Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

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Renewable and Sustainable Energy Reviews

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

A review of biomass-derived heterogeneous catalyst for a sustainable

biodiesel production
Sharifah Hanis Yasmin Sayid Abdullaha, Nur Hanis Mohamad Hanapia, Azman Azida,
⁎
Roslan Umara, Hafizan Juahira,b, Helena Khatoonc, Azizah Enduta,d,
a
East Coast Environmental Research Institute, Universiti Sultan Zainal Abidin, Gong Badak Campus, 21300 Kuala Terengganu, Terengganu, Malaysia
b
Faculty of Bioresources and Food Technology, Universiti Sultan Zainal Abidin, Tembila Campus, 22000 Besut, Terengganu, Malaysia
c
School of Fisheries and Aqua-Industry, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia
d
Faculty of Innovative Design and Technology, Universiti Sultan Zainal Abidin, Gong Badak Campus, 21300 Kuala Terengganu, Terengganu, Malaysia

A R T I C L E I N F O A BS T RAC T

Keywords: Biodiesel production is commonly carried out through the process of transesterification reaction. The reaction is
Biodiesel expedited with a suitable catalyst either homogeneous or heterogeneous. The selection of an appropriate catalyst
Biomass depends on the amount of free fatty acids in the oil. Recently, homogeneous catalysts are widely chosen for
Heterogeneous catalyst biodiesel production in large scale operation. However, they are toxic, highly flammable and corrosive in nature.
Solid base catalyst
Furthermore, the use of homogeneous catalyst produced soaps as by-product and large amount of
Solid acid catalyst
wastewater that required additional processing technologies and cost for proper disposal. On the contrary,
heterogeneous catalysts are capable to overcome the problems faced by the former ones. However, they were
mostly derived from non-renewable resources, highly expensive with low stability. Recently, heterogeneous
catalysts derived from biological waste have gotten more attention. This type of catalysts offers several
advantages, including renewable resources, non-toxic, reusable, high catalytic activity, stability in both acidic
and basic conditions and high water tolerance properties, which depend on the amount and strengths of active
acid or basic sites. Basic catalyst can be subdivided based on the type of metal oxides and their derivatives.
Similarly, acidic catalyst can be subdivided depending upon their active acidic sites. In this article, efforts have
been taken to review the bio-based heterogeneous catalyst utilized for sustainable biodiesel production and their
suitability for industrial application. Catalyst generated from bio-waste and other biocatalysts, which are
heterogeneous in nature and extensively reported in literature are also reviewed. The utilization of these
biomass derived catalysts provides a greener synthesis route for biodiesel production.

1. Introduction
Nowadays, biofuel such as biodiesel and bioethanol has become a
great interest to be the alternative source of energy as opposed to the
conventional fossil fuel. The detrimental effect of global warming,
rising numbers of environmental related problems, depletion of fossil
fuel resources become the main factors that contribute to the global
transformation in the development of biodiesel [1–4]. The used of
biodiesel as a source of fuel offers several advantages, including
renewable and sustainable resources, non-toxic, environmental
friendly where it reduces the emission of CO2, and hazardous com-
pound namely arithmetic, sulfur, particulate matter and NOx [1–5].
The application of biodiesel showed a reduction in the net carbon
dioxide emissions on a life cycle basis, carbon monoxide, particulate
matter and unburned hydrocarbons by 78, 46.7, 66.7 and 45.2%,
respectively [6]. Hence, the use of biodiesel will significantly reduce the
effect of global warming. On top of that, biodiesel can be directly used
in the engine or with little modification, blended with regular petro-
leum-based diesel at any ratio without losing the engine performance
[2]. In addition, no sulfur content in biodiesel provides greater lubricity
than conventional diesel fuel, thus improves the durability of the
engine [7]. Generally, biodiesel displays good oil qualities, including
higher cetane number, higher combustion efficiency, and less emission
[8–10].
Biodiesel or chemically known as fatty acid methyl ester (FAME)
can be derived from the chemical reaction of feedstock either vegetable
oils or animal fats and alcohol with or without the presence of a
catalyst. Several types of oil have been studied for the biodiesel

⁎
Corresponding author at: East Coast Environmental Research Institute, Universiti Sultan Zainal Abidin, Gong Badak Campus, 21300 Kuala Terengganu, Terengganu, Malaysia.
E-mail addresses: shanisyasmin@yahoo.com (S.H.Y.S. Abdullah), nhanismh@gmail.com (N.H.M. Hanapi), azmanazid@unisza.edu.my (A. Azid),
roslan@unisza.edu.my (R. Umar), hafizanjuahir@unisza.edu.my (H. Juahir), hlnkhatoon@gmail.com (H. Khatoon), enazizah@unisza.edu.my (A. Endut).

