A brief review on activated carbon derived

from agriculture by-product

Cite as: AIP Conference Proceedings 1972, 030023 (2018); https://doi.org/10.1063/1.5041244
Published Online: 05 June 2018

Mohd Adib Yahya, Muhammad Humaidi Mansor, Wan Amani Auji Wan Zolkarnaini, Nurul Shahnim Rusli, Anisah
Aminuddin, Khalidah Mohamad, Fatin Aina Mohamad Sabhan, Arif Abdallah Aboubaker Atik, and Lailatun Nazirah
Ozair

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AIP Conference Proceedings 1972, 030023 (2018); https://doi.org/10.1063/1.5041244 1972, 030023

© 2018 Author(s).
 A Brief Review on Activated Carbon Derived From
Agriculture By-Product
Mohd Adib Yahya1, a), Muhammad Humaidi Mansor1, Wan Amani Auji Wan
Zolkarnaini1, Nurul Shahnim Rusli1, Anisah Aminuddin1, Khalidah Mohamad1,
Fatin Aina Mohamad Sabhan1, Arif Abdallah Aboubaker Atik1, Lailatun Nazirah
Ozair1
1
Faculty of Science and Technology, Universiti Sains Islam Malaysia, Bandar Baru Nilai,
71800 Nilai, Negeri Sembilan, Malaysia.
a)
Corresponding author: mohd.adib@usim.edu.my

Abstract. A brief review focusing on preparation of the activated carbon derived from agriculture by-products is presented.
The physical and chemical activation of activated carbon were also reviewed. The effects of various parameters including
types of activating agents, temperature, impregnation ratio, were also discussed. The applications of activated carbon from
agricultural by products were briefly reviewed. It is provenly evident in this review, the relatively inexpensive and
renewable resources of the agricultural waste were found to be effectively being converted into wealth materials.

INTRODUCTION
Activated carbon can be defined as a carbonaceous material with amorphous structure [1], large internal surface
area and high degree of porosity [2]. It has a microcrystalline and non-graphitic form of carbon. Non-graphitic form
means a matter that consists of a small number of hydrogen or much number of oxygen in their structure [3]. It has
high performance in electrical conductivity [1], good thermal stability [4] as well as surface reactivity that becomes
the main reason why activated carbon widely used in the recent years.
Carbonaceous material primarily consists of carbon element. Due to electronic configuration of 1s 2, 2s2, 2p2,
carbon has unique bonding possibilities with other elements and with itself. When it bonds with other carbons, three
most possible and abundant allotropic forms are produced as illustrated in Fig. 1 [5]:
I. Hexagonal graphite – A graphene layered structure that formed when carbon atoms are bonded by σ-bonds
and π-bonds to three neighbouring carbon atoms resulting in sp 2 based structure.
II. Fullerene (C60) – A 3D structure that formed when the bonds between the carbon atoms are bent forming an
empty cage of sixty (C60) or more resulting in sp2+ɛ based structure.
III. Cubic diamond – A rigid and isotropic 3D structure that formed when each of the carbon atoms shares four
σ-bonds with four neighbouring carbon atoms resulting in sp 3 based structure.

FIGURE 1. Allotropic forms of hexagonal graphite (left), fullerene (middle) and cubic diamond (right)

Recent Advancement on Applied Physics, Industrial Chemistry and Chemical Technology

AIP Conf. Proc. 1972, 030023-1–030023-8; https://doi.org/10.1063/1.5041244
Published by AIP Publishing. 978-0-7354-1679-6/$30.00

