultimate atta-
dT β β inable yield.
Senneca [195] had studied three different types of agricultural Conesa and Domene [198] have also considered an nth order
residues; pine seed shell, olive husk, and wood chip. Non-isoth- kinetic decomposition. The kinetic equation for the pyrolysis
ermal kinetic under inert and oxidative conditions was studied as process was as such Eq. (15). The kinetic constants followed the
following equation: Arrhenius equation:
dm ki ¼ ki0 expð  Ei =RTÞ; i ¼ 1 to 3 ð15Þ
1=mo ¼ ko expð E=RTÞ½ð1ðm1 =mo Þα ð6Þ
dt Hu et al. [199] and Li et al. [200] had used a model with inde-
where m denotes actual weight of sample, mo represents initial pendent parallel reactions, also called three-pseudocomponents
weight of sample, and m1 denotes weight of sample residue. model to describe kinetic of pyrolysis of Chinese biomass. They opined
Sharma and Rao [196] have investigated n-order reaction for that the assumption of three-pseudocomponents was consistent due
rice husk pyrolysis under non-isothermal conditions in determin- to the existence of cellulose, hemicellulose and lignin in the biomass
ing the kinetic parameters. The nth order, the pyrolysis rate equ- composition. Depending on the reaction order n, for each pseudo-
ation is as follows: component has the following kinetic equation:
dX dαi
¼ K ð1  X Þn ð7Þ For ni ¼ 1; ¼ Ai expð  EA;i =RTÞð1  αi Þni
dt dt 8 9
where < Ai Z T =
¼ Ai expð  EA;i =RTÞexp  exp EA; i=RTÞ dT ð16Þ
Wo W : Ã To ;
X¼ ð8Þ O
Wo  Wx
The equations were as follows: dαi
For ni a 1; ¼ Ai expð EA;i =RTÞð1  αi Þni
dt
Ln½F ðX Þ ¼  E=RT þ Ln½ðAR=βEÞð1  2RT=EÞ ð9Þ ¼ Ai expð  EA;i =RTÞ
8 9
where < ðni  1ÞAi Z T =
exp  exp EA; i=RTÞ dT þ1 ni=ð1  niÞ:
F ðX Þ ¼ ½  lnð1XÞ=T 2  for n¼1 ð10Þ : Ã To ;
O
ð17Þ
F ðX Þ ¼ ½ð1  ð1  XÞ1  n Þ=ð1 nÞT 2  for na1 ð11Þ
Determination of kinetic parameters can be provided by TGA
data although the data can only provide the general information 7.2. Kinetic model for activation
on the overall reaction kinetics, not individual reactions. The data
is based on the following rate equation [192]: The studies on the effect of time and temperature of activation step
on the porosity and adsorptive properties of activated carbon have
dX
¼  Ae  ðE=RTÞ
Xn ð12Þ been done by countless researchers. However, the studies on the effect
dt of carbonization on the textural properties of the resulting activated
where X is the weight sample (kg), t denotes time (min), A is pre- carbon from a variety of raw materials have been given lesser
exponential or frequency factor (min  1), E signifies activation attention. In fact, there are almost no studies that have been
energy of reaction of decomposition (kJ mol  1), R is the universal performed to investigate the effect of the carbonization temperature
gas constant (kJ mol  1 K  1), n is the order of reaction (–). on the gasification kinetics of the biomass char during the production

Table 8
Summary of gas–solid reaction kinetic models for gasification of char.