http://dx.doi.org/10.1016/j.rser.2016.12.008
Received 4 September 2015; Received in revised form 29 July 2016; Accepted 3 December 2016
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: Sayid Abdullah, S.H.Y., Renewable and Sustainable Energy Reviews (2016),
http://dx.doi.org/10.1016/j.rser.2016.12.008
S.H.Y.S. Abdullah et al.
Fig. 1. General transesterification reaction scheme.
production, including the first generation fuels which can be categor-
ized as edible oil including palm oil [11,12], sunflower oil [13,14] and
soybean oil [15,16]. The second generation fuels component of the
non-edible oil including Jatropha curcas seed oil [17,18], neem oil
[19,20], castor oil [21] and waste cooking oil [22,23]. Lastly, the third
generation fuel comprises of microalgae-based oil [24–26]. Apart from
oil, biodiesel can also be derived from spending bleaching clay, a waste
from an edible oil refinery process [27].
At the present time, there are several methods for producing
biodiesel, including direct use and blending of raw oils, dilution,
microemulsion, thermal cracking or pyrolysis and transesterification
[28]. Among all, transesterification is the easiest and most cost effective
approach to produce biodiesel [29–31]. Transesterification or alcoho-
lysis can be defined as a reaction of fats or oils with an alcohol in the
presence of a catalyst to form fatty acid methyl ester and glycerol [32–
34]. The general transesterification routes for biodiesel production are
as illustrated in Fig. 1. Several types of alcohol can be used, including
methanol, ethanol, butanol and amyl alcohol. However, methanol is
widely used since it is cheaper, short chain alcohol, quickly reacted and
easily dissolved into the reaction medium.
The catalyst for transesterification reaction can be either alkali or
acid or enzyme. Table 1 summarizes the advantages and disadvantages
of each type of catalyst. The enzymatic transesterification is considered
to be the most effective method for biodiesel production [35,36].
However, the cost catalyst is extremely high and the reaction rate is
too slow, hence retards broader application [1,9]. Currently, homo-
geneous base catalysts have been widely chosen in industrial scale for
biodiesel production [7]. A homogeneous base catalyst such as sodium
hydroxide (NaOH) and potassium hydroxide (KOH) offer several
advantages, including high catalytic activities [37,38], shorter reaction
time [39], modest operating conditions [1], raw materials are extre-
mely cheap and abundantly available [31,32]. However, the homo-
geneous base catalyst reaction is highly sensitive to the presence of free
fatty acids (FFA) and water. Moreover, the formation of soaps as a
result of side reaction of neutralization and saponification will deter the
separation and purification process, produced a large volume of
wastewater and incur an additional cost of operation. This requirement
makes this catalyst environmentally unfriendly [29,31,39].
On the contrary, a homogeneous acid catalyst such as sulphuric acid
(H2SO4), hydrochloric acid (HCl) and phosphoric acid (H3PO4) are
suitable for feedstock with high FFA content such as waste cooking oil,
crude vegetable oils and animal fats. It significant advantages over the
former one includes the insensitivity to the presence of FFA and water,
ability to catalyze both transesterification and esterification reactions
and no formation of soap by-products [6,29,31]. However, slow
reaction time becomes the major factor that retards the wide applica-
tion of this catalyst [32,39]. It has been reported that the conversion
rate of acid-catalyzed transesterification is about 4000 times slower
than that of base catalyst [6,31]. Apart from that, homogeneous acid
catalysts are highly acidic and corrosives in nature [31,40]. Product
separation and purification in homogeneous operation required a
number of steps, produce a large amount of wastewater and contribute
to the increase in the operational cost [41]. In addition, recovery and
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
regeneration of homogeneous catalyst are difficult, not feasible, require
more processing steps and extremely expensive [42].
The application of heterogeneous or solid catalyst has gained
interest in the biodiesel production. The catalysts are neither consumed
nor dissolved in the reaction mixture which made it easier to be
separated from the product in the later [41]. On top of that, the
recovered catalyst can be reused back in the reaction, hence reducing
the catalyst consumption and cost associated [3]. The heterogeneous-
based operation offers several benefits including noncorrosive, easy
separation and longer catalyst life [31,32,39]. Numbers of catalysts are
available in the market for basic-catalyzed reaction, which includes
metal oxide, mixed oxide and hydrotalcite [43]. On the other hand,
transition metal oxide, ion exchange resin, carbon-based catalyst, and
zeolites are among the catalysts available for acidic operation [44].
However, the presence of three-phase system in a heterogeneous
system will lead to diffusion problem that will inhibit the reaction
[1]. Three phases of solid catalyst-alcohol-oil that is highly immiscible
limit the mass transfer efficiency, thus lowering the rate of reaction
[29,45]. Moreover, Sani et al. [42] stated that mass transfer efficiency is
limited within a bulky molecule hence resulted in the poor conversion
into biodiesel. Additional problems faced by solid catalyst are a low
number of active sites, micro porosity, leaching, toxic, expensive,
derived from non-renewable resources and environmentally unfriendly
[40,46,47]. Hence, in order to produce an excellent solid acid catalyst,
the catalyst must comprise of more specific surface area (hydrophobi-
city, external catalytic sites, etc.) and a large pore diameter [45].
Bio-based or ‘green’ catalyst is a term referring to a type of catalyst
derived from natural sources such as biomass. The current trend shows
that application of the natural biological source of calcium and carbon
becomes a potential heterogeneous catalyst for transesterification of
vegetable oil. This application is a promising method since it can
produce a highly efficient bio-based heterogeneous catalyst. The solid
catalysts prepared from biomass presents an environmental friendly
solution since it is non-toxic, non-corrosive and eliminate the produc-
tion of wastewater [40]. On top of that, it is mainly derived from
biomass that is considered as a low-cost material and abundantly
available [48]. Apart from that, there is no imminent disposal problem
since the catalyst itself is biodegradable [49]. The present study reviews
the development of heterogeneous base and an acid catalyst derived
from biomass for biodiesel production. The source of catalyst, methods
of preparation and performance of these catalysts is presented in this
study. This paper aims to provide useful and informative knowledge on
the current biomass-derived heterogeneous catalyst for future devel-
opment in the field of biodiesel process and production.
2. Biomass-derived heterogeneous alkali/base catalyst
2.1. Sources of catalyst
2.1.1. Waste shell
The application of solid base catalyst in biodiesel production is
advantageous since it can be easily separated and further reused back
in the process. However, the extremely high price of the available
S.H.Y.S. Abdullah et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

Table 1
Advantages and disadvantages of different types of catalyst for transesterification reaction.

Type of catalyst Examples Advantages Disadvantages References

Homogeneous
Alkali NaOH, KOH • High catalytic activity • Low FFA requirement in the [1,31,32,39]
• Faster reaction time feedstock ( < 1 wt%),
• Low cost • Highly sensitive to water and
• Favorable kinetics FFA
• Modest operational conditions • Saponification as side reaction,
• Soap formation
• High volume of wastewater
• Catalyst is non-recyclable
• Equipment corrosion
Acid H2SO4, HCL, HF, H3PO4, ρ-sulfonic acid • Insensitive to FFA and water content in • Slow reaction rate [1,31,32,39]
oil • Long reaction time
• Catalyzed simultaneous esterification and • Equipment corrosion
transesterification reactions • Higher reaction temperature
• Avoid soap formation and pressure
• High alcohol/oil requirement
• Weak catalytic activity
• Catalyst is difficult to recycle
Heterogeneous
Alkali CaO, MgO, SrO, mixed oxide and hydrotalcite • Non corrosive • Slow reaction rate compared to [1,31,32,39]
• Environmentally benign homogeneous one
• Recyclable • Low FFA requirement in the
• Fewer disposal problems feedstock ( < 1 wt%)
• Easy separation • Highly sensitive to water and
• Higher selectivity FFA
• Longer catalyst life • Saponification as side reaction
• Soap formation
• High volume of wastewater
• Leaching of active catalyst sites
• Diffusion limitations,
• Complex
synthesis route
and expensive

• High cost of catalyst synthesis

Acid ZrO, TiO, ZnO, ion-exchange resin, sulfonic modified • Insensitive to FFA and water content in • Slow reaction rate [1,31,32,39]
mesostructured silica, sulfonated carbon-based catalyst, the oil • Long reaction time
HPA and zeolites • Catalyzed simultaneous esterification and
transesterification reactions
• Higher reaction temperature
and pressure
• Recyclable, eco-friendly • High alcohol/oil requirement
• Non-corrosive to reactor and reactor parts • Weak catalytic activity
• Low acidic site
• Low micro porosity
• Leaching of active catalyst sites
• Diffusion limitations
• Complex
synthesis route
and expensive

• High cost of catalyst synthesis

Enzyme Candida antarctica fraction B lipase, Rhizomucor miehei
lipase
catalyst since it requires a number of chemical reagents and multi-step
preparation procedure retards further applications of this type of
catalyst [47]. Hence, the search for greener catalyst to replace the
use of conventional base catalyst has been reported by numerous
studies. Most of them utilized the catalyst derived from calcium
carbonate enriched organic waste such animal bones and shells [50].
Upon high temperature combustion, calcium carbonate (CaCO3) will be
converted into calcium oxide (CaO), which is a highly active base
catalyst for biodiesel production [51]. Generally, CaO can be obtained
from calcium carbonate from limestone. However, the length and cost
of the synthesis route become a burden besides the impact of the
nonrenewable sources of limestone [52]. Hence, a catalyst derived from
organic waste materials has gained much attention as they are non-
toxic, safe to handle and store, abundantly available, low cost and come
from renewable sources [47]. Waste shells mainly composed of CaCO3
(96–98%) with trace amount of magnesium carbonate (MgCO3),
• Insensitive to FFA and water content in • Very slow reaction rate [1,9,31]
the oil • Highly expensive
• Avoid soap formation • Highly sensitive to alcohol
• Non-polluting • Denaturation of enzyme
• Easy purification
• Possible reuse
strontium carbonate (SrCO3), calcium phosphate, organic substance
and water [53]. Most of them have no value, no practical use and
abundantly discarded by marine product manufacturers and local
restaurant into landfill [54]. The high amount of CaCO3 in waste shells
makes it a promising source for the synthesis of CaO-derived catalyst.
On top of that, the synthesis route for the biomass-derived catalyst is
rather simple, inexpensive and environmentally-friendly [55].
Utilization of waste shells may eliminate the waste and produce
value-added byproducts. Various types of CaCO3-enriched organic
wastes have been investigated as the potential catalyst for biodiesel
production, including waste shell [55–58], waste egg shell [59], waste
coral fragment [60], waste fish scale [61] and waste animal bones
[47,62].
2.1.2. Biomass ashes
Apart from that, several studies investigated the potential of