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 On atomic scale, most of the carbons exhibit graphite allotropic form as compared to the diamond-like and
fullerene carbons [6]. Graphite carbon is categorized into non-graphitic (without any measurable crystallographic
order) and graphitic carbons (with measurable crystallographic order). By definitions, non-graphitizable carbon is a
non-graphitic carbon which cannot be transformed into graphitic carbon whereas graphitizable carbon is a non-
graphitic carbon which can be converted into graphitic carbon by the process of heat treatment [7]. Graphitizable
carbon is soft, non-porous and has a high density. The microstructures of graphitizable carbons are arranged in
preferential direction. Meanwhile, non-graphitizable carbon is hard, porous and has a low density. It also has very
disordered microstructures. Therefore, activated carbon is categorized under non-graphitizable carbons because it has
a low density due to its porous structure. Activated carbon is known as a black solid containing major portion of fixed
carbon content and other minor contents such as ash, moisture and volatile matter, it also has physical characteristics
such as density, surface area and pore volume [8].
Presence of heteroatoms (atoms except carbon such as hydrogen, oxygen, nitrogen, phosphorus and sulphur) on
the surface of activated carbon usually used to determine its chemical properties. The presence of this atoms will
influence its type and quantity. This occurred during the introduction of activating agent or by nature of the starting
raw material. The heteroatoms and delocalized electron of the carbon on the surface of the activated carbon will form
certain functional groups that will defined the chemical properties of it surface whether acidic or basic [9, 10].
The groups that present on the surface (edge or outer surface of the activated carbon) which contains oxygen atoms
usually related to the acidic surface properties. Concentration of the oxygen atoms on the surface plays an important
role as these atoms really influenced the adsorption capability of the carbon itself. Carbonyl, carboxylic, chromene,
ether, lactone, phenol, pyrone and quinone groups are the examples of the functional groups that contains oxygen
which can be detected on the surface of the carbon [11]. In addition, the basic characteristic of the carbon surface
basically related with the presence of nitrogen atom that has ability to bind with protons and π-electrons resonance of
carbon aromatic rings that attract protons [12].

PORE SIZE CLASSIFICATION OF ACTIVATED CARBON

Activated carbon contains micropores, mesopores and macropores within its structure. These structures have
significant role in determining the properties of activated carbon such as the performance of the activated carbon as
adsorbent [13]. International Union of Pure and Applied Chemistry (IUPAC) classified activated carbon pore sizes
into micropores (< 2 nm), mesopores (2 nm - 50 nm) and macropores (> 50 nm). Figure 2 illustrates the internal pore
structure of activated carbon.

Macropores
Micropores

Mesopores

Activated
carbon
FIGURE 2. Pore structures in activated carbon [14]

ACTIVATED CARBON FROM AGRICULTURAL WASTE

Performances, characteristics and properties of the activated carbon that will be produced depend on the starting
material at the beginning of the production. Besides, the performances of the activated carbon also influenced by the
type of activations; physical, chemical or physicochemical [15] and inorganic compounds [16]. Variety of sources can
be used to produce activated carbon such as animal, mineral and plants. Basically, the price, purity, potential
expectancy will be the main focusses to choose the starting raw materials whether it from animal, mineral or plants
and also easier to be activated besides have low degradation properties by aging [17].
In recent years, many researchers have used agricultural wastes as precursors for the production of activated carbon
based on four main reasons; renewable source, inexpensive, readily available and environmental friendly. It can also

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be one of the income sources for the agro-based industries [18]. The activated carbon can be produced from
carbonaceous materials through pyrolysis method under several conditions whether by using chemical, physical or
microwave induced/assisted treatment [17]. Usually the activated carbon in the market were made from coal, lignite,
peat, petroleum residue, wood which known very expensive and exhaustible [19]. These situations lead to the new
development in producing activated carbon which utilize the agricultural bio-waste (lignocelluloses materials) in order
to reduce the cost of the production besides it is readily available and sustainable for long term usage. The examples
of agricultural wastes are palm shells, fruit shell, groundnut shell, coconut shell and Ricinus communis seed shell [20].
Activated carbon from agricultural wastes can be derived from many parts of any plant such as root, stem, bark,
flower, leave, fruit peel, husk, shell and stone. These wastes can be classified into woody and non-woody resources.
Woody resource mainly composed of cellulose, hemicellulose and lignin only whereas non-woody resource composed
of cellulose, hemicellulose, lignin, lipids, protein, sugar, water, hydrocarbon, starch and many functional groups
potentially capable in removing pollutants [21]. Amirza [21] also claimed that researchers are more likely to use non-
woody agriculture wastes in studying the applications of activated carbon due to their special compositions which can
lead to better characteristics of pore structures than woody agriculture wastes. In general, selection of raw material
depends on seven important criteria [7]:

i. High carbon content.

ii. Low inorganic matter content for low ash result
iii. High density and volatile matter content.
iv. Abundant so that the raw material is always in very low cost.
v. Potential extent of activation
vi. Low degradation rate upon storage.
vii. Possibility of producing an activated carbon with high percent yield.
Of all, the seventh criteria are actually impossible because most of the biomass wastes have lower carbon contents
as compared to the fossil fuel sources [1]. Hence, the percent yield of an activated carbon produced from biomass
waste is expected to be lower. However industrially, the cheap cost of raw material gives more significant impact as
compared to the yield percent obtained.