Model Assumption Equation rate Conversion equation Reaction rate

VRM Homogenous dX
¼ kv ð1  XÞ X ¼ 1  exp(  kvt)  ln(1  X) ¼ kvt
dt
SCM Shrinking core of non porous grains as reaction continues dX
¼ ks ð1  XÞ2=3 X ¼ 1  (1  kst/3) 3[1  (1  X)1/3] ¼kst
dt
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
RPM Pore surface creation and overlapping as reaction continues dX
¼ kR ð1 ¼ XÞ½1  Ψ lnð1 ¼ XÞ1=2 X¼ 1 exp{[1 (1þkRΨt/2)2]/Ψ} (2/Ψ)[ ð1  Ψ lnð1 XÞÞ  1¼ kRt]
dt
MVRM Apparent rate constant changes with solid conversion dX
¼ kðX Þð1 XÞ X ¼ 1  exp(  k(X)t)  ln(1  X) ¼ k(X)t
dt
 M.A. Yahya et al. / Renewable and Sustainable Energy Reviews 46 (2015) 218–235
of activated carbon [201]. Gasification is also knows as thermal
oxidation is a process that produces a high proportion of gaseous
products such as CO2 and CO, small quantities of solid product (char),
ash, and condensable compounds including tars and oils [202].
The characteristic of biomass gasification depends mainly on its type
and operating condition. Particle size, porosity of the char, mineral
content, temperature and partial pressure of the gasifying agents are
among the physical factors that can influence the gasification rate
[203]. It has been noted that the process of char gasification is a much
slower process as compared to the pyrolysis process, hence dominat-
ing the whole gasification process [204].
The use of TGA method has been practiced by researchers to study
the gasification kinetic from a variety of agricultural residues [59].
There are several types of kinetic model that have been used such as
volume reaction model (VRM), shrinking core model (SCM), random
pore model (RPM), and modified volume reaction model (MVRM).
Table 8 describes these kinetic models briefly.
Ollero et al. [205,206] had used wood matter to study the
gasification kinetics. The authors used two kinetic equations; an
nth-order and Langmuir–Hinshelwood type equation. The reactivity
R (s  1) is defined as
dw dX
R ¼ 1=ðw  wa Þ ¼ 1=ð1  XÞ
dt dt
where w defines char weight, wa is ash weight, X signifies degree
of conversion, X ¼(wo w)/(wo  wa), where wo is the initial weight
of the dried and pyrolysed sample. In the absence of CO, the nth-
order kinetics is always adopted, to express the temperature and
CO2 pressure dependence of the representative reactivity. Hence
R50 ¼ K pnCO2 ; K ¼ ko expð  E=RTÞ
By using Langmuir–Hinshelwood kinetic equation, the reactivity
is defined as
K1pCO2
R50 ¼
1 þ apCO þ bpCO2
where K1, a and b are kinetic parameters that depend solely on
parameter. Klose and Wolki [207] had also used Langmuir–Hinshel-
wood kinetic equation to describe the gasification of beech wood
and oil palm chars with CO2 and H2O.
Matsumoto et al. [208] had adopted random pore model (RPM)
to study the gasification rate on four types of biomass char. The
model assumes that the reaction occurs on the inside surface of
the micropores which occupy most of the surface area. As the
reaction progress, the micropores surface area initially increases
due to diameter expansion and then finally decreases due to
overlapping of the expanded pores. The surface area of micropores
is described as follows:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
S=So ¼ ð1  XÞ 1  Ψ lnð1  XÞ ð21Þ
The gasification reaction was assumed to occur at the micro-
pore surfaces, when only the gasification agent (H2O or CO2) exits.
The gasification reaction rate was proportional to S:
dX pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Rg ¼ ¼ kr ð1  XÞ 1  Ψ lnð1  XÞ
dt
When X¼ 0, the gasification reaction rate (kr) equals to value of Rg,
as following equation:
kr ¼ P ng Aa expð  Ea =RT g Þ
Senneca [195] studied the gasification rate on the pince seed
shells, olive husk and wood chips. A power law kinetic expression
for gasification is as follows:
df
¼ Aðf Þ2 ko expð E=RTÞpng
dt
where pg signifies the partial pressure of the reacting gas (O2/CO2/
231
H2O) in char, A(f) denotes the evolution of instantaneous conver-
sion rate along the burn-off.
8. Conclusion
In this review, a wide range of activated carbon derived from
agricultural waste materials has been presented. Promising results on
production of the activated carbon with large surface area, high
microporosity and selectivity have been achieved. Relatively inexpen-
sive, locally available and effective materials of the agricultural
residues could be used in place of commercially produced activated
carbon for many applications. It is undoubtedly comprehensible that
more detailed investigations on the production, optimization, applica-
tions of the activated carbon-agricultural residues based are needed to
prove its values.
Acknowledgments
One of the authors (M.A. Yahya) would like to thank Ministry of
Higher Education for awarding his Ph.D scholarship (MyBrain15).
ð18Þ
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