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S.H.Y.S. Abdullah et al.
biomass ashes to be the catalyst for biodiesel production. Naturally,
organic compound may contain high amount of carbon (C) and oxygen
(O) and metal salt including potassium (K), sodium (Na), magnesium
(Mg), calcium and (Ca) [48]. Upon combustion at a very high
temperature, the C and O content will abruptly reduce, leaving the
alkali metal oxides such as CaO, potassium oxide (K2O) and magne-
sium oxide (MgO) as the main active ingredients in the ashes [18]. The
presence of high basic strength oxides in the ashes increased its
catalytic ability to produce biodiesel [63]. In another study by Ofori-
Boateng and Lee [64] reported that, potash as the potential catalyst for
biodiesel production. In another study by Potash or potassium-bearing
materials can be found in the form of potassium carbonate (K2CO3) or
potassium chloride (KCl), a by-product of biomass combustion.
Inorganic-derived potash has proven to possess high catalytic ability
and being used as a base catalyst in biodiesel production, but their
synthesis is rather hazardous, environmentally damaging and unsus-
tainable. Thus, biomass-derived potash exhibits similar catalytic activ-
ities of the previous one in addition to environmentally friendly, safe
and sustainable.
2.1.3. Activated carbon supported catalyst
Activated carbon (AC) is a form of amorphous carbon with high
porosity nature [31]. It is mainly derived from high carbon content
compounds such as coal, wood, and coconut shell. AC is widely being
used in pollution control applications including air and gas filter
system, wastewater treatment, removal of toxic compounds such as
organic pollutants, heavy metals, and organic dyes as well as a catalyst
support [65]. AC provides higher surface area through the existence of
high numbers of pores where active metal particles can be anchored
[29]. The utilization of catalyst support in a heterogeneous reaction
may reduce the mass transfer limitation hence increased the rate of
reaction [66]. The commercially available catalyst supports such as
alumina and silica is highly expensive thus retard wider use. Thus, the
use of low-cost AC as support for biodiesel production will reduce the
overall cost of production [67]. Several studies investigated the
potential of biomass-derived activated AC as catalyst support by
impregnating with certain active metals to improve its catalytic
performance. Previously, Vadery et al. [18] stated that chemical
treatment with a K or CA containing compound has significantly
increased the catalytic ability of AC catalyst. A high number of active
sites in AC indicated by surface porosity provide sufficient adsorptive
sites for reaction to take place [68]. In another study by Chakraborty
et al. [59] concluded that high amount of SiO2 and Al2O3 of fly ash
provides a good low-cost catalyst support as opposed to the conven-
tional one. Hence, the overall performance for biodiesel production was
significantly increased. Quite a few biomass ashes have been studied in
their potential as a solid base catalyst including cocoa pod husk ash
[64], coconut husk ash [18] and empty palm bunch ash [68]. Table 2
summarizes the wide variety of solid base catalyst has been studied for
biodiesel production.
2.2. Catalyst preparation
Calcination is the most common method utilized for the prepara-
tion of biomass-derived solid base catalyst. Calcination involved
thermal treatment in the absence of air and oxygen in order to break
down or decompose a compound into a smaller component. Generally,
calcination can be carried out at a wide range of temperature ranging
from 300 to 1000 °C depending on the type of feedstock. Upon
combustion, CaCO3 in the organic compound will break down into
CaO and releases CO2 gas. Fig. 2 illustrates the general procedure for
preparation of CaO-derived catalyst from waste shells.
The calcination temperature plays a significant role in the forma-
tion of CaO as well as development of the surface morphology of the
catalyst. Since most waste shells are most likely non-porous material,
size of developed particles on the catalyst surface reflect the total
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
surface area of a prepared catalyst. Hence, the catalytic activity of a
prepared catalyst is highly dependent on the calcination temperature
that determined the intensity of active sites. In a study by Smith et al.
[47] investigated the effect of different calcination temperature of
bovine bone waste. It was found that, no significant changes and no
positive effect on FAME yield were observed for calcined sample in the
range of 350–550 °C. This suggests that, the utilized temperature does
not have sufficient energy for the conversion of CaCO3 into CaO. The
increment in the calcination temperature from 650 to 950 °C con-
firmed the presence of CaO in the calcined bone sample. Highest FAME
yield was obtained using catalyst calcined at the temperature of 750 °C.
On top of that, the formation of CaO created additional void on the
catalyst surface that simultaneously increase the total pore volume and
pore diameter of the prepared catalyst. Following that, higher catalytic
activity was observed. However, further increment in the calcination
temperature exceeding 950 °C showed a drastic reduction in the
catalyst activity due to low pore volume and presence of micro pores
that could relatively reduce the quantity of accessible active site on the
catalyst surface. In another study by Boro et al. [55] found that
calcination temperature does affect the surface morphology of the
calcined sample. At a lower calcination temperature of 600 °C, the
catalyst surface was observed to have non-uniform and aggregated
arrangement as a result of amalgamation of the various elemental
components including Ca, Na, Mg, Si and Sc. The total pore volume did
not show any significant change meaning that there were additional
pores present on the catalyst surface. On the other hand, at higher
temperature of 700–900 °C, Ca becomes the major compound in the
calcined sample along with the appearance of particles with various
sizes and shapes. The higher surface area was observed with a higher
degree of calcination due to the formation of crystal growth of CaO in
the calcined sample. Moreover, development of surface porosity
indicated by the increase in the pore volume in the calcined shell was
attributed to the evolution of gaseous carbonization product as well as
CaO formation. In addition, the calcination holding time also gives
significant effect on the CaO development. The short holding time may
be a great disadvantage since the CaO might be underdeveloped thus
affecting the catalytic activity. Longer calcination time is required to
ensure complete conversion of CaCO3. However, the prolonged calci-
nation process caused sintering effect to the particles that lead to
shrinkage of the catalyst grains. Hence, a reduction in the total effective
surface area resulted in significant in the catalytic activity [60].
The preparation of supported solid base catalyst can be carried out
through a tri - step procedure of calcination-wet impregnation-activa-
tion as shown in Fig. 3. Calcination can be conducted at a specific
temperature depending on the type of feedstock. Wet impregnation is a
chemical treatment in which various types of active metal precursor
mix with the calcined sample in an aqueous or organic solution in order
to produce supported catalyst. High basic strength metal salts and
oxides, including NaOH, KOH and CaO are being commonly used in
wet impregnation. Upon impregnation, the metal salt will tend to
diffuse in the porous structure of the catalyst support. Consequently,
the impregnated calcined sample will be subjected to thermal activa-
tion to remove moisture and volatile matter as well as aid in depositing
the metal salt on the catalyst surface. The catalytic activity of supported
catalyst is higher than that of unsupported one due to enhancement in
their basic strength.
2.3. Biodiesel production
2.3.1. Waste shell
Waste shells are the widely investigated as heterogeneous base
catalyst for biodiesel production. Previously, Boey et al. [70] studied
the use of the waste cockle shell of Anadara granosa in biodiesel
production from palm olein oil. The waste shell was calcined at 900 °C
for 2 h to produce an active catalyst that mainly composed of 71% of
Ca. Further utilization in the transesterification process resulted in
S.H.Y.S. Abdullah et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

Table 2
Biomass-derived solid base catalyst for biodiesel production.