ACTIVATED CARBON PREPARATION

In principle, activated carbon can be manufactured in two ways which are:

i. Physical treatment: Involves carbonization of raw material alone in the absence of oxygen and in the
presence of inert gases followed by activation using oxidising agent such as steam, air, carbon dioxide or
their combination.
ii. Chemical treatment: Involves carbonization of raw material activated with strongly dehydrating and
oxidizing agent such as H3PO4, ZnCl2, KOH and NaOH under nitrogen atmosphere.
In short, the production of an activated carbon involves two important steps which are carbonization and activation.

Carbonization
Carbonization is the thermal decomposition and the removal of non-carbon species from raw material [1]. On the
other words, it is a process of reducing volatile matter content producing charcoal with high fixed carbon content by
breaking down the cross-linkage in the raw material. During the process, lignocellulosic contents will be decomposed
leading to the elimination of non-carbon elements particularly nitrogen, oxygen and hydrogen. Then, deposition of
tars takes place. Basically, volatile matter content with low molecular weight will be diffused first followed by light
aromatics and hydrogen gas. At the same time, pore structures start to develop, and the tars produced will fill the pore
structures. Carbonization process can be divided into four phases depending on the temperatures of each stage as
summarized in Table 1 [22].

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 TABLE 1: Phases occurs during carbonization process
Phase Temperature Ԩ Process
1 Less than 200Ԩ Initial drying of raw material.
2 170 Ԩ - 300 Ԩ Pre-carbonization phase producing small amount of pyroligneous
liquids and non-condensable gases.
3 250 Ԩ - 300 Ԩ Elimination of large proportion of pyroligneous liquids and tars
produced in phase two, producing charcoal.
4 More than 300 Ԩ Increasing the carbon content of the charcoal by diffusing out any
remaining volatile matter content.

Activation
Activation is a key step to enhance the pore structures. There are two types of activation methods namely physical
activation and chemical activation.

Physical Activation

Production of activated carbon by physical treatment constitutes of two step-processes. After carbonization, the
charcoal obtained will be activated using oxidizing gaseous to upgrade and enhance the pore structures [22]. In
activation process, the oxidizing gas will remove more reactive carbon species forming pores and vessels. Finally,
activated carbon with high porosity will be produced. Physical activation is conducted at high temperature commonly
500 Ԩ to 1000 Ԩ [2]. In general, formation of pores by activating gas consist of three phases which are opening of
previously inaccessible pores, new pore formation and lastly broadening of existing pores [1]. Below are the reactions
that might take place during the activation using different types of activating agent:

i. Oxygen
C + O2 ՜ CO2
2C + O2 ՜ 2CO

ii. Carbon dioxide

C + CO2 ՜ 2CO

iii. Steam
C + H2O ՜ H2 + CO
CO + H2O ՜ H2 + CO2
C + 2H2 ՜ CH4

Chemical Activation

Production of activated carbon by chemical treatment comprises of one step-process. The raw material will be
impregnated with the activating agent before being introduced to the carbonization. Chemical activation is conducted
at a lower temperature than physical activation [22]. During the activation process, the raw material will be
impregnated with the strongly dehydrating and oxidizing chemicals. There are three types of activating agents used in
activated carbon production [23]:

i. Alkali (KOH, K2CO3, NaOH, and Na2CO3)

ii. Alkali earth metal salt (AlCl3 and ZnCl2)
iii. Acid (H3PO4 and H2SO4)
Activating agent acts as a dehydrating or oxidizing agent during the impregnation process. It promotes
lignocellulosic materials decomposition and inhibits the deposition of tar and volatile matter contents [24]. Thus, this
enhances the percent yield of activated carbon produced. Ultimately after being carbonized, the activated carbon

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produced will be washed with acid or alkali depending on the types of activating agent used in activation process. This
washing step is very important in order to remove the chemical components occupied by the pores structure in
activated carbon thus enhancing its adsorption capacity.