Type of biomass Type of feedstock Catalyst preparation conditions Transesterification reaction FAME References

CT (°C) Ct (h) CI T (°C) t (h) CL (wt%) MTOR Y or C (%)

Waste shell
Waste shell of Turbonilla striatula Mustard oil 600–900 4 – 65 3 3 9:1 93.3(Y) [69]
Waste cockle shell of Anadara granosa Palm olein oil 900 2 – – 3 4.9 0.54:1 97.4(Y) [70]
Waste fish scale of Labeo rohita Soybean oil 600–1000 2 – 70 5 1.01 6.27:1 97.7(Y) [72]
Waste oyster shell Soybean oil 1000 4 KI 50 4 1 mmol/g 10:1 85(C) [73]
Waste shell of golden apple snail Palm olein oil 800 2–4 – 60 2 10 18:1 93.2(Y) [71]
Waste shell of meretrix venus Palm olein oil 800 2–4 – 60 2 10 18:1 92.3(Y) [71]
Waste capiz shell of Amusium cristatum Palm oil 900 2 – 60 6 3 8:1 93.0(Y) [58]
Scallop waste shell Palm oil 1000 4 – 65 3 10 9:1 95.4(C) [54]
Crab shell Sunflower oil 900 2 – 60 4 3 6:1 83.1 (C) [52]

Waste coral
Waste coral fragment Vegetable oil 700 0.5–1.5 – 65 2 100 15:1 98.0(Y) [60]

Waste egg shell

Waste egg shell Palm olein oil 800 2–4 – 60 2 10 18:1 94.1(Y) [71]
Duck eggshell Palm oil 900 4 – 60 4 20 9:1 92.9(Y) [53]
Chicken eggshell Palm oil 900 4 – 60 4 20 9:1 94.4(Y) [53]
Eggshell Sunflower oil 900 2 – 60 3 3 9:1 97.8 (C) [52]

Animal bones
Bovine bone waste Soybean oil 350–1000 6 – 65 3 8 6:1 97.0(Y) [47]

Biomass ashes
Musa balbisiana Colla ash T. peruvinia seed oil – 0.5 – 32 3 20 20:1 96.0(C) [74]
Tars and alkali ashes Sunflower oil 600–800 4 – – 12 – – 75.0(C) [48]
Coconut husk ash Jatropha oil 250–500 1 – 45 0.5 7 12:1 90.0(Y) [18]

Activated carbon supported catalyst

Fly ash/CaO-derived eggshell Soybean oil 1000 2 CaO 70 5 1 9:1 96.9 (Y) [59]
Cocoa pod husk ash/MgO Soybean oil 650 4 MgO 40 0.5 7 6:1 98.7 (Y) [64]
Empty palm bunch ash Waste cooking oil – – KOH 60 2 17.3 5:1 – [68]

CT=Calcination temperature, Ct=Calcination holding time, CI=Chemical impregnation, T=Reaction temperature, t=Reaction time, CL=Catalyst load, MTOR=methanol-to-oil molar
ratio.

Fig. 3. General flowchart for the preparation of supported catalyst.

particles with various sizes and shapes were observed on the catalyst
surface. The reusability study confirmed leaching of active species that
Fig. 2. General flowchart for the preparation of CaO-derived catalyst.
significantly reduce the efficiency of the catalyst. However, the spent
catalyst regained its activity upon re-calcination at 900 °C for 3 h.
97.48% of FAME yield within 3 h reaction time. The spent catalyst can
Suryaputra et al. [58] prepared a new heterogeneous catalyst for
be reused three cycles upon treatment with methanol and hexane
biodiesel production from waste Capiz shell of Amusium cristatum.
followed by re-calcination at 900 °C for 2 h. In another study by Boro
The catalyst was calcined in a furnace at 900 °C for 2 h to ensure
et al. [69], the waste shell of Turbonilla striatula was found to be a
complete conversion of CaCO3 into CaO. A high FAME yield of 93%
promising catalyst for biodiesel production using mustard oil. Effect of
was obtained with the use of 3 wt% of prepared catalyst in a 6 h
different calcination temperature was studied (600–900 °C) and tem-
reaction. After the third cycle, the activity of the catalyst was abruptly
perature of 700 °C was found to be the most optimum temperature
decreased by almost 50% of the fresh one due to several factors
with highest FAME yield of 93.3%. At this temperature, presence of
including contact of basic sites with ambient CO2 and water.

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S.H.Y.S. Abdullah et al.
Furthermore, the number of active sites decreased caused by side
reactions with FFA and leaching of CaO into polar solvent. Another
source of CaO-derived catalyst, the waste scallop shell was investigated
by Buasri et al. [54] for biodiesel production from palm oil. Prior to
transesterification reaction, scallop shell undergoes calcination at
1000 °C for 2 h that resulted in the formation of smaller size of the
grains and aggregates on the catalyst surface. This condition led to an
increment in the specific surface area of the catalyst and simulta-
neously improves its catalytic activity. The resultant catalyst was able to
yield 95.44% of FAME within 3 h reaction time.
On the other hand, Correia et al. [52] evaluated the performance of
two different types of waste shells in the transesterification of sunflower
oil. Eggshell and crab shell were calcined at 900 °C for 2 h to
decompose organic matter and complete conversion into CaO. The
use of eggshell resulted in 97.75% of FAME yield under reaction
conditions of 3 wt% catalyst load, methanol-to-oil ratio of 9:1 and 3 h
reaction time. On the other hand, crab shell showed FAME yield of
83.1% under reaction conditions of 3 wt% catalyst load, methanol-to-
oil ratio of 6:1 and 4 h reaction time. Eggshell showed better catalytic
activity than that of crab shell owing to the higher surface content of Ca
as a result of homogeneously distributed and well-develop pores during
calcination process. A similar study was conducted by Viriya-empirikul
et al. [71] that compared the performance of three types of waste shells
on the biodiesel production from palm olein oil. Waste shells of egg,
golden apple snail, and meretrix venus were transformed into CaO
through calcination at 800 °C for 0.5–8 h before subjected to transes-
terification reaction. After 1 h reaction, the yield of biodiesel using
waste shells of egg, golden apple snail, and meretrix venus were 93, 86
and 74% respectively. Eggshell showed excellent ability as a catalyst
compared to others due to the formation of the smallest particles of
various shapes and size that provide highest surface area for the
reaction. Nevertheless, all catalysts provides FAME greater than 90% at
reaction time of 2 h. The authors also studied the effect of various
calcination time on the calcined sample. From the observation,
prolonged calcination time gave sintering effect on the catalyst particle
and shrinkage to the grains that might lower the surface area. Hence,
the catalytic activity was drastically reduced and reducing the yield of
biodiesel. The optimal calcination holding time was found to be at 2–
4 h.
Buasri et al. [53] compared the performance of chicken and duck
eggshell as the source of catalyst for biodiesel production. The catalysts
were prepared by calcination at 900 °C for 4 h before being used in the
transesterification reaction. Upon calcination, formation of particles
with irregular shapes and various sizes on the catalyst surface provide
high specific active site for reaction. However, higher surface area and
pore volume in were observed in chicken eggshell represented by BET
surface area and pore volume value of 136.10 m2/g and 0.12 cm3/g
respectively. At reaction conditions of 20 wt% catalyst loading and
methanol-to-oil ratio of 9:1, biodiesel yield of 94.49% and 92.92% were
obtained using chicken and duck eggshells respectively. Reusability
study that was carried out showed that the spent catalyst displayed
exceptional catalytic activity of ( > 80%) up to four treatment cycles.
The decrease in the activity is mainly due to leaching of active sites
attributed to the bond breaking and formation of Ca2+ and CH3O−.
Apart from waste shells, several studies investigated the potential of
other CaCO3−enriched wastes, including the waste coral fragment,
waste fish scale, and waste animal bones. Waste coral showed excellent
ability with a FAME yield of 98% when used for transesterification of
waste cooking oil. The high porosity nature of the prepared catalyst was
observed after calcination at 700 °C for 1 h that improves the number
of active sites available for catalytic reaction [60]. In another study by
Chakraborty et al. [61] demonstrated the application of waste fish scale
for biodiesel production from soybean oil. The waste fish scale was
calcined 900 °C for 2 h prior to transesterification reaction to convert
hydroxyapatite into tri-calcium phosphate, which is the main active
compound that catalyzed the reaction. A maximum FAME yield of
6
Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
97.73% was obtained under 5 h of reaction time. In another study, the
application of fish bone supported with copper was studied as solid acid
catalyst for biodiesel production. The impregnation of copper signifi-
cantly improved the catalyst performance with a maximum oleic acid
conversion of 91.86% [72]. In addition, Smith et al. [47] investigated
the potential of bovine bone waste as the catalyst for biodiesel
production. Bovine bone composed mainly of crystalline calcium
carbonate and hydroxyapatite. Calcination at 650–950 °C for 6 h
resulted in the conversion of carbonate into CaO. Bovine bone-derived
catalyst demonstrated excellent catalytic activity with a FAME yield of
97% in 3 h reaction time. The authors suggested on doubling the
amount of catalyst loading to maintain effectiveness of spent catalyst
up to six consecutive runs. Regeneration might not be a cost and energy
effective option considering the low cost and ease of catalyst prepara-
tion.
In another study by Jairam et al. [73], the applicability of KI-
impregnated oyster shell as catalyst for biodiesel production was
investigated. The catalyst was prepared through calcination at
1000 °C for 4 h, followed by impregnation with KI and re-calcination
at 300 °C for 2 h. Impregnation improves the surface chemistry of the
catalyst by formation of thick layers of KI and increment in the surface
area from 1.8 to 6 m2/g (31-fold of untreated catalyst). Further use in
the transesterification of soybean oil resulted in 85% conversion into
FAME using 1 mmol/g of catalyst loading for 4 h reaction time.
2.3.2. Biomass ashes
Deka and Basumatary [74] investigated the potential of banana
trunk ash as a solid base catalyst for transesterification of T. peruvinia
seed oil. Banana trunk of the family of Musa balbisiana Colla was
ignited and burned to produce ash. Major components presented in the
ash including K, Na, CO3, Cl, and traces amount of some other metals
such as Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb. Further use in the
transesterification reaction resulted in 96% conversion of biodiesel at
room temperature in 3 h. The biodiesel produced from this process
presented sulfur-free product with a high cetane number. In another
study, Luque et al. [48] reported the use of tars and alkali ashes as
catalyst for biodiesel production. Tars and alkali ashes are the by-
products of syngas production that become a major disposal problem.
It is mainly composed of C, O, Si and smaller quantity of metals
including Na, Mg, K, Ca, S and P. The catalyst was prepared through
calcination at 500 −800 °C for 4 h. Upon calcination, significant mass
loss was observed due to removal or carbonaceous and volatile matter
within the catalyst. Hence, metal oxides become the main active
ingredient in the catalyst with 36 wt% composition of Ca. The prepared
catalyst presented moderate catalytic activity with the production of
75% biodiesel conversion in 12 h reaction. Meanwhile, Vadery et al.
[18] investigated the potential of coconut husk as the catalyst for
biodiesel production from Jatropha seed oil. The catalyst was prepared
through calcination at 250–500 °C for 1 h. Upon combustion, carbon
and oxygen content were rapidly reduced, leaving K species, including
KCl, K2Si2O5, and K2SO4 as the main components in the ash. Further
use of coconut husk ash as a catalyst transesterification reaction
resulted in 97% of FAME yield within 30 min reaction. The prepared
catalyst showed excellent performance ( > 95%) even at room tempera-
ture and lower methanol-to-oil ratio. However, reusability study
indicated that spent catalyst loss their activity due to excessive leaching
of active components thus prevent from repeated use.
2.3.3. Activated carbon supported catalyst
Previously, Chakraborty et al. [59] utilized fly ash, a coal combus-
tion waste as CaO- supported catalyst for biodiesel production from
soybean oil. Fly ash is mainly composed of a mixture of metal oxide
with high amount of SiO2 and Al2O3 which make it possible to be used
as catalyst supports. In this study, the catalyst was calcined at 1000 °C
for 2 h prior to wet impregnation with 30 wt% of CaO derived from the
eggshell. Then, the catalyst was activated at 1000 °C for 2 h. The
S.H.Y.S. Abdullah et al.
performance of fly ash-derived catalyst was confirmed with high FAME
yield of 96.97% under the following reaction conditions; catalyst
loading of 1 wt% and methanol-to-oil ratio of 6.9:1. This catalyst
showed superior catalytic activity compared to the unsupported CaO
catalyst judging from the increase in the BET surface area up to 89.73%
than that of unsupported ones. In addition, high potential of reusability
up to 16 runs makes supported fly ash-derived catalyst a cost-effective
and sustainable option. In another study, the application of tars and
alkali ashes were investigated for biodiesel production. Another
potential source of AC supported catalyst is a cocoa pod husk was
thoroughly investigated by Ofori-Boateng and Lee [64]. The cocoa pod
husk was calcined at 650 °C for 4 h in order to produce potash (K2CO3),
which the main active compound to catalyze the reaction. The
performance of unsupported and MgO-supported potash catalyst was
investigated in the transesterification of soybean oil. The biodiesel yield
using MgO-supported and unsupported potash were 98.7% and 91.4%
respectively. High FAME yield using MgO-supported catalyst was
mainly due to the higher specific surface area of (1021.8 m2/g) than
unsupported catalyst (987.2 m2/g) that increased the availability of
active sites on the surface of the catalyst. The application of empty fruit
bunch ash as AC supported catalyst was reported by Riadi et al. [68].
1.5 wt% of KOH were wet impregnated into empty fruit bunch to
improve its catalytic ability. The KOH-loaded catalyst showed excellent
performance with the production of short chain FAME and long chain
FAME of 85.772 mg/L and 655.286 mg/L respectively.
3. Biomass-derived heterogeneous acid catalyst
3.1. Source of catalyst
Recently, the application of biomass-derived solid acid catalyst has
caught the world's interest. It was first introduced by Toda et al. [75] in
the esterification of oleic and stearic acid into FAME by using a catalyst
prepared from sulfonation of incompletely carbonized carbon material.
This sulfonated carbon-based catalyst (SCBC) shows a promising
potential since it is stable, safer, renewable, inexpensive and simpler
synthesis routes. Kastner et al. [76] stated that the most distinctive
features of SCBC when compared to the conventional solid acid catalyst
bearing single functional group, is the presence of three acid sites,
namely weak carboxylic acid (-COOH), medium phenolic acid (−OH)
and strong sulfonic acid (−SO3H). Even though, −SO3H is the main
active acid site for catalytic reaction, both -COOH and -OH will
improve the hydrophilic properties of catalyst surface thus provide
more access for reactants [77]. On top of that, SCBC has a greater
resistance towards H2O deactivation during an esterification reaction,
allowing them to maintain their activity during the reaction [78].
Generally, SCBC can be derived from a number of carbon-enriched
sources that will be further discussed in this section. Table 3 sum-
marizes the type of biomass used as the solid acid catalyst for biodiesel
production.
3.1.1. Refined carbohydrate
The earliest study conducted on sulfonated carbon-based catalyst
utilized the use of refined carbohydrate as the precursor carbon for the
prepared catalyst. Carbohydrate is a biological molecule that is mainly
consists of carbon, hydrogen, and oxygen. High carbon content in the
carbohydrate makes it a promising source as a carbon precursor for
SCBC. Various types of refined carbohydrate were extensively studied,
including simple carbohydrate; glucose [41] complex carbohydrate;
starch [79] and dietary fiber carbohydrate; cellulose [80]. The applica-
tion of refined carbohydrate as solid acid catalyst showed a great
potential, however, pre-processing is required to extract and separate
refined carbohydrate from biomass prior to transesterification process.
This may incur additional cost for the biodiesel production.
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3.1.2. Biomass residue
Biomass residue or waste biomass is a waste produce as a result of
the oil extraction process from oil-bearing plant parts which mainly
consists of large organic hydrocarbon compound. The residue presents
an environmental problem and need for a proper treatment and
disposal that may incur additional cost to a facility. Hence, to avoid
this, a study on the potential of re-utilization of waste biomass as solid
acid catalyst in biodiesel production has been conducted. A number of
potential biomass was studied including vegetable oil asphalt [46,82]
and C.inophyllum seed cake [83] and microalgae residue [84]. The
biodiesel production using biomass residue may be a great option since
it is low cost, readily available and environmentally friendly [82]. Fu
et al. [84] stated that the utilization of biomass residue as the precursor
carbon for solid acid catalyst is advantageous as it is a cheap material
and usually discarded as waste. In another study by Silva et al. [85]
stated that apart from being low cost material, the uses of biomass
residue as catalyst allows changing on the surface chemical properties
in the appropriate manner. On top of that, the alternative uses of
biomass residue may reduce the volume of waste generated as well as a
reduction in the cost associated with a proper and hygienic waste
disposal [82].
3.1.3. Biochar
Biochar can be defined biomass-derived char, a carbonaceous
compound that mainly consists of 60–90% carbon with a highly porous
structure [86]. Biochar can be obtained as a by-product of pyrolysis
process, a process where biomass is directly converted into liquid, char
and condensable gases at high temperature condition in the absence of
oxygen. Upon pyrolysis, biomass components (lignin, cellulose, and
hemicelluloses) will undergo a series of thermal reactions and mole-
cular arrangement to form a polymerized aromatic structure. The
presence of highly cross-linked and multi-ringed aromatic structure of
biochar makes it possible to be functioned with active compounds.
Biochar is widely applied to increase soil fertility in the plantation area
[87]. The nature of biochar that is highly porous with high surface area
will improve the soil characteristic thus promote the plant's growth.
Recently, the application of biochar as a catalyst has been widely
discussed, including utilization of biochar in the decomposition of
syngas [88], conversion of syngas into liquid hydrocarbon [89],
hydrolysis of hemicellulose [90] and biodiesel production [76]. The
catalytic activity of biochar derived catalyst is highly correlated to its
porosity, surface area, and mineral content. The wide applications of
biochar derived catalyst provide a value-added product to the existing
waste and residue from industrial processing.
3.1.4. Activated carbon
Generally, AC can be obtained from thermal decomposition of high
carbon content compounds such as coal, wood and coconut shells.
Upon heat treatment, water will be removed through vaporization and
lead to carbonization that converts all organic materials into elemental
carbon. As a result, a highly disorganized form of carbon with a wide
range of pore sizes, cracks and crevices is obtained [31]. The high
porosity nature of AC makes it a promising choice as a carbon
precursor for sulfonated carbon-based catalyst. Sulfonation of AC will
result in the formation of a catalyst with catalytic performance. Apart
from that sulfonated-AC catalyst offers several advantages including
low cost, high surface area, high heat resistance and stability in both
acidic and basic environments. The utilization of sulfonated-AC
catalyst in biodiesel production have been widely investigated using
different raw materials such as peanut hulls [76], corn straw [91],
Xanthoceras sorbifolia Bunge hulls [92], oil palm trunks and sugar-
cane bagasse [6].
3.2. Catalyst preparation
SCBC is prepared through incomplete carbonization of precursor
 S.H.Y.S. Abdullah et al.