FACTORS INFLUENCE ACTIVATED CARBON CHARACTERISTICS

Effect of Activating Agent

In physical activation, steam and air are good activating agents in term of reaction time. It has been proved that
steam, and air react 8 times and 10 times faster respectively with carbon as compared to CO 2 [22]. However, as air
reacts aggressively with carbon, it leads to the burnout inside of the pore structures and on the external surface of the
carbon. As a result, the yield would be lower. Therefore, due to these reasons, the use of CO2 is more preferable. In
addition, CO2 is easier to be handled and cleaned [25]. It also ensures the overall control of activation process as it
uses a slow reaction rate [26].
In chemical activation, the most commonly used activating agents are ZnCl2, H3PO4, NaOH and KOH [27]. All of
these agents give different effects to the raw materials. It was revealed that the use of KOH leads to the highest
micropore percentages for activated carbon derived from Holk oak acorn [28]. Further, to investigate the effect of
activating agents, the authors tested the production of the activated carbon using H 3PO4 and ZnCl2. It was found that
activated carbon produced using H3PO4 activation had a mesopore structure while those produced from ZnCl2
activation had a heterogeneous pore distribution consisting of micropores and mesopores. Boualem [29] got a totally
similar result from the preparation of activated carbon from sewage sludge using H 3PO4 activation. Hence, it was
suggested that the use of H3PO4 as activating agent contributes large mesoporous and some microporous for almost
activated carbon produced.
A study carried out previously proposed that the yield activated carbon obtained by using H 3PO4 as activating
agent was higher than the fixed carbon content of raw material [30]. Essentially, biomass waste is a complex composite
material formed of natural polymers (cellulose, lignin, and hemicellulose). In activation or carbonization, these
polymeric structures decompose and liberate most of the non-carbon elements mainly hydrogen, oxygen and nitrogen
in the form of liquid (called as tars) and gases leaving behind a rigid carbon skeleton in the form of aromatic sheets
and strips. The presence of H3PO4 during activation promotes depolymerization, dehydration, and redistribution of
constituent biopolymers and also favouring the conversion of aliphatic to aromatic compounds thus increasing the
yield of activated carbon.
When comparing between H3PO4 and ZnCl2, H3PO4 leads to the higher yield production of activated carbon than
ZnCl2 [31]. However, the fixed carbon content is higher when using ZnCl 2. In a research, Hura Crepitans Linn seed
shells were activated using H3PO4 and ZnCl2 and the results obtained were compared [31]. Results revealed that the
percent yield of H3PO4 activated carbon was 44.90% while ZnCl2 activated carbon was 31.94%. In terms of
adsorptivity with all the adsorbent dosages, ZnCl2 impregnated activated carbon had greater adsorption efficiency of
methylene blue than the one prepared with H3PO4. This result suggested that ZnCl2 impregnated activated carbon have
well developed mesoporosity favourably for adsorption of larger molecules of methylene blue as compared to H 3PO4
impregnated activated carbon.
Chowdury [22] claimed that chemical activation using KOH and NaOH lead to activated carbon with high surface
area of more than 1000 m2/g. Based on the research conducted previously, the surface area of activated carbon derived
from rice husk, activated using KOH had a surface area of 2551 m2/g while the surface area reached 2952 m2/g when
the rice husks were activated using NaOH [32]. These two comparable results were then concluded that the process
of intercalation of metallic sodium inside the raw material structure is slower as compared to potassium due to its high
boiling point [33].

Effect of Impregnation Ratio

Impregnation is an important step in producing activated carbon by chemical treatment. It can be defined as the
ratio of weight of activating agent to the raw material impregnated [1]. Other than carbonization, impregnation ratio
also gives a great impact on the pores development. This can be proved by the research conducted on grape industrial
processing activated using ZnCl2 [27]. The ratios of ZnCl2 to the raw material were 1:1, 2:1, 4:1, 6:1 and 8:1 and the
raw materials were carbonized at 500 ºC for 60 min. It was observed from the study that the higher impregnation ratio
lead to mesopore formation while lower impregnation ratio leads to micropore formation. This is based on the fact