Table 3
Biomass-derived solid acid catalyst for biodiesel production.

Type of biomass Type of feedstock Catalyst preparation conditions Transesterification reaction FAME References

CT (°C) Ct (h) SA ST (°C) St (h) T (°C) t (h) CL (wt%) MTOR Y or C (%)

Refined carbohydrates
D-glucose Oleic and stearic acid 400 15 Conc. H2SO4 ( > 96%) 50 15 80 1 0.2 g – 44 µmol/min [41]
D-glucose Oleic and stearic acid 400 15 Fum. SO3 (15 wt%) 50 15 80 1 0.2 g – 86 µmol/min [41]
Starch Waste cooking oil 400 – Conc. H2SO4 ( > 96%) ≥100 – 80 3 10 20:1 95(Y) 97
Cellulose Waste cooking oil 400 – Conc. H2SO4 ( > 96%) ≥100 – 80 3 10 20:1 88(Y) [97]
Sucrose Waste cooking oil 400 – Conc. H2SO4 ( > 96%) ≥100 – 80 3 10 20:1 80(Y) [97]
Glucose Waste cooking oil 400 – Conc. H2SO4 ( > 96%) ≥100 – 80 3 10 20:1 76(Y) [97]
D-glucose-starch mixture Oleic acid 400 1–1.5 Conc. H2SO4 ( > 98%) 150–160 5 60–80 12 5 10:1 96 (Y) [76]
D-glucose-starch mixture Triolein 400 1–1.5 Conc. H2SO4 ( > 98%) 150–160 5 80 12 5 30:1 60 (Y) [76]
D-glucose-starch mixture Waste cottonseed oil 400 1–1.5 Conc. H2SO4 ( > 98%) 150–160 5 80 12 5 20:1 90 (Y) [76]
D-glucose C.inophyllum seed oil 400 5 Conc. H2SO4 150 10 180 4 5 15:1 51.4 (C) [75]
Microcrystalline cellulose C.inophyllum seed oil 400 5 Conc. H2SO4 150 10 180 4 5 15:1 99 (C) [75]

Biomass residue
Vegetable oil asphalt Cottonseed oil 500–700 – Conc. H2SO4 ( > 98%) 120 4 260 3 0.2 18.2:1 89.93 (C) [46]
Vegetable oil asphalt Waste vegetable oil 500–700 2 °C/min Conc. H2SO4 ( > 98%) 210 10 220 4.5 0.2 16.8:1 80.5(C) [82]

8
Vegetable oil asphalt Waste vegetable oil 500–700 2 °C/min Conc. H2SO4 ( > 98%) 210 10 140 3 0.3 – 80(C) [101]
Petroleum asphalt Waste vegetable oil 500–700 2 °C/min Conc. H2SO4 ( > 98%) 210 10 140 3 0.3 – 50(C) [101]
C.inophyllum seed cake residue C.inophyllum seed oil 400 5 Conc. H2SO4 150 10 150 5 0.3 g 5.5 g 36.4 (C) [83]
C.inophyllum seed cake residue C.inophyllum seed oil 400 5 PTSA 150 10 150 5 0.3 g 5.5 g 14.2 (C) [83]

Biochar
Pyrolyzed harwood char Canola oil – – Conc. H2SO4 ( > 98%) 150 24 65 3 5 18:1 89 [7]
Pyrolyzed harwood char Canola oil – – Fum. SO3 (15 wt%) 150 5, 15 65 3 5 18:1 92 [7]
Peanut hull, pine and wood biochar Soybean oil 400–600 1 Conc. H2SO4 ( > 98%) 100, 150, 200 12 57–59 6 4–7.5 20:1 70(C) [76]
Woody biomass char Canola oil and oleic acid mixture 675 2 Fum. SO3 ( > 20 wt%) 150 15 150 3 5 10:30 48(Y) [102]
Rice husk char Waste cooking oil 510 480 °C/s (4 s) Conc. H2SO4 (95–98 wt%) 90 0.5 110 15 5 20:1 87.57(Y) [103]

Activated carbon
Peanut hull Soybean oil – – Conc. H2SO4 ( > 98%) 100, 150, 200 12 57–59 6 4–7.5 10:1 97(C) [76]
Peanut hull Soybean oil – – Fum. SO3 (15 wt%) 23 6 days 57–59 3 4–7.5 6:1 > 94(C) [76]
Xanthoceras sorbifolia hull Acidified soybean soapstock 400 1 Conc. H2SO4 (98%) 150 2 70 5 7 91 97(C) [92]
Corn straw Oleic acid 300 1 Fum. SO3 (30 wt%) 80 4 60 4 7 7:1 98 (Y) [91]
Oil palm trunk Palm olein 400 8 Conc. H2SO4 (95–97%) 150 15 65 0.75 2 Pseudo infinite 93 (Y) [6]
Sugarcane bagasse Palm olein 400 8 Conc. H2SO4 (95–97%) 150 15 65 0.75 2 Pseudo infinite 94 (Y) [6]
Sugarcane bagasse Waste cooking oil 400–800 5 Conc. H2SO4 (98%) 120–200 5–15 66 5 1 18:1 94 (C) [104]
Sugar beet pulp Palm fatty acid distillate 400 2 Conc. H2SO4 (98%) 300 6 85 5 3g 5:1 92 (Y) [105]

CT=Carbonization temperature, Ct=Carbonization holding time, SA=Sulfonating agent, ST=Sulfonation temperature, St=Sulfonation holding time, T=Reaction temperature, t=Reaction time, CL=Catalyst load, MTOR=methanol-to-oil molar ratio.
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S.H.Y.S. Abdullah et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

density in SCBC prepared via fuming H2SO4 [101]. Takagaki et al. [41]
highlighted that higher catalytic activity in fuming H2SO4 is attribu-
table to the high water consumption that promotes formation of
−SO3H through the reaction of water and H2SO4 hence stronger
sulfonation was observed. Another study by Dawodu et al. [82]
compared the performance of concentrated H2SO4 and P-toluenesul-
fonic acid (PTSA) to functionalize carbon catalyst. It was found that
sulfonation using concentrated H2SO4 showed superior activity than
that of PTSA due to higher sulfur content in concentrated H2SO4 that
leads to higher distribution of the acid density when compared to the
PTSA. Apart from that, sulfonation also promotes the activation and
oxidation of carbon that led to the improvement in the surface area and
pore structure [97]. However, the catalytic activity of SCBC is also
dependent on the type of precursor carbon structure as previously
mentioned in a study by Kastner et al. [76]. In the study, sulfonation
using concentrated H2SO4 generated higher acid site density in biochar
on the other hand sulfonation using fuming H2SO4 generated higher
acid density in activated carbon.

3.3. Biodiesel production

Fig. 4. General flowchart for the preparation of sulfonated carbon based catalyst (SCBC).
3.3.1. Refined carbohydrate
Previously, Takagaki et al. [41] prepared a solid acid catalyst from
carbon followed by sulfonation with various types of sulfonating agent
D-glucose as the precursor carbon for the esterification of higher fatty
as shown in Fig. 4. To this extent, pyrolysis and hydrothermal
acid mixture. The carbon sample was carbonized at lower temperature
carbonization are the widely used carbonization method to prepare a
prior to sulfonation with two types of sulfonating agents (concentrated
carbon-based catalyst. Pyrolysis is often carried out at a temperature in
and fuming H2SO4). Fuming H2SO4 displayed higher esterification
the range of 200–700 °C under nitrogen flow or argon atmosphere. The
efficiency denoted by higher rates of FAME formation of 86 µmol/min
preparation variables, including carbonization temperature, carboniza-
than only 44 µmol/min in concentrated H2SO4. In addition, the both
tion time and sulfonation temperature greatly influenced the textural
catalysts showed remarkable catalytic activity in comparison to the
properties of the prepared catalyst. The high temperature will result in
commercial solid acid catalysts such as Nafion (NR50), niobic acid and
the formation of rigid carbon structure which hindered the anchoring
H-mordenite. The presence of −SO3H groups in the prepared catalysts
of sulfonic (−SO3H) groups, thus reduced the density of active acid
significantly improved the total acid density in the prepared SCBC that
sites on the prepared catalyst [77]. On the other hand, synthesis of
contributes to their high performance. In another study by Lou et al.
carbon catalyst at a lower pyrolysis temperature (400–500 °C) will
[92] compared the performance of four different refined carbohydrates
result in the generation of soft aggregated, cross-linked polymer that is
as solid acid catalyst for the transesterification of waste cooking oil. The
susceptible to being sulfonated at the highest degree [76]. Further use
refined carbohydrate including starch, cellulose, sucrose and D-glucose
of the catalyst showed highest esterification activity. In a study by Shu
were carbonized at 300 °C followed by sulfonation with concentrated
et al. [81], SCBC that was carbonized at lower temperature (650 °C)
H2SO4. After 3 h reaction, the four corresponding catalysts prepared
showed excellent performance on the conversion of cottonseed oil and
from starch, cellulose, sucrose and D-glucose resulted in FAME yield of
FFA compared to those with high carbonization temperature (950 °C).
95, 88, 80 and 76% respectively. Thus, the type of precursor carbon
This is attributable to higher acid site concentration and larger pore
plays a big part in the determination of catalytic activity. It was found
diameter in the prepared catalyst at a lower carbonization temperature.
that higher surface area and total acid density in starch-derived catalyst
On top of that, Lou et al. [92] stated that formation of water layer was
explained the superior activity of the catalyst compared to others.
observed on the surface of catalyst at a lower carbonization tempera-
Larger pore size and volume promotes the incorporation of the bulk oil
ture that will prevent access to hydrophobic materials including FFA.
molecules into the active sites of the catalyst thus improves the catalytic
On the other hand, hydrothermal carbonization can be defined as
efficiency of starch-derived catalyst. On the other hand, Chen and Fang
pressurized thermal conversion conducted at a lower temperature
[79] investigated the potential of glucose-starch as solid acid catalyst
(150–350 °C) with the presence of water [93,94]. Hydrothermal
for biodiesel production. The glucose-starch mixture was incompletely
carbonization produces a carbonaceous residue called hydrochar which
carbonized at 400 °C for 60–90 min and sulfonated using concentrated
mainly consist of 45–75% carbon content [95]. Utilization of SCBC
H2SO4 at 150–160 °C for 5 h. The result of the study indicated that the
prepared from hydrothermal carbonization showed excellence catalytic
amylopectin content in starch greatly influenced the attachment of
activities comparable to homogeneous H2SO4 process [96]. Deshmane
−SO3H group onto the carbon compound. Further utilization of the
et al. [97] reported that SCBC synthesis using hydrothermal carboniza-
prepared catalyst in esterification and transesterification processes
tion presented low evidence in the leaching of colloidal carbon.
showed a biodiesel yield of 96% and 60% respectively. Reusability
Sulfonation is a process where precursor carbon is functionalized
study confirmed that the catalyst activity remained ≥90% up to 15
with active sulfonic acid (−SO3H) group. It was found to be an effective
cycles with regeneration of catalyst using H2SO4. The potential of
catalyst for esterification and transesterification reaction [98].
cellulose-derived catalyst for biodiesel production has been investi-
Sulfonation will result in the increased in the total acid density of
gated by Ayodele and Dawodu [80]. The catalyst was prepared by
SCBC by formation of −SO3H groups and additional weak carboxylic
carbonization under dry N2 at 400 °C for 5 h to produce carbonaceous
(−COOH) and phenolic (−OH) groups [76]. Total acid density and
solid. The resulting solid was a sulfonated using concentrated H2SO4 at
particularly sulfonic acid density are the crucial factors in the determi-
150 °C for 10 h. The esterification activity of cellulose-derived catalyst
nation of catalytic activity. Concentrated and fuming H2SO4 are widely
was investigated using C.inophyllum oil and the results displayed
used as sulfonating agent in the preparation of SCBC due to availability
superior performance of cellulose-derived catalyst as compared to
and cheaper prices [99]. Fuming H2SO4 showed superior activity than
glucose-derived catalyst with a biodiesel yield of 99 and 51.4%
that of concentrated H2SO4 indicated by the higher value of total acid
respectively. The high activity of cellulose-derived catalyst is due to