030023-5
that higher impregnation ratio results in bigger swelling and stronger release of volatile matter contents which then
leads to widening pores [34]. Meanwhile, lower impregnation ratio promotes the excretion of volatile matter contents
but at the same time it inhibits the deposition of tars resulting in more micropores formation [27].
Impregnation ratio also affects the yield of activated carbon produced. This can be proved by the research
conducted using jackfruit peel impregnated at 1:1, 2:1, 3:1 and 4:1 with H3PO4 and then each was carbonized at 350
Ԩ, 450 Ԩ and 650 Ԩ, respectively [30]. From the research, it is obvious that yield of activated carbon decreased as
the impregnation ratio increased. This trend is similar for every carbonization temperature used. This might be
attributed to the excess H3PO4 would promote gasification of activated carbon and increased the total weight loss of
activated carbon. The same result was also observed by the research conducted by [35].

Effect of Temperature
In general, carbonization temperature affects significantly on the pore structures of activated carbon produced in
terms of surface area and pore volume [1]. Basically, higher carbonization temperatures would lower the yield
production of activated carbon. In term of activated carbon compositions, increasing of carbonization temperature
would decrease the moisture and volatile matter contents and would further increase the ash and fixed carbon contents
[25].
Yorgun and Yildiz [36] prepared activated carbon from Paulownia wood at various carbonization temperatures
which are 30, 400, 500 and 600 ºC. In the study, H3PO4 was used as the activating agent at the impregnation ratio of
4:1. It was found that the yields of activated carbon decreased as the carbonization temperature increased. It was also
observed that with the increasing of carbonization temperature from 300 to 400 ºC, both BET surface area and pore
volume increased. However, when the carbonization increased from 400 to 600 ºC, the surface area and total pore
volume decreased. These temperatures range might have induced the shrinkage in the activated cabon structure. It was
reported that activated carbon obtained from the carbonization temperatures of 300 to 600 ºC contain both microporous
and mesoporous structures.
This trend was similar to the result obtained previously when using other lignocellulosic material which is Fox nut
shell in producing activated carbon although the carbonization temperatures used were different [30]. The
carbonization temperature used were from 600 to 800 ºC and H3PO4 was used as the activating agent at the
impregnation ratio of 3:2. From the research, the yields of activated carbon produced decreased as well when the
carbonization temperatures increased. Microporosity of the activated carbon produced were found to decrease as the
carbonization temperatures increased. This might be attributed to the increment of the mesoporosity. It was found that
the BET surface area and the total pore volume decreased when the carbonization temperatures increased from 700 to
800 ºC. Due to same reason, this result was affected by the shrinkage of activated carbon structure and oxidation of
the raw material compositions.

ACTIVATED CARBON APPLICATION

There are many applications on activated carbon since its early development in 1970’s including waste-water
treatment, industrial water treatment, water purification [37], CO2 particles capturer [10], pharmaceutical [38], gold
purification and electrodes for electric double layer capacitors.
Better performances of its physicochemical characterization give advantages for removal of organic dye in water.
There were many considerable amounts of researches were reported with their study suggested that activated carbon
has been used for dyes removal mainly for methylene blue, levafix red and remazol brilliant blue [39]. Activated
carbon from cashew nut that undergo chemical treatment with ZnCl2 has a better adsorption of methylene blue due to
its development in the composition of functional group and porosity as reported in the previous study [40]. For
activated carbon that has been treated with HCl, it has been reported that the negative surface development and the
existence of mesopores due to the impurities removal were the important factors that influenced the adsorption of
methylene blue [39].
Several studies also showed that activated carbon from agricultural precursors can be applied in pharmaceuticals
industries mainly as adsorbent for example acetaminophen, tetracycline, norfloxacin, caffeine and penicillin [41].
Compared to other methods such as biological treatment, chemical oxidation and membrane filtration, activated
carbon adsorption has created the best results against the pharmaceuticals pollutant as reported previously [39].

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 CONCLUSIONS
In this brief review, activated carbon produced from agricultural waste materials has been presented. Its
availability, relatively low-cost, promising results and effectively produced could be our priority to replace non-
renewable commercial activated carbon to be used in many applications. It is understandable that more detailed studies
on the production and application of activated carbon from renewable resources are deeply required to prove its values.

ACKNOWLEDGMENTS
The authors are grateful to Faculty of Science and Technology and Universiti Sains Islam Malaysia (USIM) for
funding this project under Head Start programme (PPP/HSP1317/FST/051013-24117).

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