9
S.H.Y.S. Abdullah et al.
high acid density and better porous structure than that of D-glucose-
derived catalyst.
3.3.2. Biomass residue
Previously, Shu et al. [46] investigated the potential of solid acid
catalyst derived from vegetable oil asphalt for biodiesel production.
Vegetable oil asphalt consists mainly of hydrocarbon, a solid residue of
biodiesel production. Vegetable oil asphalt was first carbonized at 500–
700 °C at a rate of 2 °C/min under argon atmosphere. The sulfonation
of carbonized product was performed using concentrated H2SO4 at
120 °C for 4 h to obtain sulfonated vegetable oil asphalt. The carboni-
zation process produced a carbon catalyst with loose irregular network
structure with several micropores. Upon sulfonation, the pore sizes
become larger due to particle agglomeration and disintegration. The
sulfonated vegetable oil asphalt catalyst displayed high catalytic activity
with 89.93% conversion of cottonseed oil into FAME. This is mainly
due to the accessibility of reactant into the active acid sites on the
surface of the catalyst, hence better activity. Comparison with sulfo-
nated multiwalled carbon nanotube (s-MWCNT) showed higher per-
formance of the prepared catalyst. It can be noted that surface area and
porosity greatly influenced the activities. The author further investi-
gated the use of vegetable oil asphalt derived catalyst for the transes-
terification of waste vegetable oil [86]. The results of the study showed
higher activity of the prepared catalyst with 80.5% conversion. This
indicated that different feedstock gives minimal impact on the catalyst
performance. In another study, the activity of two different catalyst
sources was investigated [100]. Solid acid catalyst derived from
vegetable oil asphalt and petroleum asphalt was prepared using the
same procedures. The catalysts differ in their textural properties and
surface porosity due to the difference in their elemental compound and
molecular structure. Vegetable oil asphalt-based catalyst exhibited
superior activity than that of petroleum asphalt derived catalyst
attributable to high acid density and larger pore diameter. Higher
conversion of FFA and triglyceride was observed using vegetable oil
asphalt derived catalyst. Dawodu et al. [87] investigated the potential
of the seed cake residue of C. inophyllum as precursor carbon for
SCBC. The catalyst was carbonized at 400 °C for 5 h to obtain
incompletely carbonized compound. Sulfonation of carbon compound
was carried out using two different sulfonating agents which are
concentrated H2SO4 and PTSA. Carbon catalyst sulfonated using
concentrated H2SO4 exhibited high activity due to the high degree of
sulfonation compared to PTSA with FAME conversion of 36.4% and
14.2% respectively.
3.3.3. Biochar
A study by Dekhoda et al. [7] investigated the use hardwood char as
a catalyst for biodiesel production. The char was commercially
obtained and sulfonated using concentrated and fuming H2SO4 at
120 °C for 24 h and 15 h respectively. From the observation, sulfona-
tion greatly improved the textural properties of the catalysts. However,
higher total acidity, surface area, and porosity were observed in the
catalyst sulfonated with fuming H2SO4 compared to concentrated
H2SO4. The transesterification capacity of both catalysts was studied
using canola oil resulted in higher conversion of biodiesel of 89 and
92% using concentrated and fuming H2SO4 respectively. Higher sur-
face area and porosity in the prepared catalyst indicated that high
availability of the active site for reaction to take place. Thus, the
catalytic performance will be significantly improved. In another study,
mixture of peanut hull, pine logs residue, and wood chips were used to
generate biochar [76]. The biochar was functionalized with concen-
trated and fuming H2SO4 at 150 °C for 12 h to produce sulfonated
biochar. The result of the study showed that the prepared catalyst had a
high esterification efficiency with 70% FAME conversion. The reusa-
bility study indicated that the catalyst loss its activities to half of its
original conversion capacity due to strong water absorption, particle
attrition and leaching of active site. In another study by Dekhoda and
10
Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
Ellis [101] investigated the effect of different alcohol to oil molar ratio
and alcohol to FFA molar ratio of the biodiesel yield. Biochar-derived
solid showed high efficiency with 48% yield in 3 h reaction time. On the
other hand, Li et al. [102] compared the performance of rice husk char
derived catalyst with commercial catalyst Amberlyst-15 for biodiesel
production. Rice husk char was sulfonated using concentrated H2SO4
at 90 °C for 30 min to produce sulfonated char with high sulfonic acid
density. The transesterification of waste cooking oil showed a high yield
of biodiesel using the prepared catalyst as compared to Amberlyst-15
with 87.57% and 45.17% respectively.
3.3.4. Activated carbon
Kastner et al. [76] studied the performance of sulfonated AC from
peanut hulls for biodiesel production. The sulfonation procedure was
conducted using two different sulfonating agents which are concen-
trated and fuming H2SO4. It was found that, fuming H2SO4 provide
higher acid density in the sulfonated AC due to the fact that fuming
H2SO4 is more reactive and selective than concentrated H2SO4. Both
catalysts showed excellent performance with > 90% biodiesel conver-
sion. The novel solid acid catalyst for biodiesel production was derived
from residual lignin of Xanthoceras sorbifolia Bunge hulls [90]. The
catalyst was carbonized and sulfonated using concentrated H2SO4. The
performance of catalyst was later investigated in the esterification of
acidified soapstock. The high performance of the prepared catalyst was
observed with 98% of FFA conversion. The recycled catalyst loses its
activity after fourth cycles, thus affected the FFA conversion. A study by
Liu et al. [90] prepared sulfonated corn straw AC as solid acid catalyst
for the esterification of oleic acid. The catalyst was heated under N2
flow, followed by sulfonation using fuming H2SO4. A high acid density
catalyst with good dispersion and hydrophobic properties was obtained
from this study. The hydrophobic nature of the catalyst will prevent
from hydration thus retained its stability in the presence of water.
Biodiesel production using sulfonated corn straw AC produced 98% of
FAME yield. Previously, Zhang et al. [104] evaluated the performance
of sugarcane baggase derived catalyst in biodiesel production. The
catalyst was prepared through a series of carbonization and sulfonation
process in order to produce highly active catalyst. The effects of
pretreatment conditions on the catalytic activity were extensively
studied. The outcome suggested that, carbonization temperature of
600 °C and a sulfonation temperature of 200 °C is the optimal
condition in production highly active solid acid catalyst from sugarcane
baggase. In another study by Babadi et al. [104] investigated the
potential of sugar beet pulp as solid acid catalyst for biodiesel
production from palm fatty acid distillate (PFAD), a major by-product
in palm oil industries. The solid acid catalyst was successfully prepared
by sulfonation of incompletely carbonized AC using concentrated
H2SO4. The morphology study revealed a porous solid acid catalyst
with high total acid density. Further use in the transesterification
reaction of PFAD and ethanol resulted in 92% FAME yield.
4. Future perspective
The utilization of biomass-derived heterogeneous catalyst for
biodiesel production seems to be a promising choice as it eliminates
the tedious and problems faced by homogeneous operations. The
exploration of biomass or waste as the source of catalyst may reduce
the associated cost for commercially available solid catalyst as well as
provide new applications for the waste. However, further investigation
and development of biomass-derived catalyst are necessary to improve
the catalytic performance for biodiesel production as well as other
chemical processes.
Acknowledgement
The authors would like to acknowledge the MyBrain15 scholarship
provided by Ministry of Higher Education, Malaysia and research
S.H.Y.S. Abdullah et al.
financial support from FRGS Research Grant, Project No. RR067,
Project Code FRGS/1/2014/STWN01/UNISZA/02/2.
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